Carbon 168 (2020) 748e845

Contents lists available at ScienceDirect

Carbon
journal homepage: www.elsevier.com/locate/carbon

Review article

Transition metal impurities in carbon-based materials: Pitfalls,

artifacts and deleterious effects

ski*, Sławomir Dyjak
Wojciech Kicin
Institute of Chemistry, Military University of Technology, 2 Kaliskiego Str., PL 00-908, Warsaw, Poland

a r t i c l e i n f o a b s t r a c t

Article history: From carbides in steel to cobaltecarbon covalent bonds in vitamin B12, transition metal (TM)ecarbon
Received 6 January 2020 interactions play a critical role in so many aspects of human life that we rarely realize it. While insoluble
Received in revised form in organic and inorganic solvents, elemental carbon does dissolve in transition metals of specific valence
12 May 2020
electron configurations. This property, accompanied by carbon’s low vapor pressure, high melting/sub-
Accepted 3 June 2020
Available online 15 June 2020
limation point, resistance to corrosion and reducing properties create both challenges and opportunities
for the handling and separation of carboneTM systems. Natural and synthetic carbon-based materials
are contaminated by transition metals to various extents, which hinders or totally precludes their
advanced applications. Whether it is high-rank coal to be burned in power plants, graphite for electric car
batteries or nuclear reactors, or graphene and single-wall carbon nanotubes (SWCNTs) for nano-
electronics or medical purposes e TM impurities can cause a range of unexpected deleterious effects
even at parts per billion levels. Despite impressive progress in the field of carbon-based material
chemistry and physics, a commercial breakthrough in advanced carbon-based technology has not yet
been achieved. One of a few major reasons for this failure is that the industrial production of homo-
geneous and truly metal-free carbon (nano)structures with particular properties remains a great chal-
lenge yet to be overcome and hence impedes high-end applications. A part of the scientific community
erroneously considers the purification of carbon (nano)structures a resolved issue, however there is still
much to be done in this area. Herein we discuss the problem of TM impurities in carbon-based (nano)
materials in a broad context concerning the vast spectrum of materials from natural high-rank coals and
graphite to synthetic SWCNTs and graphene. Fundamental considerations on TMecarbon interactions,
artifacts and deleterious effects of TM impurities (e.g. in catalysis or medical applications), analytical
techniques for the assessment of their concentration, purification and demetalation of carbonaceous
materials and catalyst-free synthesis of carbon nanostructures are discussed in detail. Finally, we also
show how seemingly detrimental TM impurities may present unexpected benefits.
© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 750
2. Classification and nomenclature of carbonaceous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 753
3. Modeling and experimental observations of transition metal (TM)-carbon interactions: from organometallics and single-atom catalysts to ultra-high-
temperature ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 755
4. Analytical techniques for quantification and qualification of TM impurities in carbon matrices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 769
5. Artifacts and deleterious effects of TM impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 776
5.1. TM impurities govern the electrocatalytic properties of carbon (nano)structures: the groundbreaking discoveries of Compton and Pumera . 776
5.2. Traces of TMs in heterogeneous (electro)catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 778
5.2.1. Carbocatalysis: non-precious metal, single-atom and metal-free carbon-based catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 779
5.2.2. Stability of metallic species on N-doped carbon electrocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 785

* Corresponding author.

ski).
E-mail address: wojciech.kicinski@wat.edu.pl (W. Kicin

https://doi.org/10.1016/j.carbon.2020.06.004
0008-6223/© 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin 749

5.2.3. Examples of metallic impurity artifacts in carbon-based (electro)catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 785

5.3. Influence of TM impurities on the toxicity of engineered carbonaceous materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 787
5.4. Metallic impurities and the intrinsic magnetism of graphenic carbon structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 789
5.5. Influence of metal impurities on the adsorption capacity of carbon nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 790
5.6. Metallic impurities govern the reactivity of carbon (nano)structures, their mechanical strength and the stability of their composites . . . . . . 791
6. Purification of carbon-based materials from TM impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 792
6.1. Removal of TM impurities from CNTs: a review of the main achievements in 30 years of research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 792
6.1.1. Diversity of commercial carbon nanotubes: Content and type of metallic impurities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 794
6.1.2. Specific examples of CNT purification procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 795
6.2. Carbon nanomaterials as polydentate macro-ligands for transition and heavy metal complexation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 807
6.3. Natural and synthetic graphite purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 810
6.4. GO purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813
6.5. Demineralization and demetallation of fossil fuels: coal and crude oils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 813
6.6. Processing of CVD-grown graphene: common sources of contamination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 816
6.7. Synthetic approaches to produce bulk quantities of GBMs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 818
7. Transition metal catalyst-free synthesis for metal-free carbon (nano)materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 820
8. Turning metallic impurities into an advantage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823
8.1. Metallic impurities as a proxy for detection and tracking of carbon (nano)structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 823
8.2. Advantages of metallic impurities in (electro)catalysis and energy storage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
8.3. Carbon materials with residual metallic impurities for diagnostic and medical treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 825
9. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 827
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 829

List of abbreviations GNR graphene nanoribbon

GO graphene oxide
AAS atomic absorption spectroscopy HAADF-STEM high-angle annular dark-field scanning
AC-HRTEM aberration-corrected high-resolution transmission transmission electron microscopy
electron microscopy HACNTs horizontally aligned carbon nanotubes
AES atomic emission spectroscopy HER hydrogen evolution reaction
AFC ash-free coal HiPco high-pressure carbon monoxide
BPY bipyridine-based covalent triazine framework HOPG highly oriented pyrolytic graphite
CCG chemically-converted graphene HPC hyper-coal
CCN charged carbon nanomaterial HR-CS-AAS high-resolution continuum source atomic
CMG chemically modified graphene absorption spectrometry
CNF carbon nanofiber HRTEM high resolution transmission electron microscopy
CNM carbon nanomaterial IBA ion-beam analysis
CNT carbon nanotube ICP-AES inductively coupled plasma atomic emission
CoMoCAT cobalt/molybdenum catalyst spectroscopy
CO2RR carbon dioxide reduction reaction ICP-MS inductively coupled plasma mass spectrometry
CPAA charged particle activation analysis ICP-OES inductively coupled plasma optical emission
CVD chemical vapor deposition spectroscopy
DFT density functional theory INAA instrumental neutron activation analysis
DIM defect-induced magnetism IUPAC International Union of Pure and Applied Chemistry
DMAc N,N-dimethylacetamide LA laser ablation
DMF N,N-dimethylformamide LA-ICP-MS laser ablation-inductively coupled plasma-mass
DV double vacancy spectrometry
DWCNT double-wall carbon nanotube LIB lithium-ion battery
EC electrochemical capacitor MAG magnetic analysis
EDX (EDS) energy dispersive X-ray spectrometry MIC microwave induced combustion
EDXRF energy dispersive X-ray fluorescence MOF metal organic framework
EELS electron energy loss spectroscopy MRI magnetic resonance imaging
EPR electron paramagnetic resonance m-SWCNT metallic single-wall carbon nanotube
ETV electro-thermal-vaporization MWCNT multi-wall carbon nanotube
EV electric vehicle NAA neutron activation analysis
EXAFS extended X-ray absorption fine structure NACS neutron absorption cross-section
fWCNT few-wall carbon nanotube NaNp sodium naphthalide
GBM graphene-based material NIR near-infrared
GF-AAS graphite furnace atomic absorption spectroscopy NIRF near-infrared fluorescence
GIC graphite intercalation compound NIST National Institute of Standards & Technology
GiO graphite oxide NMMO N-methylmorpholine-N-oxide
GND graphene nucleation density NMP N-methyl-2-pyrrolidinone
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NP nanoparticle SS-NMR solid state nuclear magnetic resonance

NRC National Research Council s-SWCNT semiconducting single-wall carbon nanotube
OER oxygen evolution reaction SV single vacancy
OES optical emission spectrometry SW Stone-Wales defect
ORR oxygen reduction reaction SWCNT single-wall carbon nanotube
PC phthalocyanine TEM transmission electron microscopy
PGAA prompt gamma-ray activation analysis TG (TGA) thermogravimetric analysis
PGM platinum group metal TM transition metal
PIXE particle induced X-ray emission TMS transmission 57Fe Mo € ssbauer spectroscopy
PPV polyphenylenevinylene TXRF total reflection X-ray fluorescence
PTCDA perylene tetracarboxylic dianhydride UCC ultra clean coal
rGO reduced graphene oxide USS-ETV-ICP-MS ultrasonic slurry sampling electrothermal
ROS reactive oxygen species vaporization ICP-MS
SAC single-atom catalyst UVeVIS ultravioletevisible spectroscopy
Sc-CO2 supercritical carbon dioxide VACNTs vertically aligned carbon nanotubes
SEM scanning electron microscopy VPE vapor phase epitaxy
SHE standard hydrogen electrode WDXRF wavelength dispersive X-ray fluorescence
SN slurry nebulization XANES X-ray absorption near-edge structure
spICP-MS single particle ICP-MS XAS X-ray absorption spectroscopy
SRM standard reference material XPS X-ray photoelectron spectroscopy
SS-CS-GF-AAS solid sampling graphite furnace atomic XRD X-ray diffraction
absorption with a continuum source XRF X-ray fluorescence
SS-GF-AAS solid sampling graphite furnace AAS ZIF zeolitic imidazolate framework

1. Introduction (CNTs) and nanofibers (CNFs). The ease of surface functionalization,

Advanced materials constitute the foundation of modern civi-
lization. For instance, carbothermal reduction of iron oxides is one
of the oldest technological processes that shaped our civilization,
arguably starting the Iron Age. The iron oxide reduction reaction (in
simplified form: Fe2O3 þ 3C þ energy / 2Fe þ 3CO) laid the
foundation of modern civilization [1]. In fact, we live in the Iron Age
now more than ever before since an alloy of iron with up to 2%
carbon known as steel remains a critical material in every aspect of
our lives. From suspended bridges to hypodermic needles, transi-
tion metal (TM)ecarbon interactions yield materials of the utmost
technological and medical importance. Steel production is only
possible because certain transition metals act as solvents towards
elemental carbon. Approximately 80000 tons of steel was used to
build the Golden Gate Bridge. If on average structural steel contains
0.3% of carbon, then 240 tons of that steel account for pure carbon.
Nowadays about 1.6 billion tons of steel are produced annually and
interestingly, synthetic graphite is essential for its production
through the electric arc furnace and blast furnaces routes [2,3].
About 70% of worldwide crude steel production is based on coal
metallurgy. Carbonaceous materials (coal, coke or biomass) are
indispensable to extract metals from their ores [4]. From a broader
perspective, carbon materials have been at our disposal since the
dawn of humanity, either simply as a fuel or for more sophisticated
purposes. For instance, charcoal has been utilized as a medicament
since at least 1550 BC [5], while diamonds have served for millennia
as ornaments and attributes of social status. The versatile chemistry
of carbon as an element and as a material gives it the ability to
create endless chains, sheets and three-dimensional structures.
Carbon (particularly in the sp2 hybridization state) can create a
virtually unlimited number of structures and forms usually referred
to as graphenic carbon materials. Graphenic carbonaceous solids
are made up of carbon atoms bonded through sp2-hybridization.
Such materials include, inter alia, graphite, activated carbons, chars,
cokes, glass-like carbons, carbon blacks and also popular nano-
structures of graphene, carbon nanohorns, carbon nanotubes
interlayer intercalation and substitutional doping by heteroatoms,
further amplifies the range of possible graphenic carbon-based
structures. Such versatility creates great opportunities to develop
new functional materials for specific advanced applications. While
researchers often glorify the immense diversity of carbon as its
greatest advantage, rarely do they add that this blessing comes at a
high price. Great opportunities to design new carbon materials
come with even greater challenges to control, characterize, classify
and master such a diversified menagerie [6]. Furthermore, a whole
range of new carbon structures have been theoretically predicted
and remain waiting to be prepared [7]. Still, despite many chal-
lenges, carbon-based materials are the hope for the next techno-
logical breakthrough in electronics, medicine and materials
engineering. To find an advanced application of a new functional
material (e.g. in medicine) its fundamental properties must be
determined. The basic properties of a material (phase transition
temperatures, band gap, magnetic susceptibility, catalytic activities,
etc.) are dependent on its purity. However, a substance/material of
absolute purity is to some extent a theoretical concept. By the
fundamental laws of nature, impurities and defects are always
present in crystals and alter their basic properties. Indeed, in the
reality of laboratory studies, materials with various degree of purity
are investigated and impurities, even at levels below parts per
billion (ppb, 0.0000001%, mg/L, mg/kg, etc.), may profoundly alter
their basic physicochemical properties. In other words, if one wants
to determine the properties of a new material, a specimen of the
highest possible purity and uniformity (in the case of nano-
structures) must be produced first. One must note though that
contaminations detrimental in one particular application may not
necessarily exhibit deleterious effects in other application. Conse-
quently, specific methods of purity characterization should be
selected deliberately to meet the purity requirements of the final
application.
Until recently single-wall carbon nanotubes (SWCNTs) were
considered one of the most promising nanomaterial of countless
applications yet they have never met expectations and have been

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
recently outranked by graphene. SWCNTs or graphene are yet to be
used to build smartphones or design new drugs and diagnostic
techniques in medicine, and whether this day will actually come
remains uncertain [8]. Advanced carbon (nano)materials, which
were expected to ignite a new technological breakthrough (e.g.
CNTs, graphene-based materials (GBMs) or graphene oxide (GO))
are currently utilized merely as unorganized powders no different
to carbon black, graphite powders or activated carbon. They are
simply incorporated in bulk as loose powders into polymer
matrices or deposited as films. Just like old-fashioned carbon black,
advanced carbon nanomaterials (CNMs) are utilized as conducting
fillers in battery electrodes or as additives in inks/pigments. And
still, even in such basic applications a much better control of these
materials’ quality is necessary. Why do new carbon-based nano-
materials keep failing to make a significant commercial impact?
First, we must remember that a physicist who performs clean-room
studies of SWCNT samples is able to isolate (through painstaking
work) a perfect tube of particular chirality, length and diameter and
study its intrinsic properties. A chemist usually works with bulk
powder representing a complex mixture, which contains a fraction
of the variety of SWCNT-like structures. This is an important
discrimination to consider. Engineers who design electronic de-
vices consider graphene as a perfectly flat crystalline substance.
However, if graphene is used in bulk materials it is no longer flat.
Graphene sheets in a nanocomposite are crumpled, stacked and
highly deformed. A free-standing, defect-free, ideally flat graphene
does not exist. Besides, from the chemist’s point of view, a defect-
free graphene might indeed be useless as it is chemically inert
and only non-covalent physisorption on its basal plane is possible.
As perfect graphene is devoid of any catalytic activity, its applica-
tions in chemistry are limited [9]. It must be wrinkled, doped and
distorted to possess certain chemical activity. But this brings
another problem e how can one manage and control the properties
of randomly defective and poorly defined materials? While physi-
cists are able to measure fundamental properties of a particular
carbon nanostructure, chemists study some “average”
Fig. 1. Theory vs reality: comparison of theoretical (top) and realistic (bottom) structures of SWCNT and graphene. In reality, carbon-based nanomaterials are very different than
their theoretical models. The most common defects encountered within graphenic carbon structures are non-hexagonal rings causing bending and curvature, sp3-hybridization
defects, heteroatom-containing functional groups and vacancies (holes) within the hexagonal lattice. Note that this scheme does not highlight the problem of surface adsorption of
impurities and bundling/restacking of SWCNTs/graphene sheets due to van der Waals forces.
751
characteristics of bulk powders originating from a vast number of
discrete objects with variable structures.
Chemical vapor deposition (CVD) processes are currently the
dominant methods for industrial production of high-quality carbon
nanotubes, carbon nanofibers and graphene. CVD is usually assisted
by TMs since they can act as hydrocarbon cracking catalysts and as
elemental carbon solvents [10,11]. Unfortunately, an abyss still ex-
ists between CVD-derived carbon materials and their correspond-
ing theoretical structures (Fig. 1). As a matter of fact, it was obvious
since the first SWCNT studies that - as aptly stated by Ebbesen and
Takada - Evidence is accumulating that carbon nanotubes are rarely as
perfect as they were once thought to be [12]. They also highlighted
that defects and impurities determine all the observed properties of
CNT samples. The same concerns other carbon nanostructures. All
feasible CNMs synthesis methods lead to complex mixtures of
various molecules/objects with a range of structures, and hence a
range of properties. Additionally, the CVD process inherently con-
taminates the obtained materials with TM catalysts. Commercial
carbon-based nanomaterials represent very different substances,
depending on suppliers and batches even if they are sold under the
same names. Moreover, the current classification of graphene flakes
and graphene oxide materials used in the market is erroneous and
unscientific [13,14]. More generally, terms like SWCNT, GO, or
graphene nanoribbon (GNR) stand not for a particular structure but
for a diversity of structures. For instance, multi-wall carbon nano-
tubes (MWCNTs) can be bamboo-like, branched and kinked, with
different diameters, number of walls, chiralities and lengths, while
GNRs exhibit a huge range of widths and edge structures. Fuller-
enes are currently the only existing nanocarbons that can be
refined into pure homogeneous molecules, while other carbon
nanomaterials are never structurally pure molecules. The difficulty
in synthesizing these materials precisely is mostly due to harsh
synthesis conditions (high-temperature decomposition, pyrolysis,
cracking, etc.). Preparing pure and structurally uniform nano-
carbons by the construction of identical single molecules is the
greatest challenge in the field of CNMs, but this is crucial for the
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W. Kicin
development of new, carbon-based functional materials. Up to this
day, there are no advanced applications of SWCNTs due to the
structure and property heterogeneity in current SWCNT products.
Most research reports on carbon nanostructures concern properties
of inhomogeneous and undefined mixtures of structures, not “the
SWCNT” or “the carbon nanohorn”, as such structures do not exist.
For instance, band gaps of SWCNTs are determined by their
chirality (sidewall structures) and diameters, giving them metallic
(m-SWCNT) or semiconducting (s-SWCNTs) properties. Besides
chirality, SWCNTs can also be categorized by the helical structures
into left- and right-handedness (enantiomers/optical isomers) [15].
From a chemist’s point of view, m-SWCNTs are chemically more
reactive than their s-SWCNT counterparts of similar diameter. Yet,
the chemical reactivity of SWCNTs is also related to their diameter.
The coexistence of both semiconducting and metallic CNTs in the
samples currently available hinders their utilization in integrated
circuits. Application of SWCNTs in electronic devices requires
chirality-selective synthesis of exceptionally pure SWCNTs with
uniform diameter and length. In principle, organic chemistry
bottom-up construction allows synthesis of a single molecule of
carbon (nano)structures with a nominal purity of 100% [16,17].
However, nanocarbon molecules exhibit unusual sizes which are
exotic to typical organic synthesis procedures and hence require
development of new, unconventional synthesis techniques. There
are also difficulties associated with structural analysis as most
nanocarbon molecules are insoluble and exhibit propensity to van
der Waals coagulation. Consequently, totally new characterization
techniques would be required to fill the gap between the traditional
chemistry of small organic molecules and carbon nanoobjects of
unusual size. Either way, organic synthesis of carbon functional
materials is still in its infancy, the yields are low and unlike CVD it is
not a feasible method for mass production of advanced carbon
materials. Some carbonaceous materials such as GO and reduced
GO (rGO) are obtained by means of more benign liquid-based
chemistry. But in these cases, the problem of purity and hetero-
geneity can be even more severe. Unlike typical organic molecules,
GO is not a unique entity with constant atomic composition, but a
collection of nanoobjects with highly polydisperse sizes and
chemical compositions (GO and rGO are nonstoichiometric mate-
rials) [14,18]. Just like CNTs, GO structure and hence properties are
extremely variable. In addition, the abundance of oxygen functional
groups results in GO affinity for metallic ion adsorption. As a result,
a common understanding of GO properties is missing among re-
searchers. GO batches vary by purity, flake size and O/C atomic
ratio. The variation in flake dimension spans over many orders of
magnitude. A generalization of the observed properties of GO is not
possible. It has recently been proven that GO synthesis by the
commonly used improved Hummers’ method is extremely irre-
producible [19]. A few batches of graphene oxide were prepared
under strictly identical conditions yet numerous deviations and
heterogeneities among the obtained materials were observed
(wide distribution of flake dimensions and difference in the content
of Mn and Fe impurities). Such variability results in variations in
chemical activity. At the same time many authors claim that they
can precisely dope graphene-based materials with single atoms yet
in reality they assign random differences in these material prop-
erties to swimmingly successful manipulation of the materials with
atomic precision. Carbon (nano)materials may never find practical
advanced applications without a significant breakthrough in their
synthesis and purification.. The observed variations in the perfor-
mance of carbon-based devices reported by different research
groups are due to the highly variable properties of these materials.
For instance, since graphene is a 2D material of large specific sur-
face area, any adsorbed contaminant alters its intrinsic properties.
As a result, the performance of graphene-based devices relying on
surface-dependent phenomena is purity-sensitive and varies from
case to case [20].
Even if metals are not directly involved at the synthesis stages
carbon materials may still contain some metallic impurities due to
incidental contamination. On the other hand, metals can be also
intentionally introduced into carbon structures to boost their per-
formance. Dopants are often referred to as impurities. The differ-
ence between a dopant (deliberately introduced) and an impurity
(incidentally introduced) is semantic. Indeed, there is a blurred line
between intentional doping of carbon materials and incidental
contamination by ubiquitous TMs (e.g. Fe or Cu) [21]. Without
efficient purification procedures a large proportion of carbon-based
materials will remain inapplicable as their intrinsic properties are
imperceptible. This review targets only one important parameter
affecting carbonaceous material properties: transition metal im-
purities, with special emphasis on the 3d metals from Ti to Cu. Due
to the solubility of carbon in transition metals, they are common
impurity. While synthesis of carbon (nano)materials results in
various types of impurities (e.g. amorphous carbon, polycyclic ar-
omatic hydrocarbons, etc.), TMs represent a special kind of
contaminant. According to International Union of Pure and Applied
Chemistry (IUPAC), a transition metal is an element whose atom
has an incomplete d sub-shell, or which can give rise to cations with
an incomplete d sub-shell. Hence group 12 elements (Zn group) are
usually excluded from the TM family. TMs possess partially filled
d sub-shells and they create compounds in numerous oxidation
states due to the low energy gap between different possible
oxidation states. The ability to adopt multiple oxidation states and
to form complexes grant TMs exceptional catalytic properties,
while the presence of unpaired d electrons results in para-
magnetism. Consequently, TM impurities influence a whole range
of carbon material intrinsic properties including catalytic, elec-
tronic, electrochemical, optical, magnetic, sorption, mechanical,
and toxicological to name a few. Purification and refining tech-
niques of advanced carbon materials are urgently needed since only
pure and well-defined materials can find applications in the
demanding electronic, chemical or medicine industries. Recently,
carbon-based metal-free [22] or single-atom catalysts (SACs) [23]
are getting increased attention yet complete demetalization
methods for carbonaceous materials have never been achieved.
Even purified and/or apparently pure carbon materials can still
contain trace amounts of metallic impurities (at content below
100 ppm (0.01%)) which are not easily detected by commonly uti-
lized analytical techniques. This peculiar state of carbon material
research raises doubts and, in practice leads to conflicting experi-
mental results. On one hand researchers are able to dope carbons
with single atoms of a certain chemical state and concentration, yet
we still cannot efficiently remove traces of metallic impurities from
SWCNTs, CNFs, GO or graphene-based materials. How should the
scientific community interpret results concerning carbon material
properties in light of such uncertainties? Is complete demetaliza-
tion of carbon-based materials possible? Purification methods of
carbonaceous materials rely on the exceptional properties of
elemental carbon. Its chemical inertness allows removal of metallic
impurities by acid/base leaching while its high sublimation/melting
point accompanied by reductive properties (high-temperature
carburization) allow evaporative removal of metals [24]. Never-
theless, carbon creates protective layers around metallic nano-
particles (NPs) and metal atoms can easily intercalate into layered
graphitic structures or substitute carbon atoms within the hexag-
onal graphene lattice creating strong covalent bonds. All of this
makes obtaining metal-free carbons or doping carbon with atomic
precision a truly formidable task.
In this review we tackle one of a few issues restraining the
commercial success of advanced carbon-based functional

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
materials. Our ambition is to present the problem of TM contami-
nation of graphenic carbon materials in the broadest possible
context. TM impurities are a source of numerous and often unex-
pected deleterious effects both in engineered carbon nano-
structures and in raw carbon-based minerals and fossil fuels. By
presenting some prominent examples we elucidate how TM resi-
dues within carbon (nano)structures lead to conflicting experi-
mental results and eventually impede applications of carbon-based
materials in the field of nanoelectronics, medicine or catalysis. We
pursue various methods to produce metal-free carbon materials via
targeted removal of metallic impurities. To this end we discuss
purification of not only sophisticated carbon nanostructures but
also natural graphite and coal. Indeed, in the era of growing de-
mand for Li-ion batteries, cheap yet effective purification of
graphite has become an urgent issue to study. In addition, if we
want to make better use of coal, we must learn how to deal with its
deleterious effects on the environment. We refer to deep purifica-
tion of carbon-based materials as demetalation. According to the
definition demetalation (synonym: demetallation, demetalization)
stands for breaking of a chemical bond between a substrate and a
metal atom. It also refers to removal of traces of metals from ma-
terials and surfaces. In this sense demetalation/demetalization
(often used interchangeably) refers to the deepest possible removal
of metallic impurities from carbon matrixes.
2. Classification and nomenclature of carbonaceous materials
The most common classification for carbon materials is based on
the type of hybridization of the valence orbitals (sp3, sp2, and sp).
Nevertheless, carbon materials can exhibit mixed hybridization
types. They can contain carbon atoms in two or three different
hybridization states (for example co-existence of sp3 and sp2 hy-
bridization in amorphous carbon or sp and sp2 hybridization in
graphyne). To make things even more complex, intermediate hy-
bridization states of various degrees (denoted as spn, where n is a
non-integral yet fractional number (1 < n < 3, n s 2) can also exist
[25e27]. For instance, for spn hybridization where 2 < n < 3, the
intermediate carbon forms comprise various non-planar, gra-
phene-related structures. The fractional degree of hybridization is
in this case caused by the curvature of the sp2 hybridized frame-
work, resulting in strained CeC bonds. Pure sp2 hybridization dic-
tates a perfectly flat surface, however the degree of hybridization of
carbon atoms in a curved sheet must be > 2. For instance, the hy-
bridization of spherical buckminsterfullerene C60 can be described
as sp2.28. Carbon atoms in sp2 hybridization can organize them-
selves not only in hexagonal, but also in a variety of different
polygonal rings. The non-hexagonal rings can either introduce
curvature or keep the sheet flat if the polygon arrangement fulfils
certain symmetry rules. Pentagons induce positive (spherical)
while heptagons or octagons induce negative (saddle-like)
Gaussian curvature. Thus, sp2 hybridized carbon materials can be
categorized as (i) positively curved fullerene-type (containing
hexagonal and pentagonal carbon rings) (ii) negatively curved
schwarzite-type (e.g. Mackay crystals containing hexagons and
either heptagons or octagons [28]), and (iii) zero-curvature gra-
phene-type (containing only hexagons). In symmetrical arrange-
ments of pentagons and heptagons positive and negative
curvatures can cancel each other out and the total curvature re-
mains zero, yet small local deviations from a perfectly flat structure
may be present e.g. in Stone-Wales defects (two pentagons and two
heptagons). Due to mixed and transitional hybridization states that
occur within carbonaceous solids, the classification scheme for all
carbon materials can be conveniently represented by a triangular
diagram (Fig. 2) [25]. This diagram includes existing and hypo-
thetical carbon allotropes (corners of the triangle) and
753
intermediated and mixed forms of carbon located at the edges and
inside of the triangle, respectively. Carbon forms located inside the
triangle have contributions of all three types of hybridization (sp3,
sp2, and sp) co-existing together in various combinations (ill-
defined carbon materials, e.g. amorphous or vitreous carbon).
Carbon forms with the transitional spn hybridization of 2 < n < 3 are
located along the sp2‒sp3 edge of the triangle. For the spherical
structure of Cx (where x ¼ 20, 28, 32, …) the ratio of pentagonal (P)
to hexagonal (H) rings changes from P/H ¼ 0 for perfectly flat
graphene to P/H ¼ ∞ for the solely pentagonal ring cluster C20 of a
“diamond-like” fullerene (the C20 sphere contains 12 five-
membered rings and as an unstable form it collapses into the dia-
mond structure). The forms along the sp2esp3 side of the triangle
between fullerene and graphite are referred to as graphenic car-
bons with distorted sp2 hybridization often referred to as sp2þε or
sp2þx types. One should also bear in mind that, except for SWCNTs
with a very small diameter, the curvature of larger CNTs and ful-
lerenes does not significantly affect the hybridization of carbon
atoms and hence it can be approximated to nearly pure sp2 state.
Besides hybridization state, carbon materials are also classified
according to their dimensionality. This is because unlike other
materials, carbon creates a diversity of very stable nanoobjects.
Consequently, one must distinguish between nanostructures
(discrete independent objects of nanometer size) and nano-
materials (objects of macroscopic nature with some structural units
in sizes up to 100 nm). Nanocarbons can be classified into 0, 1, 2 or
3D materials according to their dimensionality, where 0 corre-
sponds to clusters of atoms or single molecules (e.g. carbon dots or
fullerenes), 1 to fibers (e.g. nanotubes), 2 to films (e.g. graphene)
and 3 relates to macroscopic objects with one nanosized structural
element (for instance nanoporous zeolite-templated carbons). Ac-
cording to the above presented classifications, carbon dots are the
0D structures made of a co-existing mixture of sp3 and sp2 carbon
Fig. 2. The ternary carbon allotropy phase diagram of confirmed and hypothetical
allotropes and transitional forms of carbon (both mixed and intermediate) based on
carbon valence bond hybridization. The diagram describes materials consisting of
carbon in a single hybridization state (at the vertices), materials containing mixtures of
two types of hybridizations (along the edges), and materials with a mixture of all three
hybridization states (inside the triangle). Adapted with permission from Ref. [25].
Copyright 1997 Elsevier.
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W. Kicin
atoms (amorphous carbon). Similarly, nanodiamonds are 0D ob-
jects, but they have a more complex hybridization state of atoms.
Nanodiamonds exhibit coreshell structure based on a diamond
core (sp3 carbon atoms) with a middle layer of intermediate, highly
strained sp2 hybridization (sp2þε), and a graphitic outer shell (with
sp2 hybridization approaching that of graphene). In turn, a good
example of co-existence of perfect sp and sp2 hybridization within
one carbon material is graphyne. Graphyne is a generic name,
which stands for a 2D planar carbon structure, where two adjacent
sp2-hybridized carbon atoms are connected by eC^Ce linkages
[29]. However, unlike in carbon dots where the ratio and distri-
bution of sp2/sp3 bonding is random and obscure (amorphous
phase), in graphyne the ratio and distribution of sp/sp2 bonding is
precisely defined (crystal lattice). As presented above the family of
carbon materials is complex and to add to this complexity, carbon
composites often referred to as carbon superstructures can now be
created by combining different carbon nanostructures (e.g.
graphene þ carbon nanotubes, fullerenes covalently bonded into
3D nanoporous matrix, etc.). Yet from the diverse carbon material
family, graphenic carbons of sp2 and sp2þε hybridization, constitute
by far the most diversified and versatile group of carbonaceous
materials. Interestingly, despite their extreme versatility all these
materials still exhibit common properties due to sp2/sp2þε hy-
bridization. Special databases are being created to help researchers
navigate this murky field of carbon material chemistry and physics.
For instance, hundreds of hypothetical 3-periodic allotropes of
carbon are collected in an open, evolving project - the Samara
Carbon Allotrope Database (sacada.sctms.ru) [30].
While classification of carbon-based materials is complex, the
nomenclature of graphenic structures, especially in the form of
nanoobjects, became truly messy and out of control. Researchers
started to use their personal impressions to give a name to obtained
carbon nanomaterials, usually referring to commonly known
macroscopic objects that might resemble the carbon objects.
Consequently, the scientific community ended up with an overflow
of confusing names, which makes searching and comparing pub-
lished results extremely difficult. In addition, some of the terms
concerning carbon nanoforms used by commercial manufacturers
are contradictory and without any scientific merit. Terms like car-
bon nanotube, graphene or graphene oxide are used in a very
Fig. 3. Classification of different types of graphene-based materials according to three
fundamental properties: number of graphene layers, average lateral dimension, and
atomic C/O ratio. Reproduced with permission from Ref. [33]. Copyright © 2014 WILEY-
VCH Verlag GmbH & Co. KGaA, Weinheim. (A colour version of this figure can be
viewed online.)
generic manner and stand for a whole class of extremely diverse
materials. Even though the nomenclature is now a bit more orga-
nized it is still common practice that a particular name is used to
refer to completely different carbon nanoforms or that the same
carbon nanoobjects are reported with totally different names.
There are two great Editorials published in the Carbon journal,
which try to deal with the chaos in sp2-bonded carbon nanoform
nomenclature [31,32]. This problem is pivotal because as stated in
the Editorial concerning the nomenclature of graphene-based
materials: To build a new scientific field, one needs a rational scien-
tific nomenclature [31]. In that Editorial, graphenic carbon materials
were defined as the broadest class of carbonaceous solids that consist
primarily of elemental carbon bonded through sp2-hybridization. As
graphene became a new star among carbonaceous materials, an
urgent need to come up with a nomenclature for graphene-based
materials has appeared. The most common approach is to base
the nomenclature on morphological descriptors [31,33]. Proper
names for GBMs could be based on their dimensions and hence one
of the proposed nomenclature models considers the di-
mensionalities (the number of graphene layers and the average
lateral size) and the carbon-to-oxygen (C/O) atomic ratio as the
basic properties that characterize the range of common graphene
materials (Fig. 3). The addition of the C/O ratio as a functional
attribute is important as GBMs are highly heterogeneous not only
from the structural but also from the chemical composition point of
view. Similarly, the classification of graphene oxide materials is
usually based on their chemistry and morphology. More generally,
attempts to develop a nomenclature for graphenic carbon nano-
forms beyond 2D GBMs are based on their morphological and
structural differences. For instance, for multiply-encapsulated
closed carbon layer structures commonly referred to as carbon
onions, a new more scientific name multi-wall fullerenes was pro-
posed, while bamboo nanotubes could be more appropriately
named as partitioned nanotubes or partitioned stacked nanocones
[32]. A helpful guide might be a glossary on carbon terminology
containing 114 terms compiled by an IUPAC subcommittee. Data is
now available on-line in the IUPAC Gold Book (goldbook.iupac.org)
[34]. However, the only carbon nanoforms currently defined in that
book are fullerenes and graphene.
Fig. 4. Chemical structures of vitamin B12 and its derivatives. Reproduced with
permission from Ref. [35]. Copyright 2015 The Royal Society of Chemistry. (A colour
version of this figure can be viewed online.)

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin 755

Fig. 5. Two possible CoeC bond cleavages (homolytic and heterolytic) in cobalamins. Reproduced with permission from Ref. [35]. Copyright 2015 The Royal Society of Chemistry. (A
colour version of this figure can be viewed online.)

3. Modeling and experimental observations of transition
metal (TM)-carbon interactions: from organometallics and
single-atom catalysts to ultra-high-temperature ceramics
Carbon/metal interactions (especially with transition metals)
are a subject of extensive research for a number of reasons. This
issue is important for designing new materials including carbon-
containing alloys, graphite intercalation compounds, metal matrix
(nano)composites reinforced by carbon materials, for creating
electrical junctions between carbon nanostructures and metal
electrodes, for elucidation of the growth of carbon nanostructures
from catalytically active metals and molten catalyst-assisted pro-
duction of diamonds under high pressure, for application of carbon
as a metal support in catalysis including a single-atom catalyst, or
for studying the magnetic properties of doped carbon structures, to
name a few examples. Carbon/metal interactions can be considered
from the standpoint of single atoms bonding and interplay in bulk,
which expands the range of possible cases from soft organometallic
chemistry to ultra-high-temperature ceramics.
Vitamin B12 is a naturally occurring organometallic compound
with a cobaltecarbon covalent bond. The formation/cleavage of the
CoeC bond allows generation of organic radicals and plays a crucial
role in biological processes, including DNA synthesis and red blood
cell formation [35]. When vitamin B12 is ingested, the axial cyanide
ligand (1a, Fig. 4) is replaced by a complex organic group. In stable
forms of vitamin B12, cobalt has a þ3 oxidation state. Under bio-
logical conditions, depending on the complex, the CoeC bond un-
dergo either homo- or heterolytic cleavage, which provides the
Co(II) moieties and an organic radical or the “supernucleophilic”
Co(I) species with a lone electron pair (Fig. 5).
In organometallic compounds, where the interplay between
individual carbon and metal atoms are considered, not only typical
sp3 carbon-metal covalent bonding (e.g. vitamin B12) but also
strong interactions with sp2-hybridized carbon nanoobjects on an
angstrom scale are essential [36]. Haddon et al. distinguished four
limiting cases concerning interactions between metals and the
graphitic surface: (i) physisorption - a weak interaction where only
marginal charge transfer between the metal and the graphitic
surface occurs (e.g. Au on graphene), (ii) ionic chemisorption with
pronounced charge transfer from the metal to the graphitic surface,
but with full preservation of the carbon band structure (typical for
Li), (iii) covalent chemisorption with formation of an organome-
tallic hexahapto(h6)-metal bond that preserves the graphitic band
structure (e.g. dibenzenechromium) and (iv) covalent chemisorp-
tion involving strong rehybridization of the graphitic band struc-
ture and some degree of charge transfer (which often results in
carbide formation) [37e40]. The effect of functionalization of the
graphitic carbon surface by chemical addition has been described
by two limiting cases: the so-called destructive and constructive
rehybridizations. The destructive rehybridization (from sp2 to sp3)
removes carbon atoms from the polygonal honeycomb and from
the electronic band structure of graphene, yielding a decrease in
conductivity. In contrast, constructive rehybridization concerns the
covalent chemisorption of metal atoms on the carbon surface with
formation of an organometallic hexahapto-metal bond that fully
preserves the graphitic band structure and hence allows the for-
mation of atomic scale interconnects for electronic (nano)devices.
Fullerenes, SWCNTs and graphene-based structures constitute
versatile ligands of variant hapticity (e.g., hexa- (h6), penta- (h5) or
even heptagons (h7)) to adsorb single TM atom (Fig. 6). Hexahapto
coordination of transition metals to benzenoid rings has already
been applied to interconnect SWCNTs or graphene layers (Fig. 6)
[37e41]. SWCNT or graphene bind transition metals through the
h6-coordination mode and they constitute excellent ligands to form
single-atom conductive interconnects.
The ability of the organometallic chemistry to functionalize sp2-
hybridized carbon surfaces is illustrated by the distinctive organ-
ometallic compound - bis(benzene)chromium, Cr(h6-C6H6)2 - a
stable complex in which the metal atom coordinates to two ben-
zene ligands (Fig. 6). Cr possesses 6 valence orbitals and 6 valence
electrons (3d54s1) [42]. By covalent coordination with two benze-
noid ligands, it shares a total of 18 electrons where the metal and
the two benzene ligands each donate 6ee (fulfilling the 18-electron
rule analogous to the octet rule). The commonly known ferrocene
(bis(h5-cyclopentadienyl)iron) is structurally similar to Cr(h6-
C6H6)2 and they both belong to the family of “sandwich-complexes”
(Fig. 6).
In addition to group 6 transition metals (Cr, Mo, and W), Ti (4

Fig. 6. Examples of sandwich compounds of various hapticity following an 18-electron principle (note that (h7-C7H7)2Ti has not yet been synthesized). Reproduced with permission
from Ref. [42]. Copyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. On the right: model of the metal atom trajectory, showing the initially formed (h6-SWCNT)M
complex with subsequent metal atom migration to form the (h6-SWCNT)2M bis-hexahapto-SWCNT carbon nanotube junction. Reproduced with permission from Ref. [40].
Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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valence electrons), V (5), Mn (7), and Fe (8) also form (h6-C6H6)2M
complexes. The metal exists in a zero-oxidation state and such
compounds are highly covalent due to the large degree of electron
delocalization to the ligand. Nonetheless, despite the formation of a
covalent bond, the ligands (benzene or graphene) retain planarity
and full delocalization of p-electrons, which is essential for the
electronic properties of p-electron systems [40]. Carbonemetal
interactions can also be considered from a standpoint where indi-
vidual carbon-based entities interact with the bulk metal surface.
Theoretical consideration showed that the bond energy between
C6H5 (the simplest aryl group) and a metal surface is chemical in
nature (chemisorption) and the binding strength decreases from Ti
to Cu as the number of d-electrons increases [43].
Among many excellent researchers, Banhart contributed
significantly to our understanding of the chemical interaction be-
tween transition metals (both single atoms and metal clusters/
crystals/nanoparticles) and graphene layers/CNTs/graphite sur-
faces. Banhart and his co-workers performed essential experi-
mental studies of the behavior of individual metal atoms in
graphitic phases and investigated the role of physical processes
such as metal diffusion through the graphitic lattice and carbon
solubility [44,45]. The type and length of bonds between carbon
and metal atoms and specific sites within the graphite lattice that
can be occupied by metal atoms were also considered. The bonding
of a transition metal with carbon relies on the overlapping of metal
d-orbitals with carbon’s p-orbitals. As a result, the metal’s reactivity
towards carbon is determined by the number of electron vacancies
in d-orbitals [46,47]. This corresponds with the increasing solubility
of carbon in transition metals. Solubility increases as the number of
d-vacancies increases, reaching maximum values with iron sub-
group and then declining due to over-reaction between metal and
carbon. When mutual reactivity exceeds a certain value, carbon
atoms lose their mobility in the solution and are locked up in the
structure as carbides. Elements with fully occupied d-orbitals (no d-
vacancies) such as Cu (3d104s1), Zn (3d104s2) or Ag (4d105s1) are
chemically inert toward carbon while elements with seven to nine
d-vacancies such as Sc (3d14s2), Ti (3d24s2), V(3d34s2), or Ta
(4f145d36s2) show very strong interactions with carbon, forming
extremely stable carbides. This behavior is reflected in an increase
in the enthalpy of formation of the carbonemetal bond and hence
the melting point of the corresponding carbides. TMs can be
divided in the group of early (e.g. Sc, Ti, Y, Zr), middle (e.g. Cr, Mn,
Mo) and late (e.g. Ni, Cu, Ag) transition metals depending on the
number of d-vacancies. Each group is characterized by different
chemistry. The increasing reactivity between metals and carbon is
also reflected in the maximum carbon/metal ratio of stable carbides
formed by the metals [46]. For example, for third period of transi-
tional elements this ratio decreases with decreasing electron va-
cancies according to the order: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu (and
Zn). It is also important to note that the reactivity of metals towards
carbon corresponds to their reactivity to nitrogen, oxygen and
hydrogen - that is, transition metals with an increasing number of
electron d-vacancies become more reactive not only towards car-
bon, but also to nitrogen, oxygen and hydrogen.
The ability to grow crystalline carbon from solid TM solutions is
dependent on their affinity to carbon. Elements with a moderate
number of d-vacancies (two to four) such as Ni (3d84s2), Co (3d74s2),
or Fe (3d64s2) exhibit moderate interactions with carbon. They
dissolve a certain yet low amount of carbon that in excess leads to
formation of metastable carbides. The stability of the respective
carbides of the iron subgroup decreases in the sequence:
Fe > Ni > Co. In the presence of carbon, along with the formation of
solid solutions based on Fe, Ni and Co, their melting point decreases
by several hundred degrees from the moment of creating eutectic
mixtures. [48,49]. For the FeeC phase diagram the range of stability
of the solid solution is indeed narrow but of extremely important
practical implications. The ability of Fe to create carbides is critical
in the production of steel. The solubility of carbon is relatively low
in Fea (0.02 wt% at 727  C) yet quite high in Feg (2.14 wt% at
1147  C), (Fig. 7). Generally speaking, the addition of carbon de-
creases the melting point of ironecarbon alloys from ca. 1538  C for
pure iron to 1147  C in the eutectic state with 4.3 wt% of C. Carbon
content in steel is usually up to 1.5 wt%, however it can go up to
2.14 wt% maximum (which corresponds to maximum solubility of
carbon in Feg). For nickel the solubility is of 0.6 wt% at 1326  C, and
for Coa of 0.9 wt% at 1320  C, (Fig. 7). Above 800  C carbon in nickel
forms a solid solution. Lowering the temperature decreases solu-
bility. Formation of the metastable Ni3C phase promotes the pre-
cipitation of carbon out of Ni. Similarly, Co forms a metastable
carbide at high temperatures, which separates into pure metal and
graphite during cooling of the cobalt-carbon solid solution. In
comparison to Ni, iron forms a rather stable carbide and therefore
graphite precipitation from Fe can be obtained only under very
specific cooling rates [50]. In the case of Fe there is competition
between the formation of graphitic carbon and stable carbide
(cementite, Fe3C). Iron exhibits an asymmetrical distribution of
electrons in the d-shell, leading to mutual repulsion, which may
explain its higher affinity towards carbon (with respect to Co and Ni
where the 3d shell is progressively filled creating less reactive
configurations) [51].
TMs constitute efficient catalysts for mass production of high-
quality carbon nanostructures (e.g. carbon nanotubes, nanofibers
and graphene) via the catalyst-assisted CVD process. Metals char-
acterized by non-zero but limited carbon solubility in the solid bulk
phase and few d-vacancies such as Ni, Co or Fe display the highest
catalytic activity, since they form metastable carbides and easily
release carbon atoms under typical CNT/CNF synthesis conditions
[52]. Metals with numerous d-vacancies (e.g. Sc, Ti, V) are active
CNT growth catalysts but only when their stable carbides are
capable of decomposing carbon precursors (e.g. hydrocarbons).
Metals with full d-orbitals are relatively poor catalysts and their
activity appears only at nanoscale (nanoparticles  1 nm) [47]. In
case of graphene formation, the most suitable catalysts are TMs
that have relatively low solubility and affinity towards carbon but
can stabilize carbon atoms on their surfaces by forming weak
bonds. For this reason, Cu and to lesser extent Ni are the optimal
substrates for high-quality graphene film growth. Although binary
phase diagrams of CeNi and CeCu are similar (Fig. 7) the mecha-
nisms and the final thickness of the CVD-grown graphene films are
very different due to much lower solubility of C in Cu than that in Ni
[53,54]. Nickel substrate promote graphene formation by precipi-
tation/segregation mechanism - carbon dissolves into the metal
bulk at high temperatures and segregates to the metal surface upon
cooling leading to the formation of graphene. The disadvantage of
using Ni as the catalyst is that patches of single and few layered
graphene are obtained over large micrometric regions and not
homogeneously over the entire substrate. The lack of control over
the number of layers is attributed to the fact that carbon prefer-
entially precipitates at the grain boundaries of polycrystalline Ni
substrate and consequently, the thickness of the graphitic layers at
the grain boundaries is larger than within the grains. In contrast,
the Cu-assisted surface-mediated mechanism results in monolayer
graphene. In this case, carbon species form graphene directly on the
metal surface without penetrating the bulk. After full coverage of
the Cu film by a single layer of graphene, growth terminates [54].
This self-limited process is crucial for controlling graphene growth.
Cu has very low carbon solubility (only 0.001e0.008 wt% at
1084  C) and hence it does not form any carbide phases [55]. Cu has
filled d-orbitals and therefore forms only weak bonds with carbon
via charge transfer of the p electrons in the sp2-hybridized carbon

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
Fig. 7. Binary phase diagrams of CeFe, CeNi, CeCo and CeCu. Reprinted with permission from Ref. [48]. Copyright 2004 Elsevier.
to the empty 4s state of Cu. As known, the formation of interme-
diate strength bonds at the adsorbateesubstrate interface defines a
good catalyst. The exceptional combination of low affinity of carbon
to Cu accompanied by the ability to form intermediate soft bonds
makes Cu a real catalyst (i.e. catalyst in the actual meaning of this
term) for graphene growth [51]. Considering that both Cu and Ni
constitute good catalysts for graphene formation by CVD, a CueNi
alloy has been proposed as an optimal compromise, since carbon
atoms can be supplied through both surface diffusion and bulk
segregation processes, increasing the growth rate yet allowing
graphene quality control [56].
TMs with intermediate affinity to carbon are not only efficient
catalysts of graphitization, but they also catalyze the graphite %
diamond transition, which is a reversible process [46]. The activity
of selected TMs in catalytic graphitization corresponds with their
ability to assist diamond synthesis. Co, Fe, Mn, Ni and Cr are the
most efficient catalysts for commercial production of synthetic di-
amonds in molten metal under high pressure. The catalytic activity
of metals in graphite / diamond conversion depends on two
factors: atomic size and reactivity with carbon. The metal’s atomic
size should be as close to 2.46 Å as possible (this distance corre-
sponds to the gap between every other carbon atom on a graphite
hexagon). The atomic interaction with carbon should be interme-
diate; i.e. high enough to destabilize the p bond of the sp2-hy-
bridized carbon honeycomb to form a movable solute, yet weak
enough to prevent the formation of stable metal carbides. From a
broader perspective, the catalytic activity of TMs in the graphiti-
zation and diamond formation processes also relates to the ability
757
of catalytic cracking of hydrocarbon gases on the surfaces of tran-
sition metals [10]. The ability of TMs to catalyze reactions where
elemental carbon is the final product (e.g. CH4 / 2H2 þ C; 2CO /
CO2 þ C, or CO þ H2 / H2O þ C) can be conveniently applied for the
synthesis of carbon nanostructures. However, there are always two
sides to every story. Engineering alloys containing Fe, Ni or Co, such
as stainless steels or heat-resisting materials catalyze gas-phase
processes that release carbon. The resulting carbon deposit can
destroy structural elements of these alloys at a catastrophically
rapid corrosion rate (a phenomenon referred to as metal dusting)
[57]. Interestingly, the detrimental carbon deposit on structural
alloys often occurs in the form of carbon nanotubes. Even more
interestingly, TMs also catalyze reverse processes as they help to
turn CO and H2 mixtures (syngas) into hydrocarbons. This is the
principle behind the Fischer-Tropsch synthesis, which utilizes Fe,
Co or Ni oxides as active catalysts to convert syngas into useful
liquid hydrocarbons [58]. Indeed, is has been shown that TM
nanoparticles can be utilized as nanoscissors to cut graphene layers
with atomic precision and controlled crystallographic direction to
produce graphene nanoribbons [59]. TM particles catalyze hydro-
genation of carbon to methane (C þ 2H2 / CH4), which allows
graphene cutting (Fig. 8). This process can be regarded a reverse of
catalytic-assisted CVD growth of carbon nanostructures and has
also been used to unzip MWCNTs to graphitic nanoribbons [60].
These examples show that TMs and elemental carbon or carbon-
containing molecules form very complex systems, where TMs can
catalyze various transformations. In catalyses involving TMs, the
so-called d-band center model of Hammer and Nørskov is
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W. Kicin
Fig. 8. Ni nanoparticle utilized as a nanoscissor for cutting of graphene. Reproduced
with permission from Ref. [59]. Copyright 2009 American Chemical Society. (A colour
version of this figure can be viewed online.)
commonly used to understand the role of the d-electrons in the
interaction between the adsorbate and the TM surface [61]. The d-
band center model predicts a uniform decrease (increase) in the
adsorption energy of a given molecule from one TM surface to
another where the number of d-electrons increases (decreases).
Another important aspect of TM/sp2-carbon interactions is
metal wetting. Metals characterized by good wetting like Ti or Pd
can be deposited as continuous layers on carbon surfaces whereas
metals with poor wetting, for instance Ag or Au are usually
deposited as isolated islands [62,63]. Weakly wetting metals create
clusters due to the high cohesive energy caused by strong d-d in-
teractions. Only strong interplay between the metal and the carbon
surface can prevent metal aggregation. The interaction of graphenic
carbon nanostructures with a TM is strongly dependent on the
presence of structural defects. Undercoordinated carbon bonds at
the edges as well as defects such as non-hexagonal rings enhance
metal adhesion [64]. Uniform metal distributions on defect-free
graphene are difficult to achieve due to its chemical inertness.
Vacancies and strains in the graphene sheet allow stabilization of
the metal adatoms. In fact, this phenomenon has practical impli-
cations as it was utilized for detection of defects in SWCNTs via
selective electrodeposition of nickel nanoparticles [65]. SWCNTs
selectively nucleate TM deposition at sites of enhanced chemical
activity. Similarly, steep edges on a highly oriented pyrolytic
graphite (HOPG) surface constitute a line of chemical defects with
high affinity for metal nucleation. Electrochemical studies revealed
that edge-plane sites in graphite powders and CNT ends are the
reactive centers in carbon materials [66]. Importantly, the size of
the metal deposits on CNTs increased with the time of deposition
yet without nucleating new sites [65]. This means that relatively
large metal clusters would grow at defect sites, but areas free of
defects remain completely metal-free (a perfect graphene surface is
(electro)chemically inert). Metals nucleate at defects of various
natures, including oxygen-containing functionalities, StoneeWales
(SW) defects, substitutional dopants, mechanical strains or adsor-
bed contaminations. In reality, transition metals create large clus-
ters at the most active sites leaving the inert areas free of metal and
hence the metal distribution on defected nanocarbons is expected
to be highly heterogeneous. Additional processing of carbon-based
materials (e.g. ultrasonication or acid leaching) yields even higher
numbers of TM nucleation sites. These observations are of the
utmost importance for the new field of carbon-TM systems, the so-
called single-atom catalysis. Increasing interest is observed in the
subject of a single metal atom interaction with graphenic carbon
supports in the pursuit of new catalytic materials, as SAC lies
somewhere between hetero- and homogeneous catalysis [23].
When a single metal atom on a carbon surface is considered, it is
important to differentiate between various forms of single atom
states in/on the graphene surface/structure. Single atoms can
interact with the graphene layer/graphite surface by weak
adsorption on top of a non-defective graphene sheet (when metal
adatom d-orbitals hybridize with the 2pz-orbitals of carbon
creating p bonds) or by full incorporation into the layer by
replacing carbon atoms (substitution, also referred to as metal-
monovacancy or metal-divacancy complex). In the case of substi-
tution within the hexagonal carbon layer or bonding at the edge, a
carbon-metal s bonding is created. An intermediate case is the
trapping of a metal atom on reconstructed vacancy defects where a
vacancy is healed by construction of pentagonal/heptagonal rings
in place of the missing carbon atom. In such reconstructed defect
sites, a bonding energy greater than that of an atom on a perfect
graphene is expected due to the increased reactivity of non-
hexagonal defects. The possible adsorption sites of TM atoms on
the graphene basal plane are the tops of carbon atoms, the bridge
sites at CeC bonds and the hollow sites at the center of hexagon
carbon rings. The theoretical adsorption energy of TM adatoms on
defect-free graphitic materials (from ca. 0.2e2.5 eV) is lower than
the metal-metal bonding energies which, together with the low
diffusion energies of TM on graphene, lead to metal clustering due
to high cohesive energy [67,68].
The nature and strength of the adsorption of TMs on graphitic
surfaces are correlated to carbon hybridization (sp2 vs sp2þε). Gra-
phenic materials with curved surfaces (with transitional sp2þε hy-
bridization) have higher binding energies. While graphene is
perfectly flat, the geometrical structure of the carbon bonds in the
fullerenes is pyramidalized (non-planar) [69]. An increase in cur-
vature leads to stronger pyramidalization of the sp2-hybridized C
atoms and hence higher affinity to undergo addition reactions [70].
Elimination of pyramidalization of carbon atoms in curved struc-
tures (e.g. fullerenes) release strains and therefore it is the driving
force for metal complexation reactions. SWCNTs exhibit lower
curvatures than fullerenes and the pyramidalization strain is
consequently not as severe; in this case the p-orbital misalignment
between adjacent carbon atoms has greater influence on their
reactivity than the pyramidalization. For CNTs with larger external
diameters >10 nm or for giant fullerenes this phenomenon is
negligible and their chemical reactivity approaches that of planar
graphene. Binding energies of 3d TM adatoms to C60 fullerene
surface reach up to 3 eV, but due to the high cohesive energy of
metals, they still tend to form clusters even at surfaces as curved as
the fullerenes. Theoretical study of the adsorption of individual 3d
TM atoms on planar and curved graphenic surfaces (graphene and
SWCNT) showed that both structures adsorb 3d metals in a similar
manner regardless of the curvature or its absence. 3d TM atoms are
chemisorbed with a h6 hollow geometry (binding energy of up to
1.74 eV) except for Cr, Mn, and Cu [71]. Cr and Mn with half-filled
(d5) and Cu with completely filled (d10) sub-shells are only phys-
isorbed on these sp2 and sp2þε surfaces. As known, Cr and Cu have
anomalous electron configurations (3d54s1 instead of the theoret-
ically expected 3d44s2 for Cr, and 3d104s1 instead of 3d94s2 for Cu).
These configuration anomalies are due to the enhanced stability
associated with half-filled and totally-filled d sub-shells (observed
for Cr, Cu and Mn), which in turn affect interactions of these metals
with carbon. Density Functional Theory (DFT) calculations per-
formed for 3d, 4d, and 5d TM atom adsorption on the graphene
surface (adatoms) showed that TMs prefer to be located on the
hollow sites when chemisorbed and on the bridge and the top sites
when physisorbed [72]. The adsorption strength is governed by the
relative stability/instability of the isolated TM atoms. The adsorp-
tion energy values follow a double hump trend, where d5 and d10
elements with half- and fully-filled atomic orbitals exhibit

ski, S. Dyjak / Carbon 168 (2020) 748e845
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physisorption, Fig. 9. The semi/full-occupancy of d orbitals (d5 or d10
configuration) stabilize the isolated metal atom (or ion), hence
their binding energy to graphene is low. The trends for diffusion
energy barriers on graphene surfaces follow adsorption energy
trends. Except Au, all TMs were found to n-dope graphene and the
doping degree weakens along a given d-series due to the increase in
metal electronegativity [72]. Interactions between alkali-metal
adatoms and graphene are ionic. Alkali adatoms donate their
valence electrons to graphene and act as strong n-doping agents. In
contrast, stronger hybridization between the TM adatoms and
graphene electronic states results in covalent bonding. 3d TM
adsorption exhibits a diffusion barrier on graphene of ca.
0.2e0.5 eV while the ionic bonding of alkali metal adatoms is much
weaker (for instance 0.055 eV for potassium) [73].
Atoms or molecules adsorbed on perfect graphene surfaces are
weakly attached and easily migrate or evaporate and exhibit high
mobility even at room temperature. With an activation energy for
migration of ca. 0.2 eV an atom migrates over a distance of 10 mm in
1 s at room temperature [74]. For this reason, the defect-free re-
gions of graphene do not host metal adatoms. Adatoms migrate
rapidly on the graphene surface until they find a stable site for
binding (e.g. edges, patches of hydrocarbon contaminations or va-
cancies with unsaturated bonds or reconstructed vacancies with
strained bonds). The StoneeWales, single vacancies (SVs) and
double vacancies (DVs) are examples of typical point defects in
graphene lattices with formation energies in the range of 5e10 eV.
Graphene lattices exhibit a unique ability to heal the “holes” (i.e. to
reconstruct) by forming non-hexagonal rings [75]. The vacancies
can undergo reconstruction into various planar and non-planar
structures which creates a coherent defective lattice without
under-coordinated atoms (without “holes” in the sheet), Fig. 10.
Since an even number of missing atoms permits full reconstruction
(total saturation of dangling bonds), such vacancies are energeti-
cally favored over structures with an odd number of missing atoms
(where an open bond remains unsaturated). Reconstructed defects
(even if they do not contain dangling bonds) increase the local
reactivity of the carbon surface. In the case of DV, the defect of three
pentagons and three heptagons V2(555e777) is energetically more
favorable than V2(5555-6-7777) or V2(5-8-5) [76] (see Fig. 10 for
Fig. 9. Adsorption and diffusion energies (Eads, Edif) of 3d TM atoms on the surface of
graphene. PBE-D2 DF simulation results are shown. These plots were prepared using
numerical data presented in Ref. [72]. Adapted with permission from Ref. [72]. Copy-
right 2015 Elsevier. (A colour version of this figure can be viewed online.)
759
vacancy definitions). DV is rather immobile since its activation
energy is of ca. 7 eV. On the other hand, the barrier for SV diffusion
is ca. 1.3 eV, which makes it mobile at temperatures as low as 200  C
[75]. Fig. 11 shows experimental observations of mono-, di- and
trivacancies in graphene sheets produced by ion bombardment
[77].
As expected, the binding energies of individual metal adatoms
adsorbed at the surface of carbon nanotubes or graphite/graphene
change according to the number of d-vacancies rule that is:
Ti > Ni > Pd > Fe > Al > Au, which means that Ti binds strongly to
the surface while Au is highly mobile on the carbon surface even at
cryogenic conditions [78]. However, the Ti adatom becomes highly
mobile on the defect-free graphene surface even at room temper-
ature. This unrestricted diffusion of metal atoms adsorbed on car-
bon surfaces and the low energy of the metalecarbon p-bonding
lead to aggregation of metals into clusters. Some theoretical pre-
dictions suggest that Sc, Ti, Fe, and Co could be stable as isolated
atoms on any graphitic carbon surface, while Cr, Mn, Ni and Cu are
predicted to diffuse instantaneously and form aggregates [79]. On
the other hand, all TM atoms strongly bind to graphene with va-
cancies or unsaturated edges forming s bonds at the defects. Even
noble metals like Au form covalent bonds with undercoordinated
carbon atoms around a vacancy [80]. TM propensity to form bonds
with the adjacent carbon atoms favors substitutional over
Fig. 10. Examples of point defects in graphene sheet: (A) single vacancy (SV), (B)
reconstructed SV, (C) double vacancy (DV), (D) reconstructed V2(5-8-5) DV, (E)
reconstructed V2(555e777) DV, (F) reconstructed V2(5555-6-7777) DV, and (G)
StoneeWales defect SW(55e77). (A colour version of this figure can be viewed online.)
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Fig. 11. HRTEM images of (a) a monovacancy, (b) a bivacancy, and (c) a trivacancy. Scale bar: 1 nm. (def) Atomic models and (gei) simulated HRTEM images for the three different
vacancy types in (aec). These vacancies were created by high-energy atom/ion bombardment. Adapted with permission from Ref. [77]. Copyright 2012 American Chemical Society.
(A colour version of this figure can be viewed online.)

interstitial metal positions in graphitic structures. For instance, the

binding energies of Fe in graphene vacancies are of 7 eV for an iron
atom in a single vacancy and 6 eV for Fe in a double vacancy [80]. In
fact, TM can bind extremely strongly to pre-existing vacancies, with
binding energies sufficiently high to make the atoms immobile up
to very high temperatures (>1000  C). Thus, vacancies act as traps
to metal atoms migrating freely over the surface of graphene/
nanotube. Binding energies of less than half-filled and more than
half-filled 3d TMs either adsorbed on defect-free graphene or
substitutionally bound at the single vacancy are shown in Fig. 12.
Theoretically predicted binding energies for the TM-SV complexes
(substitution of carbon atom in the hexagonal lattice) are in the
range of ca. 4e8 eV which is higher than the cohesive energies of
TMs [81]. The binding energies of 3d TM adatoms adsorbed on a
defect-free graphene sheet (at the center of the hexagonal ring) are
in the range of 1.0e1.5 eV, which is lower than the cohesive en-
ergies of the 3d TM elements.
TMs as substitutional impurities located in graphene SV are
displaced from the flat graphene layer because the transition metal
atomic radii are larger than that of the carbon atom. The height over
the plane defined by its three nearest carbon neighbors is in the Fig. 12. DFT calculated binding energies of TM atoms located at a hexagon-top position
range of 0.9e1.7 Å. These three carbon atoms are also displaced off of a perfect graphene sheet (circle) and on a single vacancy defect (square). The
the graphene layer by 0.3e0.5 Å and hence the total height of the cohesive energies of the respective TM atoms (triangle) are given for comparison.
metal atom over the graphene plane ranges between 1.2 and 1.8 Å Reproduced with permission from Ref. [81]. Copyright 2010 American Chemical So-
ciety. (A colour version of this figure can be viewed online.)

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Fig. 13. Optimized atomic structures of Fe in monovacancy (left) and in divacancy
(right) defects: (a and b) top view; (c and d) side view (Fe atoms are shown as larger
orange spheres). Reproduced with permission from Ref. [83]. Copyright 2016 American
Chemical Society. (A colour version of this figure can be viewed online.)
[82]. Substitutional metal impurities (except for noble metals)
present an almost perfectly symmetric threefold configuration with
C3v symmetry. However, some of the TM atoms substitutionally
embedded into graphene undergo a Jahn-Teller distortion and
break the C3v symmetry [82]. The metalecarbon bond length, the
height of the impurity/dopant over the layer and the binding en-
ergies correlate with the size of metal atoms. The carbonemetal
bond length reaches its minimum for Fe (1.76 Å), and for Co and
Ni similar values are observed. Fig. 13 depicts an iron atom in a
mono- or a divacancy in graphene [83]. The off-plane position of
the metal atom is smaller when the atom resides in a divacancy. The
TMeC bond length decreases from Sc to Fe (since the size of tran-
sition metal atoms decreases from left to right), but then it goes up
since the bonding with d-orbital-filled atoms becomes weaker [80].
For Cu and Zn the distances increase, due to the fully occupied 3d
shell and the large size of the 4s orbitals. Fe impurity presents one
of the smallest carbon metal bond lengths and one of the largest
binding energies among the 3d transition metals. Generally, bind-
ing energies at SV for non-precious TMs are in the range of 8e6 eV
while for noble metals they are much smaller and mirror the
reverse behavior of the bond lengths (e.g. ~3.7 eV for Cu) [82].
The tetravalent Ti atom (four valence electrons (3d24s2)) is a
perfect substitution for a tetravalent C atom (2s22p2) in a single
vacancy in the sp2-carbon honeycomb [80]. Three of the valence
electrons are involved in the TieC covalent s bonds, while the
Fig. 14. Theoretical adsorption energies (in eV) for atomic adsorption at the SV using PBE calculations. Reproduced from Ref. [85] with permission from the PCCP Owner Societies. (A
colour version of this figure can be viewed online.)
761
fourth electron replaces the p electron of the missing carbon atom.
This yields three s bonds and one (slightly out-of-plane) p bond. As
a result, four valences are saturated, and the spin is zero. In this case
the binding energy is the largest among all TM atoms substituting
carbon atoms in the conjugated carbon sheet [82]. Theoretical
consideration of 4d series TMs (from Y to Pd) as substitution im-
purities in a graphene monolayer (filling SV) showed that all 4d
TMs create covalent bonds with three neighboring C atoms
exhibiting C3v symmetry [84]. The 4d atoms locate above the va-
cancy in a graphene layer and substitute carbon atoms with binding
energies >6 eV.
Generally, while a single vacancy is an ideal trapping site for
non-metallic atoms of similar atomic radii as carbon (B and N
atoms), noble and TM atoms are usually trapped by larger vacancies
[77]. Systematic DFT analyses were performed to assess adsorption
energies at the SV sites (substitutional doping of the missing C atom
at the hexagonal lattice) of graphene for nearly all the periodic table
elements, Fig. 14 [85]. For a majority of the elements, strong binding
(2e13 eV) at the SV site was found. As expected, the highest
adsorption energy was found for C, B and N. Generally, TMs exhibit
strong affinity for the SV site with energies between 6 and 8 eV. A
very weak bonding was observed for Cu, Ag, Au, Zn, Cd and Hg
(group 11 and 12). Shallow minima of adsorption energy were also
observed for the elements with half-filled d-band configurations.
It was found that the energy of adsorption at SV correlates with
the cohesive energies of the elements: the stronger the cohesive
energy of an element the stronger its interaction with the SV site
[85]. No correlation either between the adsorption energies on
pristine graphene and on SV or between the cohesive energies and
adsorption energies on pristine graphene was found. This is
explained by different bonding occurring in these two cases (sur-
face adatoms interacting via p-electrons vs covalent bonding at SV
site). The observed stabilization of metal atoms at the SV in com-
parison to their pure phases was correlated to the tendency of these
atoms to dissolve from SV-graphene (Fig. 15). This allows assess-
ment of the M@SV-graphene system stability at conditions where
dissolution and corrosion can take place (e.g. heterogeneous
catalysis in acidic liquids). The standard electrode potentials of the
following process:
Mzþ þ SVgraphene þ ze- / M@SVgraphene
were calculated to assess the dissolution potential for TM im-
purities in the graphene lattice. The majority of typical
catalytically-active TMs (e.g. Fe, Ni) are more resistant to dissolu-
tion when bound in SV than when they occur in their metallic
phases. In other words, TMs located at graphene vacancy are more
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Fig. 15. Average electrode potentials for the dissolution of metal adsorbed in the SV site of graphene. Numbers next to symbols denote the group of the periodic table of elements.
Data points give the average electrode potential obtained using four computational schemes while the error bars indicate their variation among the methods used (see Ref. [85] for
details). The data points for the electrode potentials of the metals considered are not linked to pH scale. Horizontal lines give electrode potentials for the pure metallic phases of the
given elements. Reproduced from Ref. [85] with permission from the PCCP Owner Societies. (A colour version of this figure can be viewed online.)

“noble” than in bulk. This means that TMs substitutionally
embedded in graphene lattices are less prone to dissolution than
impurities in the form of metallic nanoparticles decorating the
carbon scaffold. In contrast, some elements are expected to easily
dissolve from the SV site at the whole pH range (e.g. Cd or Zn). The
high stability of substitutional TM impurities should (and in fact
already did) allow synthesis of robust single TM atom-based cata-
lysts (the so-called SAC systems).
The trapping of metal atoms in the graphene mono- and diva-
cancies is indeed highly exothermic and has been experimentally
observed, e.g., for Ni atoms in irradiation-induced vacancies of
spherical graphitic layers [44,86]. Fig. 16 shows a Ni crystal
encapsulated in a multi-layer graphitic shell. Carbon atoms in the
shell have been substitutionally replaced by Ni atoms under ener-
getic electron irradiation. As elucidated above (Fig. 13), the position
of the metal atom in the sp2 carbon layer is slightly off the carbon
layer due to the differences in metalecarbon and carbonecarbon
bond lengths within the layer (0.18 nm for a CeNi and 0.14 nm
for CeC).
In fact, there is a profusion of experimental data proving
successful infusion of Ni atoms into hexagonal carbon layers. Ushiro
et al. showed that Ni substitutional defects were present in CNF
samples even after thorough acid leaching [87]. After purification,
100 ppm of residual Ni catalyst was found to be still adsorbed/
absorbed at the CNFs and Ni impurities occupy substitution sites in
the graphene sheet or edge sites with strong NieC s bonds of 1.83 Å
in length. Strong covalent NieC bonds prevent the Ni atoms from
being removed by acid leaching. The proposed structure of Ni in the
graphene layer as shown in Fig. 17 had been suggested earlier by
Banhart et al. [44,86].
Due to the growing interest in metal-free and single-atom cat-
alysts, the observations reported by Banhart et al. 20 years ago [86]
and by Ushiro et al. 15 years ago [87] are now being “rediscovered”
and the number of direct observations of acid-resistant, single TM
atoms trapped in SV or DV of graphene lattices grows rapidly. For
instance, simple wet impregnation, followed by annealing and acid
leaching of an excessive metallic phase is routinely used to prepare
graphitic materials with embedded single Ni atoms with loading of
up to a few wt% [88,89], Fig. 18. TEM observations demonstrated
that the Ni atom is trapped in the graphene defects to form a direct
NieC bond. Additionally, it was observed that a four-coordinate
NieC4 structure with square-planar geometry exhibited high

Fig. 16. Incorporation of Ni atoms into spherical graphitic shells surrounding a Ni Fig. 17. Local structures of a carbide model (where each Ni atom is surrounded by two
crystal nanoparticle (the arrows show Ni atoms). The structure has been generated carbon atoms) and Ni atom in graphene single vacancy. Adapted with permission from
under electron irradiation. Reproduced with permission from Ref. [44]. Copyright 2009 Ref. [87]. Copyright 2006 American Physical Society.
The Royal Society of Chemistry.

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W. Kicin 763

Fig. 18. Preparation and structure of Ni-doped defective graphene: (A) The fabrication schematic. (B) STEM-EDS elemental mapping. (C) HAADF-STEM image (D) Bright-field STEM
image with high resolution. The defective sites (vacant and with single Ni atom trapped) are marked with red arrows. (E) The corresponding HAADF-STEM image of (D). (F) The
zoomed-in image of the defective area (vacancy) marked with the yellow dashed frames in the bottom left of (E). (G) The zoomed-in image of the defective area (with atomic Ni
trapped) marked with the yellow dashed frames in the top left of (E). The di-vacancy is marked with the red dashed line. Adapted with permission from Ref. [89]. Copyright 2018
Elsevier. (A colour version of this figure can be viewed online.)

electrochemical stability in hydrogen and oxygen evolution re- covalently bonded transition metal atoms in graphene layers as
actions [89]. they studied the migration of Au and Pt atoms in MWCNTs attached
Annealing of metal and carbon precursor mixtures yields
random systems of metal-carbon defective sites. More precise
methods to substitutionally dope graphene with single atoms
entail formation of vacancies by high-energy atom/ion bombard-
ment or electron irradiation and filling these vacancies with the
desired dopants. This approach was utilized to dope graphene with
single atoms of Pt, Co, and In, Fig. 19 [77]. It has been also noted that
the state of a TM atom at a graphenic carbon structure depends on
the concentration of the metallic phase. An interesting example is
the study of the expected state of palladium deposited on CNF with
stacked structure depending on the metal concentration [90]. The
concentration range of 0.04e0.5 wt% was considered. Pd was found
to exist as single atoms attached to CNF at concentrations of up to
0.2 wt%. Below 0.04 wt% Pd intercalates deeply into the CNF
graphitic structure. At concentrations in the range of 0.04e0.2 wt%
Pd atoms also populate the CNF surface, while at concentrations
>0.1 wt% metal clusters appear on the nanofiber surface (Fig. 20).
As elucidated above, perfect graphene is chemically inert, but it
Fig. 19. HRTEM images of a Pt atom trapped in (a) a bivacancy and (b) a trivacancy. (c,
can be transformed to an active catalyst by embedding impurities d) Atomic models and (e, f) simulated HRTEM images for the Pt-vacancy complexes in
(dopants) either substitutionally, interstitially, or as surface ada- (a, b). (g) Binding energies for different configurations. For the monovacancy, the Pt
toms. However, the diffusion of doped metal atoms in the resulting atom resides out of the lattice plane in order to minimize the energy of lattice
carbon structures is still not fully understood. Banhart et al. deliv- distortion due to atom size mismatch. Adapted with permission from Ref. [77].
Copyright 2012 American Chemical Society. (A colour version of this figure can be
ered one of the first direct observations of the incorporation of
viewed online.)
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Fig. 20. HRTEM image of the 0.5 wt% Pd/CNF catalyst sample reduced at 250  C and population of the various CNF near-surface sites depending on the Pd concentration (possible
locations of Pd atoms based on the EXAFS analysis and quantum-chemical calculations). Reproduced with permission from Ref. [90]. Copyright 2012 Elsevier.

to bulk metal crystals [91]. They elucidated how metal atoms
diffuse into the graphenic structure at the carbon/metal interface
and under what circumstances intentional or incidental contami-
nation of graphenic structures by metal atoms/clusters can occur.
The diffusion of a metal atom via substitutional sites exhibits a high
activation energy because the breaking of strong metalecarbon and
carbonecarbon bonds is required. Fig. 21a shows presence of
2e4 Pt atoms in the layers of a MWCNT (at 600  C). Fig. 21b shows a
nanotube attached to an Au crystal where a few Au atoms migrated
into the layers of the nanotube. The activation energy for the in-
plane migration of both Au and Pt atoms in graphene was deter-
mined to be around 2.5 eV, and 2.3 eV for the migration of Pt atoms
in the shells of MWCNTs which indicates covalent bonding between
metal and carbon atoms.
Direct observation of substitutional Au and Pt atoms in the
structure of CNTs [91], leads to a few very important conclusions: (i)
if Au, which is known to weakly interact with carbon, can substitute
carbon in graphenic structures then virtually all TM atoms can be
incorporated in graphene structures, (ii) TM atoms and clusters
from the catalyst particle (in case of catalyst-assisted CVD synthe-
sis) can easily contaminate graphitic structures by diffusion, (iii) it
is impossible to remove such impurities by any known liquid-based
purification methods. Only vacuum-based high temperature heat
treatment techniques can be efficient purification procedures in
such instances.
Recent advances in transmission electron microscopy tech-
niques enabled direct observation of interactions between transi-
tion metals and carbon nanostructures at the atomic level. The
structure of graphene can be imaged nondestructively with great
resolution using an aberration-corrected high-resolution
transmission electron microscope (AC-HRTEM) at low accelerating
voltages of 80 kV. Because of the low-energy bonding between
the p-electronic system of the CNTs/graphene and the adsorbed
metal adatoms (in the range of 0e2 eV) and hence high diffusivity
of the metal atoms (e.g. tens of micrometers for Au on graphene),
the study of their interactions with carbon structures is challenging
[92]. Yet the high mobility of metal adatoms combined with very
low mobility of TM-vacancy complexes can be used to conveniently
control the position of metal atoms with atomic precision. In this
procedure a vacancy is first created and then the temperature is
increased to mobilize the metal atom until it falls into the vacancy
trap [74,77]. As single- and double-vacancies provide s-bonding
they can be utilized for permanent metal atom immobilization.
Moreover, studies of the escape process of immobilized metal
atoms at different temperatures enable estimation of the in-plane
metalecarbon s-bonding energy [74]. For instance, Fe, Co, and
Mo were deposited and then trapped on CNT and graphene samples
where defects were created by an electron beam. The subsequent
escape of the metal atoms from the trapping centers provided in-
formation concerning the bonding of the metal atom at the defect
[74]. The trapping and detrapping phenomenon was studied in a
temperature range of 20e670  C. The activation energies for
diffusion in graphene were estimated to be in the range of
2.1e3.6 eV for metal-SV and around 5 eV for metal-DV complexes.
AC-HRTEM has been used in other experiments to study real time
dynamics of Fe atoms filling the mono- and divacancy sites in
graphene with high atomic resolution [93,94]. The Fe-filled defects
obtained are very stable in comparison to Fe atoms incorporated
into the graphene edge. Importantly, despite the fact that the doped
iron atoms are fully exposed to atmospheric oxygen, these active

Fig. 21. a) Pt and b) Au atoms in MWCNTs. Substitutional Au atoms in the shells of a MWCNT attached to an Au crystal are arrowed. The presence of substitutional Au atoms in the
layers indicates stable incorporation of Au atoms into the CNT lattice. Reproduced with permission from Ref. [91]. Copyright © 2008 WILEY-VCH Verlag GmbH & Co. KGaA,
Weinheim.

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surface atoms still remain unoxidized even if stored in air [95].
While oxidation of metals may preclude their use as catalysts
because of deactivation, graphene grants oxidation resistance to
single atoms/small clusters, yet without isolating them from the
environment. This observation is of crucial importance for appli-
cations of carbon-supported single-atom catalysts. The covalently
bonded TM atoms not only have a significantly lower diffusion rate
and are much more stable in comparison to the weakly interacting
surface adatoms, but they are also resistant to air oxidation.
The behavior of bulk metal quantities locked in tight graphitic
shells has been also studied. When a metal crystal in graphitic
shells is exposed to electron irradiation the shells contract without
losing mass, but the size of the metal crystal decreases until, at a
critical size, it suddenly disappears from the shell [96]. This phe-
nomenon was elucidated by the migration of metal atoms through
the graphitic shells which is caused by forcing the metal atoms to
occupy vacancies in the graphitic lattice. Spherically curved gra-
phene layers are permeable to large TM atoms such as Co or Au and
such peculiar “porosity” on an atomic scale is enhanced by electron
irradiation [96], Fig. 22. Indeed, it was observed even earlier that
when transition metals encapsulated in graphitic shells are sub-
jected to an electron beam or high temperature annealing, they
exhibit a tendency to migrate out of the concentric carbon cage,
which closes itself again afterwards [97,98]. Carbon shells of the so-
called carbon nano-onions are indeed permeable to core metal
atoms and ions and they cannot be considered as impermeable
sheaths [99,100].
Much can be learned about metal-carbon interactions by
experimental preparation of CNTeTM particle junctions, which are
usually created by passing an electric current through CNTs con-
taining encapsulated metal particles (Joule heating) or by electron
irradiation of CNTs with a metal particle in an electron microscope
environment. Carbon-based nanostructures are considered prom-
ising materials for next-generation integrated circuits. However,
the high contact resistance at the interface with metal electrodes is
one of the performance-limiting factors [101]. As elucidated above,
Fig. 22. Micrograph series showing the shrinkage of an encapsulated cobalt nano-
crystal and the contraction of the graphitic shells under electron irradiation at a
temperature of 1000 K. The irradiation time is indicated in each micrograph. Repro-
duced with permission from Ref. [96]. Copyright 1998 Elsevier.
765
theoretical calculations pointed out that the contact between metal
atoms of the main groups IeIII and graphene is ionic (alkali metals
are electron donors) while transition metals make covalent bonds
with graphene [102]. Calculations of the interfacial structure of
metal electrode/graphene interfaces for 12 different metals (K, Ca,
Li, Sc, Ti, Co, Ni, Al, Cu, Au, Pt, Pd) showed that two types of contacts
(a strong chemical or a weak physical contact) exist depending on
the strength of interaction between d-orbitals in metals and pz-
orbitals in graphene. As expected, Ti leads to the lowest contact
resistance of the metaleCNT junction followed by Pd, Pt, Cu, and Au
[103,104]. Ti and Pd are often indicated as the best two candidates
as contact metals while the cohesion for other metals is much
weaker [103]. Ti forms an Ohmic contact as it exhibits the strongest
bonding with graphene by far, with a separation slightly above
2.1 Å, compared with interplanar spacing of 3.5 Å for graphite.
However, the high reactivity of the Ti electrode at the contact may
at some cases distort the graphene or nanotube structure by for-
mation of TiC and leads to metal oxidation. Experimental works
showed that the resistance of the carbon/metal electrode contact
follows the rule of wettability [105]. Good wettability (which in-
creases with increasing numbers of d-vacancies) reduces resistance
by enhancing the contact area with CNTs. Early/middle transition
metals (Ti, V, Cr, W, Mo and Nb) form carbides at the metal/CNT
interface under heat treatment. These metals are considered
excellent contacts for practical CNT-based electronic devices. Their
carbides are good metallic conductors with high melting points,
high corrosion resistance and are suitable for interconnects in
ultra-large-scale integrated circuits. Carbides form at the carbon/
TM interface once a sufficient temperature is reached for the re-
action to occur (ca. >700  C) [106e108]. In the case of contact with
MWCNT-WC-W junctions (nanotube/carbide/tungsten), all the
shells of a MWCNT solder directly to the surface of a tungsten wire
[109], Fig. 23. Tungsten exhibits exceptionally strong adhesion with
carbon attributed to the formation of strong covalent WeC bonds
between CNT and tungsten. The remarkably high tensile strength
was in the range of 5e15 GPa. A tensile strength measured for a
junction between metals with less d-vacancies, for instance for
cobalt and a MWCNT end-contact, is indeed weaker (5 GPa) but its
strength still indicated formation of strong covalent CoeC bonds
[110].
Strong carbon-titanium interactions were utilized to cover
suspended SWCNTs by various metals [111]. Typical TMs/heavy
metals form discrete particles on SWCNTs due to weak interactions
(high surface diffusion rate of absorbed metal adatoms). Yet
continuous nanowires of virtually any metal can obtained by using
Ti as a buffer layer. TEM micrographs in Fig. 24 show that Au, Pd, Fe,
Al, and Pb deposited on bare SWCNTs form only discrete particles.
In contrast, if a tube is first covered by Ti layer formation of a
continuous and uniform coating of weaker interacting metals is
possible. Consequently, Ti constitutes good connector for uniform
carbon-TM interfaces.
The influence of the valence d-orbital occupancy of 3d transition
metals on the interaction strength with CNTs was thoroughly
inspected experimentally [112,113]. Using AC-HRTEM and electron
energy loss spectroscopy (EELS) techniques the interactions be-
tween MWCNTs and the early (Cr, V) and late (Ni, Cu) 3d metals
were studied. In the case of the late transition metals, Ni interacts
more strongly with the MWCNT walls than Cu (for which no
interaction was observed) [112]. TEM images show better wetting
and a smaller gap at the NieMWCNT interface, as compared to the
Cu interfaces since Ni particles form covalent NieC bonds. The EELS
spectra revealed a slight carbon rehybridization from sp2 to sp3 of
the outermost MWCNT layer at the Ni/C interface, Fig. 25.
Unlike Ni and Cu, the early transition metals, e.g. Cr and V,
showed much stronger reactivity, once again confirming the
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W. Kicin
Fig. 23. In situ fabrication of a CNT-carbide-tungsten junction inside the TEM. a) The
end-to-end physical contact between a single MWCNT and the W tip. b) Joule-heating
induced interfacial reaction leads to the formation of tungsten carbide at the CNT/W
contact, which can be also confirmed by the spatially resolved EELS map (c) showing
the carbon distribution within the junction. The TEM image (d) and the corresponding
EELS maps (e) show that the whole ball-like head of W tip has been transformed into
carbide. The arrows in (e) indicate the boundary between the carbide region and the
metal. Reproduced with permission from Ref. [109]. Copyright © 2010 WILEY-VCH
Verlag GmbH & Co. KGaA, Weinheim.
Fig. 24. TEM images of: Au, Pd, Fe, Al and Pb coating on bare SWCNTs with a nominal thickness of 5 nm (on the left) and corresponding coating on carbon nanotubes with a 2 nm
thick Ti buffer layer (on the right). Reproduced with permission from Ref. [111]. Copyright 2000 AIP Publishing.
importance of the occupancy of the valence d-orbitals for control-
ling the contact behavior of the transition metals with CNTs [113].
For V, an interfacial vanadium carbide (VC) layer appears at the
interface with MWCNTs when the sample is heated to 750  C. Cr
reacts with the MWCNTs at 500  C to form Cr3C2 and is able to
dissolve (consume) the MWCNT completely. Another example of
heterojunctions formed in situ from metal-filled MWCNTs (Fe, Co,
Ni) via electron beam irradiation was provided by Banhart et al.
[114]. Structures consisting of two MWCNTs joined by a short
transition metal nanowire were obtained. A large lattice mismatch
between the metal and the nanotube lattice was observed (Fig. 26,
inset). Large strains at the interface (seen as the bending of the
MWCNT walls) show that the bonding between the nanotube and
Co or Ni is strong (presence of covalent bonds). However, no evi-
dence for the formation of carbides at the interface was found at
that point.
All the observations and experiments performed for TMeCNT
junctions were later repeated for graphene with similar results.
As in the case of CNTs, transition metals can break the CeC bonds in
graphene and lead to the formation of carbides. The carbon disso-
lution can occur spontaneously upon metal deposition on CVD-
grown graphene. For instance, formation of nickel carbide at
100  C when Ni is deposited on the as-synthesized graphene was
observed [115]. In comparison to the spontaneous reaction at room
temperature, annealing can substantially enhance the
nickelgraphene chemical reaction [116]. This leads to formation of
end-contacted metalgraphene contacts arising from the carbon
dissolutionprecipitation process at the carbon/metal interface.
This phenomenon occurs at Ti-, Co-, Ni- and Pd-graphene in-
terfaces, whereas Au- and Pt-graphene interfaces are only weakly
bonded. The formation of carbides can totally consume the gra-
phene layer when wetting metals such as Pd and Ti are deposited
on graphene, just like previously observed for CNT junctions [117].
Carbon/TM interfaces are also of crucial importance in the case
of metal matrix (nano)composites reinforced by CNFs or CNTs. Ti-
tanium and titanium aluminide (TiAl) have received special atten-
tion as metal matrixes due to their strength and corrosion
resistance [118]. Mechanical tests reveal the higher strength of the
CNT-Ti over the CNT-Al interface. The strong CNT-Ti binding inter-
face is due to the chemisorption of Ti atoms on CNT surfaces, while
Al atoms are only physisorbed on CNT. Nevertheless, the presence

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W. Kicin
Fig. 25. In this STEM HAADF image of an equatorially positioned Ni particle on a
MWCNT, some Ni atoms appear to be integrated into the graphitic system of the CNT
wall (indicated by the white arrow). The inclusion of metal atoms into the graphitic
CNT system suggests enhanced interaction of the metal particle with the CNT. Adapted
with permission from Ref. [112]. Copyright 2015 Elsevier.
of oxide layers on the aluminium surface enhances the mechanical
strength of CNT-Al interfaces, yet weaken CNT-Ti interfaces. This
example shows that active TMs exhibit high affinity to oxygen and
their surfaces are often covered by layer of oxides, which must al-
ways be considered in real-life applications of carbon/metal
systems.
The examples discussed above assume interactions of metal
atoms with idealistic, that is, perfect graphite/graphene or nano-
tube surfaces. The discussed experiments are also usually per-
formed in the very special conditions of electron microscopy
environments. However, in reality carbon surfaces are very com-
plex systems as they are always functionalized by oxygen/hydrogen
groups and accompanied by amorphous carbon phases or organic
impurities. Consequently, the interaction of transition metals with
carbonaceous materials is influenced or even dominated by the
presence of such surface entities. Similarly, metal surfaces are
usually covered by an oxide/hydroxide layer. For instance, it was
shown that the presence of oxygen at the CNT-copper interface can
improve interfacial strength [119]. Also, the presence of oxygen
groups improves the dispersion of Au and Rh clusters while oxygen
groups at the TieCNT interface reduce the net charge transfer from
Ti atoms to the CNT, leading to partial de-bonding of the metal. If
carbon materials such as graphene or nanotubes contain a fraction
of amorphous phase (and they always do) metal atoms tend to bind
preferentially to this amorphous phase. Single atoms and small
clusters of Pb and Te tended to attach only to the regions of the
Fig. 26. High-resolution images from metaleMWCNT junctions. (A) Bright-field STEM image of a MWCNTeCo interface. Strain is introduced at the interface as can be seen by the
local bending of the graphitic layers at the interface. The inset shows a detail of the interface where the bending of the nanotube layers to match the metal lattice is visible. (B)
HRTEM image of a MWCNTeNi interface. Reproduced with permission from Ref. [114].
767
amorphous carbon phase residing at the graphene surface, but not
to the areas of pure graphene [120]. This suggests that it will be
extremely difficult to form metallic nanocrystals that are in direct
contact with pristine graphene/nanotube, since they tend to bind
preferentially to the amorphous carbon residues. It was also
observed that metals favor sites contaminated with hydrocarbon
residues rather than the clean graphene surface, which precludes
formation of continuous metal films and leads to local clusters of
metallic phases scattered randomly on the graphene surface [121].
Interestingly, from the standpoint of materials engineering,
metal-carbon interactions determine the mechanical and corrosion
durability of metal-carbon-based tools. For instance, if a diamond
tool is used for TM cutting, the frictional force at the diamond/
metal interface increases with the number of d-vacancies in the
metal [46]. The friction raises the temperature during cutting
which leads to the chemical wear (oxidation, graphitization or
carbide formation) of diamonds. For this reason, diamond tools are
only suited to cut transition metals with a low number of d-va-
cancies (e.g. Cu, Zn). More inert materials should be used for pro-
cessing metals with higher numbers of d-vacancies (e.g. Ti, Fe).
Synthetic diamonds used as superabrasives are made using metal
catalysts, so they contain inclusions of such catalyst impurities.
These impurities cause catalytic back-conversion from diamond to
graphite (diamond % graphite) which is the main cause for
weakening and degradation of synthetic diamonds in industrial
applications. Finally, it should be mentioned that while catalytic
graphitization is usually associated with high-temperature
annealing [10], surprisingly it can also occur at room tempera-
ture. Amorphous carbon deposited at room temperature on a clean
nickel surface (without any surface oxides) formed several layers of
graphenic carbon, while on an oxidized Ni surface, annealing was
required for carbon graphenization [122]. Consequently, to induce
spontaneous graphenization of amorphous carbon, an oxygen-free
pure TM surface is required. This is yet another example of how
oxygen disrupts carbon-metal interfaces. In fact, the presence of p-
block heteroatoms (e.g. N, S, P, B, etc.) in the structure of graphenic
carbons significantly alters carbon-metal interactions. The presence
of N or S increases the strength of the metal binding to the carbon
matrix. The stability of 3d TMs embedded in N-doped graphene has
been assessed theoretically and the TM adatoms can form TM-N4
structures characterized by high values of binding energies (Fig. 27)
[123]. The TM atoms embedded into N4V2 vacancy (TMN4V2,
where N is in a pyridinic configuration) exhibit extraordinary sta-
bility and possess extremely large binding energies, and among
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ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
Fig. 27. (a) Optimized configurations and (b) formation energies for TM atoms
embedded into different types of N-doped graphene (a first-principles study). Repro-
duced from Ref. [123]. Copyright © 2015, Author(s), distributed under a CC BY license.
(A colour version of this figure can be viewed online.)
them Fe and Ni atoms possess the largest binding energies of ca. 8
eV. The bond lengths of NieN and FeeN are 1.88 Å and 1.90 Å,
respectively, which are shorter than for other atoms. Carbon sup-
ported FeeN4 structures are part of a well-established field of the
so-called transition metal-nitrogen-carbon (TMNeC) (electro)
catalysts of generic TMN4/C structure [124]. TM atoms can be
easily anchored on graphenic carbons as single atom sites if the
carbon scaffold is N-doped. By employing a simple wet
impregnation-adsorption method using N-doped microporous
carbon as a support, a single-atom Pt catalyst was obtained with no
need for thermal annealing [125]. The single-atom catalyst with Pt
loading of up to 2.92 wt% showed high activity in the hydrogen
evolution reaction (HER). Studies of the effect of N-doping on car-
bon black samples revealed that only individual Pt atoms were
present in N-doped carbon black (Pt content of 0.4 wt% and N-
doping of 2.7 wt%) while in the absence of nitrogen doping, metal
NPs were observed at the same Pt loading [126]. Large scale syn-
thesis of SACs was proposed using a 1,10-phenanthroline ligand for
complexing various TM cations followed by adsorption of the
resulting complexes onto commercial carbon black [127]. Inter-
estingly, metal atoms can also be captured from a vapour phase and
trapped by N-doped carbons [128].
N-doped carbons derived from a zeolitic imidazolate
framework-8 (ZIF-8) are routinely used as a model material to
entrap single TM atoms. A large range of thermally and (electro)
chemically stable catalysts with single metal atomN4 sites were
produced using this approach. All TM particles (even Au) can be
transformed to thermally stable single atom sites (with the metal
atom filling the N4V2 defects) by applying thermal diffusion at the
surface of the N-doped carbon at around 900  C, Fig. 28 [129,130].
The anchoring effect of nitrogen defects was verified experimen-
tally. When metal particles loaded on N-free carbons were
annealed under the same conditions, the particles sintered into
large seeds instead of transforming into single atom sites. This
proves that N-coordination sites are indispensible to transform
metal particles into singe atoms; thermal atomization of TM par-
ticles does not occur over carbon supports without N-chelating
sites [131]. The outstanding thermochemical stability of metalN4
sites was also confirmed under a reducing atmosphere by anneal-
ing the single-atom containing carbons in a H2/Ar atmosphere at
900  C [129]. As calculated for nickel, the most stable adsorption
site is the symmetrical center of pyridinic N-dopants (the NieN4V2
vacancy, also denoted as NiN4C10) with a binding energy of 7.75 eV
(see Fig. 29) [130]. It has recently been shown that metal-nitrogen
single atom sites can also be exceptionally resistant to leaching by
electrochemical oxidation [132]. Yet the thermal stability of carbon-
based metalN4 structures is limited by the stability of the N-
doped carbon itself. While pyridinic nitrogen is one of the most
thermally stable configurations within the carbon matrix, it de-
sorbs from the carbon scaffold at temperatures above 950-1100  C
(as N2, C2N2, etc.) causing decomposition of the metalN4 sites
[133].
Another important class of metal-carbon structures are graphite
intercalation compounds (GICs). As a highly anisotropic, ampho-
teric material (the p-bonds in graphite can accept or donate elec-
trons), graphite can undergo intercalation by enabling a guest to
reside between the graphene layers. Graphite can accommodate a
whole range of inter-gallery acceptor and donor moieties via vapor/
solvent transport or electrochemical intercalation [134e138].
Considering their bonding character, GICs are divided into covalent
and partially ionic. The most popular covalent GICs are graphite
oxide and carbon fluorides, while ionic GICs include a rich family of
graphite salts (e.g. graphite-bisulphate or graphite-alkali metal
compounds). The majority of GICs belong to the class in which the
bonding between intercalate and carbon has a certain degree of
ionic character. Intercalation is usually accompanied by electron
transfer into the antibonding p*-band (in case of donor) or from the
bonding p-band (for acceptor). Acceptor species oxidize graphite
by accepting electrons from the graphitic sheets to form anions
intercalated into positively charged sheets (e.g. dihalogens, p-type
GICs), while donors reduce graphite and form cations (e.g. alkali
metals, n-type GICs). The ease of alkali metals (except for Na) and
H2SO4 to penetrate graphite layers has significant ramifications
when it comes to purification and processing of graphitic carbon
structures. For instance, K is used for chemical activation to obtain
microporous carbons, formation of LiC6 is the principal reaction in
lithium-ion batteries (LIBs) while H2SO4 is utilized to exfoliate
graphite to graphene oxide [137,138]. Interestingly, the weak
intercalation of Na into graphite could be the reason that KOH is a
more efficient activating agent to obtain microporous carbon than
NaOH.
To conclude, the ability of a transition metal to react with carbon
increases with its number of electron vacancies in d-orbitals. While
elements with no d-vacancies are inert, elements with numerous d-
vacancies can form ultra-high-temperature carbides. For instance,
the melting point of TaC or Ta4HfC5 approaches 4000  C. Elements
with a moderate number of d-vacancies are good carbon solvents.
The interaction of TMs with carbon materials usually increase from
right to left and from bottom to top of the periodic table. The
highest affinities to carbon observed for early TMs (e.g. Sc, Ti) and
middle-late TMs (e.g. Fe) are due to their propensity to lose one or
two electrons for achieving the full/half-filled steady states. These
interactions are of the utmost importance in steel production or in
catalytic processes involving transition metals and carbon

ski, S. Dyjak / Carbon 168 (2020) 748e845
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Fig. 28. Transformation of Pt and Au from nanoparticles to single atoms (on ZIF-8 derived N-doped carbon) and corresponding structural characterizations. High-resolution HAADF-
STEM images of Pt-NPs (a), PteSAs (b), Au-NPs (d) and AueSAs (e) and corresponding HAADF-STEM images at lower magnification (insets). Fourier transforms of k3-weighted Pt
and Au L3-edge EXAFS experimental data for Pt-NPs and PteSAs (c) and Au-NPs and AueSAs (f). Reprinted with permission from Ref. [129]. Copyright © 2018, Springer Nature. (A
colour version of this figure can be viewed online.)
elements. Despite the fact that FeeC mixtures have been utilized
since the Iron Age, our understanding of the structure, stability and
formation TMcarbon bulk structures is still at a premature stage
[139]. Transition metal adatoms adsorbed on the surface of perfect
graphene possess high mobility at room temperatures and this
limits their use as reliable dopants to produce stable catalysts,
sensors, etc. In contrast, substitutional doping of a metal impurity
in graphene forms very stable structures. Metal-mono- or -diva-
cancy complexes show surprisingly high thermal stability and
resistance against acid leaching and air oxidation. Once defects are
created metal atoms will find their way to the trapping center
through the extended potential around each defect [140,141]. The
strain fields around point defects such as reconstructed vacancies
reach far (up to a few nm) into the unperturbed hexagonal network
and mobile metal atoms are attracted by the defects. The recon-
structed defects (without dangling bonds) increase the local reac-
tivity of the graphene surface and can trap TM adatoms by forming
bonds with energies of about 2 eV [140]. This moderate bonding
energy allows release of the trapped atom at higher temperatures.
Substitutional doping of metal atoms in the graphene layer
(replacement of carbon atoms in the hexagonal lattice) is on the
other hand more difficult since metal atoms can only be incorpo-
rated into the graphene lattice when filling already existing va-
cancies before their reconstruction or saturation by oxygen or other
non-metallic heteroatoms. Indeed, the strong covalent CeC bonds
within the hexagonal carbon lattice and their ability to reconstruct
defective sites (saturating dangling bonds by creating non-
hexagonal rings) make substitutional doping of sp2-hybridized
carbon difficult. Yet it is a double-edged sword. Once a TM atom is
trapped at a substitutional defect site (TM@vacancy complex) it
remains permanently bonded and it is resistant to removal by
common purification techniques. Studies on SAC materials based
on carbonaceous supports (especially on N-doped ones) showed
that multiple acid leaching and annealing do not allow total
removal of TMs. In fact, highly active SACs with TM loading as low
769
as 0.01 wt% are being reported, which means that impurities at
ppm level dominate the catalytic properties of carbon-based ma-
terials. Finally, it is important to note that most of the results
concerning CNMTM interactions rely on DFT calculations. In re-
ality, it is not the direct carbonmetal interaction but the chemi-
sorption of metals (or metal oxides, hydroxides, etc.) onto
functional groups that could be the dominant mechanism of metal
bonding to carbon matrixes. This is because all the defective sites in
graphenic carbon materials are readily saturated by oxygen,
hydrogen or nitrogen atoms once in contact with the external
environment (air, water, etc.), which yields a profusion of surface
functional groups.
4. Analytical techniques for quantification and qualification
of TM impurities in carbon matrices
Before any experiments concerning properties of advanced
carbon-based materials are undertaken, the quantitative and
qualitative composition of the material must be determined
comprehensively to get to know what we are really dealing with.
Careful monitoring of purification efficiency and its impact on the
carbon material’s structure is also required to select methods,
which could completely remove metallic impurities while leaving
the carbon matrices intact. Quantitative and qualitative character-
ization of metallic impurities in graphenic carbon-based materials
constitute an unusual analytical challenge. Not only are carbon-
based materials extremely diverse, but transition metals can also
occur within them in diverse forms and structures (including pure
metals, alloys including refractory and insoluble non-
stoichiometric compounds, inorganic and organic ionic com-
pounds, organic complexes or as single-atom sites). They may be
present as major constituents or only as ultra-traces; metal nano-
particles may be loosely coordinated to the carbon surface or firmly
incorporated between layered structure, encapsulated in graphitic
tight shells or in strong covalent bonds with the sp2 carbon lattice.
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Fig. 29. Representative movie TEM images acquired at 25e800  C (aef) of Ni NPs@NC
(nickel particles on the N-doped carbon surface) pyrolyzed in situ. g) The adsorption
energies of Ni adatom and Ni dimer vertical of pyrrolic N, pyridinic N, quaternary N,
and graphene. All values are in eV per Ni atom. (C gray, Ni blue, and N red). Reprinted
with permission from Ref. [130]. Copyright © 2018 Wiley-VCH Verlag GmbH & Co.
KGaA, Weinheim.
While the range of available techniques for a solid-state material
purity assessment is large (atomic spectroscopy, X-ray spectros-
copy, microscopy, magnetometry, gravimetry, nuclear techniques,
etc.) a reliable and precise techniques must be deliberately selected
depending of the required level of precision and the nature/pro-
posed application of the studied carbon-based material. If one
studies the intrinsic magnetic properties of carbon, then the most
sensitive techniques are compulsory to detect ultra-trace level of
metals (ppb). On the other hand, if carbon materials are to be used
as fillers in reinforced polymer (nano)composites, ultra-trace levels
of metallic impurities are less relevant (e.g. as in the case of carbon
fibers). As the carbon matrix and metallic impurities are of a
complex nature, a range of complementary methods must often be
used in order to fully determine not only the quantity but also the
structure and form of the residual metals. This information in turn
helps to further optimize the purification processes.
While the inherent properties of sp2-hybridized carbons such as
extreme corrosion resistance, lack of solubility in almost any sol-
vent and refractory character, make them useful for sophisticated
applications, they also make them challenging materials for purity
analysis. Traditionally, the common methods utilized for purity
assessment of carbonaceous materials include thermogravimetric
analysis (TGA), Raman spectroscopy (invalid for metal particles),
scanning or transmission electron microscopy/energy dispersive X-
ray spectrometry (SEM/EDS, TEM/EDS), electron energy loss spec-
troscopy (EELS), X-ray photoelectron spectroscopy (XPS), and X-ray
fluorescence (XRF) [142]. Even X-ray diffraction (XRD) is sometimes
misinterpreted as a method for evaluation of carbon-based mate-
rial purity. Nevertheless, all these methods have serious limitations.
Sensitivity and selectivity of these popular techniques range from
trace element contents to wt% in the tens. TGA can only determine
the content of non-combustible/non-volatile components and its
actual sensitivity is often limited to 0.1 wt%, hence it is only a
semi-quantitative technique. The advantage of surface-sensitive
XPS and EDS techniques is the number of elements they can
detect (almost all elements, except H and He - for XPS, and ele-
ments between atomic numbers of 4 and 92 for EDS). The disad-
vantage of using these surface sensitive techniques for the analysis
of a heterogeneous carbon powder sample originates from their
high spatial resolution. XPS or EDS are not sensitive enough to
detect trace levels of metal impurities, especially when these are
intercalated deep into the carbonaceous structure. In such in-
stances, XPS/EDS significantly underestimate the real content of
metallic impurities. XPS sensitivity quickly decreases with the
depth of the investigated element where the maximum depth de-
pends on the atomic mass of an element. XRF is somewhat more
useful as it is a direct, multielemental analysis technique with high
sensitivity down to low ppm level, but it has limitations for quan-
titative determination. For instance, when it comes to the level of
impurities that can interfere with the intrinsic magnetic properties
of carbon materials, XRF is not sensitive enough. Generally, XRF
spectrometry (including wavelength dispersive (WDXRF), energy
dispersive (EDXRF) and total reflection (TXRF) X-ray fluorescence)
is a convenient technique for analysis of materials at major, minor
and trace levels of elements (from wt% to ppm levels) in a variety of
matrixes, however expensive reference materials are required.
TEM/EDS is a truly powerful nanoscale analytical method which is
indispensable when one needs to determine the composition of an
individual metallic nanoparticle. In such cases, TEM/EDS offers a
detection limit of about 1 wt% and it is useful to detect fractions of
metallic impurities present within larger metallic nanoparticles.
However, as with all microscopic approaches, it is not a bulk
analytical technique and cannot deliver a representative composi-
tion of impurities. In brief, one must consider that microscopic
methods are too localized, XPS, EDS and at some cases even XRF are
surface-limited, while Raman spectroscopy and gravimetric
methods do not provide an accurate quantitative analysis of trace
metal elements. However, these methods are ubiquitous since they
allow direct analysis of solid-state carbon without any pre-
treatment (leaching or decomposition of samples) and are easily
accessible in numerous laboratories worldwide. A comparative
study of five techniques including EDS, XPS, TGA and less common
magnetic techniques (direct current magnetic susceptibility and
electron paramagnetic resonance (EPR, also referred to as electron
spin resonance), for quality control of CNTs in terms of metallic
impurities revealed that the most sensitive methods for detection
of trace amount of metals are those based on measurements of the
magnetic effects [143]. While magnetic susceptibility allowed
detection of metal impurities embedded in MWCNT at concentra-
tions as low as 3 ppm, other methods (XPS, EDS, and TGA) provided
false negatives. However, these conclusions were later challenged
by showing that in particular cases even higher detection sensi-
tivity is required. Extended X-ray absorption fine structure (EXAFS)
is an advanced version of X-ray absorption spectroscopy (XAS) - a
surface spectroscopy with detection ability down to ppt, which
allows characterization of the coordination environment of an
element. EXAFS has been utilized for detection and phase identi-
fication of trace magnetic impurities in SWCNTs purified by
annealing at 2200  C under a dynamic vacuum [144]. While other

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin 771

Fig. 30. ICP-OES (AES) and ICP-MS detection limit guidance (to be used as a guide, not absolute information). These detection limits are theoretical best case scenarios assuming
there are no spectral interferences affecting the best isotope or wavelength for a given element. For any given determination, the actual method detection limit can be an order of
magnitude higher or more. Courtesy of EAG Laboratories | A Eurofins Company | © 2017 Eurofins Scientific. (A colour version of this figure can be viewed online.)

sensitive methods (including direct current magnetization and themselves rather than just electromagnetic radiation (photons).
alternating current susceptibility measurements) suggested a The higher sensitivity of ICP-MS allows detection limits in the ppt
complete absence of magnetic impurities, EXAFS confirmed the ranges [146]. However, the operating costs of an ICP-MS system are
presence of residual iron in the form of iron oxides. Consequently, it usually greater than those of an ICP-AES system since special con-
was proved that the apparently pure and diamagnetic samples may ditions must be established to test in the ppt range and expensive,
still contain a tiny amount of magnetic phases undetectable by high purity grade reagents must be utilized. The ICP-AES technique
techniques commonly considered as highly sensitive [144]. To ul- is also somewhat easier to conduct than ICP-MS. Of all three
timately exclude the presence of any metallic/magnetic impurities, elemental analysis techniques (ICP-AES, ICP-MS and AAS), ICP-MS
highly sensitive local probes such as EXAFS must be applied. is able to detect the largest number of elements (>80) with the
Analyses by atomic and mass spectroscopies such as inductively highest detection limit (Fig. 30). High sensitivity, accuracy and
coupled plasma (ICP) burner-assisted techniques including atomic
(optical) emission spectrometry (ICP-AES (-OES)), atomic absorp-
tion spectroscopy (AAS) or mass spectrometry (ICP-MS), yield
precise information on concentration and type of elements down to
ppb (mg/L) or even ppt (ng/L) levels (depending on the technique
and analytical procedure), Figs. 30 and 31. Note that ICP-AES and
ICP-OES represent the same analytical method and the names are
used interchangeably. ICP-MS or ICP-AES techniques are suitable
for the detection of more than 70 elements. They are commonplace
in public and commercial laboratories globally and hence they are
easily accessible. The ability to simultaneously measure multiple
elements is a major advantage of AES over AAS. Unlike ICP-based
techniques, AAS is basically a single-element method, hence AAS
is less universal. ICP-MS is one of the most practical techniques
applied for coincident multi-element measurements of trace im-
purities in carbon-based structures such as graphene, graphite,
carbon nanotubes, activated carbons or coals. In fact, Pumera, who
is one of the leading debunkers of reports on “metal-free” carbon
catalysts, recommends using ICP-MS/ICP-AES as indispensable
tools for researchers to check for incidental metal impurities [145]. Fig. 31. Typical detection limit ranges for the major atomic spectroscopy techniques
One of the advantages of ICP-MS over ICP-AES is its higher detec- (ICP-OES with radial and axial torch configurations). Courtesy of PerkinElmer,
tion power. ICP-MS provides the ability to detect the ions ©2010e2020 PerkinElmer, Inc. All rights reserved. Printed with permission. (A colour
version of this figure can be viewed online.)
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ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
compound-independent element response ensure the leading po-
sition of ICP-MS in detecting, identifying and quantifying trace el-
ements. ICP-MS limitations include high Si and P detection limits,
the inability to analyze C, H, N, O, S and most of the radioactive
elements, and problems in assessing elements that form negative
ions (e.g. halides).
However even these well-established methods have serious
limitations when it comes to carbon-based material analysis. A
multi-elemental analysis covering a wide range of atomic masses
and levels of occurrence is already very challenging. While ICP-
based techniques offer pg/mlesubpg/ml (ppt-subppt) detection
limits for the majority of elements, the most serious disadvantage
of such methods is sample preparation necessitating sophisticated
pre-treatments of the carbon/metal composites. From the sample
preparation standpoint, analytical techniques are divided into
destructive and nondestructive. Destructive analytical techniques
include wet digestions and combustion while non-destructive
techniques refer to those that require minor to no sample prepa-
ration. However, non-destructive techniques are often difficult to
calibrate as they are very matrix-sensitive. ICP-MS or ICP-AES
methods are critically dependent on sample preparation proced-
ures hence sample preparation is the crucial step in the whole
process of trace element analysis. Most analyses via ICP-based
methods are carried out on solutions using a conventional pneu-
matic nebulizer and hence thorough digestion of the solid sample
into a solution is required. Carbon matrices (graphite, carbon fibers,
CNTs, coals, chars, etc.) constitute refractory samples which are
extremely difficult to leach since residual metals are often tightly
entrapped or encapsulated between the graphene layers. For
organic, biological or environmental specimens, preparation pro-
cedures are well-established, but preparation of carbon-based
samples is complex. Complete digestion of the carbonaceous
sample prior to analysis is imperative to generate reliable quanti-
tative data (unless laser ablation is used). Consequently, the metal
impurity content determined by ICP-based methods is dependent
on the pre-treatment of the carbon sample. Moreover, the homo-
geneity of carbon samples is also an essential issue in ICP-MS/AES
measurements. Carbon-based materials are often highly hetero-
geneous and hence small, poorly representative samples may cause
serious errors. While some carbon materials are characterized by
very low content of impurities (e.g. carbon blacks), others exhibit
high contents of certain transition metals (e.g. SWCNTs). To validate
the results obtained via wet digestion procedures, standards of
carbons (nano)materials (e.g. CNTs, CNFs or carbon blacks) are
required. This is a challenge in the case of CNTs as no single metric
defines nanotube purity.
CNT products usually constitute heterogeneous multi-
component powders. A definition of CNT purity is a bit of a
deceptive concept as it refers to a bulk mixture of diverse nano-
tubes which are not identical. In fact, no one has ever found two
CNTs that are exactly alike [147]. As a result, the purity of CNTs is
often referred to as content of carbon phase vs non-carbon phases
and not to the actual content of a particular type of nanotubes. The
challenge of obtaining carbon (nano)material references with
certified metal content must still be overcome. Three reference
materials have recently been released by the National Institute of
Standards & Technology (NIST, USA) and the National Research
Council (NRC, Canada) for single-wall carbon nanotubes. The ref-
erences are: (i) NIST standard reference material 2483 SWCNT soot
(SWCNT raw soot produced via the CoMoCAT process), (ii) NIST
RM8281 SWCNT (dispersed, three length-resolved populations)
and (iii) NRC SWCNT-1 certified reference material [148e151]. For
MWCNTs only representative test materials (JRC multiwall carbon
nanotube representative test materials) are available. The two
standard reference materials (SRMs) for SWCNTs available with
certified metal concentrations are: NIST 2483 SWCNT, and NRC
SWCNT-1 (please see Table S4 of Ref. [150] for more details). It has
recently been realized that a crisis is indeed growing in the field of
easily available, yet sufficiently sensitive and selective analytical
techniques to determine metallic impurities within carbon-based
materials [152]. Obviously there are methods of high sensitivity
and selectivity for a range of elements allowing direct analysis of
solid samples, e.g. ion-beam analyses (IBA, including Rutherford
backscattering spectrometry, elastic backscattering spectrometry,
proton elastic scattering analysis, particle induced gamma-ray
spectrometry, particle induced X-ray emission (PIXE) spectros-
copy) and neutron activation analysis (NAA) [153]. IBAs constitute
near-surface techniques which utilize megaelectron-volts ion
beams to probe the composition of solids. Solid-state nuclear
magnetic resonance (SS-NMR), terahertz spectroscopy, magnetic
susceptibility and EPR are also very sensitive techniques for
detecting trace levels of magnetic impurities. Nevertheless, all
these approaches require very sophisticated equipment and unique
training, and therefore remain out of reach for routine day-to-day
analysis. Vejpravova et al. recently presented a comprehensive re-
view concerning techniques for the determination of magnetic
impurities in SWCNTs, which in fact can be applied to all carbon-
based structures [154].
While the complete digestion of graphite, CNTs, graphene
nanoplatelets or coals is difficult, impressive progress has been
made in this area over the last 20 years. A number of effective
digestion methods (involving open or closed systems) of carbon
materials have been proposed making ICP-MS/ICP-AES the primary
techniques to quantify/qualify metallic impurities in carbon-based
structures. The digestion methods include: acid digestion, dry
ashing coupled with acid digestion and extraction [155], Carius
tube digestion (closed-system procedure) [156], microwave-
assisted acid digestion [157,158], microwave-assisted fusion (alka-
line oxidation) [152,159], microwave-induced combustion (MIC)
[160e165] and water extraction [157]. Wet digestion processes may
be performed in an open or closed system. To minimize drawbacks
arising from using open systems (e.g. incomplete digestion and/or
escape of volatile elements) closed vessel combustion systems have
been proposed (for instance the MIC approach). In addition, alka-
line oxidation (so-called fusion) can be applied as an alternative to
disintegrate samples of materials that are extremely resistant to
aggressive acids such as refractory carbides or mineral ores [159].
Advanced digestion methods allow reduction of interference
caused by carbon residues in the sample solution [160]. A paper by
Ge et al. where four pre-treatment methods for assessment of
metal impurities in SWCNTs and MWCNTs by ICP-MS technique
were compared is often considered a point of reference in this field
[155]. The studied pre-treatment methods included: dry ashing
coupled with acid extraction, wet digestion, a combination of dry
ashing and wet digestion, and microwave-assisted digestion. They
used the NAA technique as a quantification method of the actual
metal-impurity content because at that time there were no stan-
dard CNT materials for which the quantity/quality of metallic im-
purities were known. They noted that dry ashing coupled with acid
extraction formed complex metal oxides (i.e. refractories which are
very difficult to dissolve). Thermal pre-treatments of carbonaceous
materials may result in the formation of difficult to dissolve phases
(including carbon compounds such as carbides). On the other hand,
microwave-assisted acid digestion assured complete leaching of
SWCNTs and yielded results in agreement with data derived from
NAA. However, the procedure proposed by Ge et al. involving the
combination of two digestion procedures (dry ashing and wet
digestion) and a further acid evaporation step is now considered
impractical for routine analyses [155]. Microwave-induced com-
bustion combined with ICP-AES and TXRF was also utilized to

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
determine Fe, Cr, Mn and Ni impurities in graphene samples [161].
The experimental results were compared with those from other
pre-treatment methods including dry ashing/acid digestion and
microwave assisted digestion and showed that the MIC pre-
treatment procedure is superior. The advantages of MIC in closed
vessels include the possibility of digestion of high amounts of
sample up to 500e1000 mg using diluted solutions, low generation
of effluents and lower risks of analyte contamination. Flores et al.
published a range of papers concerning digestion techniques for
the determination of trace metal contents in carbon materials using
ICP-MS/AES techniques [162e164,166]. For instance, they studied
three carbon matrix destruction procedures: conventional multi-
step microwave-assisted acid digestion, dry ashing at 450  C and
microwave-induced combustion in an oxygen pressurized quartz
vessel for the determination of metallic impurities (Ni, Mo, Fe, Pb,
Co, Cr and Hg) in SWCNT samples [166]. They compared the results
obtained from ICP-MS with NAA and solid sampling graphite
furnace atomic absorption with a continuum source (SS-CS-GF-
AAS), using SWCNT-1 (NRC, Canada) as a standard reference ma-
terial. The ICP-MS results agreed with the certified values; however,
multi-step microwave-assisted digestion was required for complete
metal leaching. Incomplete leaching of the residues occurred using
the single step MIC procedure due to the high content of Ni and Co
and the poor solubility of their oxides during the reflux step. They
also noticed that Mo and Cr are difficult to recover as they may
occur as refractory carbides. However, most importantly, they
pointed out that the quality of various CNT samples is highly vari-
able and hence the recommendation of a single universal pre-
treatment procedure for carbons of different natures is nearly
impossible [166]. Since there is no such material like “the SWCNT”
or “the graphene oxide”, and carbon (nano)materials differ from
batch to batch, it is difficult to compare results presented by
different analytical laboratories. Consequently, there is an urgent
need for a standard inter-laboratory approach for carbon nano-
material sample preparation procedures to yield reproducible and
comparable results, not only for ICP-MS/AES techniques but for all
commonly-utilized characterization methods. In trying to meet this
need, Decker et al. proposed descriptions of sample preparation
protocols including pre-treatment for general physicochemical
characterization of SWCNTs [158]. Methods of these protocols
included scanning and transmission electron microscopy, atomic
force microscopy, ICP-MS, NAA, Raman, photoluminescence and
UV-VIS-NIR absorption spectroscopies, manometric isothermal gas
adsorption and thermogravimetric analysis. Another interesting
proposal for a routine laboratory procedure for an elemental
analysis of SWCNT soot using widely-available bulk analytical
methods to monitor batch-to-batch variability and to minimize
sample size requirements to <100 mg was presented by Braun and
Pantano [167]. A combination of CHNS/O combustion analysis, ox-
ygen flask combustion/anion chromatography (Scho € niger flask
technique), graphite furnace-atomic absorption spectroscopy (GF-
AAS), and ICP-MS was used to generate a 77-element analysis of
two commercial SWCNT soot products (CoMoCAT, SouthWest
NanoTechnologies Inc). It was shown that the combination of
CHNS/O and ICP-MS for the analysis of SWCNT soot constitutes a
powerful tool to study the purity and composition of carbonaceous
materials. It was also demonstrated that the surface-sensitive XPS
analysis did not detect sixteen of the nineteen major elements in
the SWCNT sample detected by the combined bulk analysis
methods [167].
Lim et al. studied conventional microwave acid digestion and
microwave oxygen combustion using three SRMs of carbon sam-
ples (coal standard reference 1632d (trace elements in bituminous
coal), 2483 SWCNT soot, and SWCNT-1) for the quantification of
metal impurities (i.e. Cr, Mn, Fe, Co, Ni, Cu, Zn, As, La, Ce, Sm, Eu, Gd,
773
Dy, and Pb) in CNTs by ICP-MS [168]. They also provided a
comparative list of recently reported digestion methods for CNTs
showing that the microwave assisted digestion techniques are
generally more efficient and hence more often used than others (i.e.
dry ashing with acid extraction) [168]. There are many modifica-
tions of microwave-assisted digestion procedures including
microwave-assisted fusion [152,159] based on exposure of carbon
materials to alkaline oxidation (e.g. to carbonate melt (Na2CO3/
K2CO3) at 1000  C). Improvements of microwave-assisted acid
digestion to obtain transparent solutions of CNTs have been
recently proposed [169]. A microwave-induced combustion pro-
cedure is also a good option for acid-resistant samples like coals
[170,171] or graphite [172e174], where the utilization of concen-
trated acids and high temperature/pressure still results in incom-
plete sample decomposition and dissolution. MIC was proposed for
the decomposition of graphite samples and final digests were
successfully analyzed by ICP-MS/AES for the simultaneous deter-
mination of seventeen elemental impurities (Ba, Ca, Cd, Co, Cr, Cu,
Fe, K, Li, Mg, Mn, Mo, Na, Ni, Sr, V and Zn) [164]. This same approach
was evaluated for the digestion of high purity nuclear flexible
graphite (which exhibits enhanced resilience, impermeability to
fluids and chemical inertness in comparison to raw graphite ma-
terials) for determination of embrittling elements (Ag, As, Bi, Cd, Ga,
Hg, In, Pb, Sb, Sn and Zn) [165]. Microwave-induced combustion
was also successfully applied for coal digestion for subsequent
determination of As, Cd, Pb and Hg (a volatile element) content
using cold vapor generation coupled with ICP-MS [163]. Assess-
ment of metal impurities in coals is especially important since el-
ements such as Cr or Fe cause severe corrosion inside combustion
boilers and reduce their lifespan [175]. Analysis of coal impurities is
also essential because coal is commonly used to produce a range of
more advanced carbonaceous materials (i.e. activated carbons). As
heterogeneous materials of natural origin, coals contain most ele-
ments of the periodic table [176]. Al, Ca, K, Mg, Na, Si and Fe are
especially abundant in coals. Laser ablation-inductively coupled
plasma-mass spectrometry (LA-ICP-MS) is a rather common tech-
nique utilized for direct coal sample analysis [175]. Another natural
fuel often used for advanced carbon material synthesis is pitch from
crude oils. Consequently, procedures for its purity assessment have
also been pursued [177].
The complexity of batch-scale elemental quantification of car-
bon (nano)materials has turned neutron activation analysis into the
“gold standard” of analytical methods dealing with solid-state
carbon samples [151]. NAA does not require the use of standards
and covers a broad range of elements and concentrations; it can
detect more than 70 elements [178]. NAA relies on conversion of
nonradioactive elements to radioactive ones by neutron
bombardment, and then the elements of interest are determined
from their induced radioactivity. It is one of the most sensitive,
direct analytical techniques for multielement determination; the
analysis is blank free and since it relies on nuclear instead of
chemical reactions, the results do not depend on the chemical state
of an element. The neutrons interact with the nucleus of the
investigated element independently of the oxidation state and the
physical surroundings. Samples can be analyzed without dissolu-
tion/decomposition, eliminating measurement errors due to
incomplete dissolution or loss of volatile species. Unlike other
multielement analytical techniques, NAA does not require any
special sample pretreatment/preparation. In fact, because of the
high accuracy, good precision, and no matrix blank requirement,
NAA is commonly used in the certification process of reference
materials. Analysis of samples by NAA provides quality assurance
when SRMs are not available. Results obtained by ICP-MS/AES
methods are often benchmarked against those derived from
neutron activation analysis. Instrumental neutron activation
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W. Kicin
analysis (INAA) and IBA were recently proven to be very useful
techniques for the characterization of a variety of carbon allotropes
either with very low (acetylene carbon black) as well as high
(SWCNTs) content of transition metals [153]. Six commercial car-
bon materials representing various carbon allotropes (acetylene
carbon black, expandable graphite (purified and non-purified),
reduced graphene oxide, and two specimens of SWCNTs) were
tested for mass fractions of more than 40 elements using INAA and
IBA. In the case of SWCNTs, besides the expected high content of Co
and Mo (growth catalysts), at least 10 additional elements were
determined (for instance Cl, Cr, As, Br, I, Na, Al, Ca, W, Mn) [153]. A
significant batch-to-batch variability of elemental impurities was
also found for commercial SWCNT sooths. These results show that
with few exceptions, carbon materials are rich in heteroatoms and
hence analytical control is of the utmost importance in applications
where chemical purity determines the fundamental properties of
carbon-based materials. INAA is often accompanied by prompt
gamma-ray activation analysis (PGAA). PGAA is an important nu-
clear analytical technique that complements INAA as it allows
quantification of the light elements (H, B, C, N, Si, P, S) that cannot
be determined by INAA. The sequential use of PGAA and INAA can
determine more than 50 elements in a single sample test
[179e181]. Nuclear-based techniques including NAA and charged
particle activation analysis (CPAA) have also been used to evaluate
the quality of nuclear grade graphite [182]. CPAA is useful for
analysis of the light elements which are inaccessible to NAA, but it
is especially effective in the detection of medium-heavy trace ele-
ments. CPAA can be used as a routine method for multi-elemental
determination of trace elements as an alternative to the INAA
method in case of non-availability of a neutron source.
Analysis of spent nuclear graphite is an urgent issue to address
as the radiological characteristic of irradiated graphite is crucial for
the choice of its final treatment technology (geological disposal,
landfill storage or recycling) [183]. The concentration of radioactive
contaminants in spent graphite must be identified before disposal.
For instance, samples of graphite from a nuclear power plant
reactor from different construction elements (stack, sleeve, and
bushing) were analyzed by INAA, PGAA and ICP-MS [183]. A com-
parison of the obtained results allowed validation of the less sen-
sitive, but more affordable ICP-MS technique, which does not
require a thermal neutron source for analysis. Indeed, as good as it
is, NAA requires a large nuclear reactor facility for irradiating
samples, which results in its low availability and high cost. While
NAA is the best method to study metallic impurities in solid carbon
materials, analytical laboratories usually use other more accessible
techniques. In fact, ICP-MS/AES techniques are the most common
methods for bulk quantitative elemental analysis of carbon-based
materials worldwide [151]. Also, when it comes to measuring
ultra-trace levels of metallic impurities, INAA lacks imaging capa-
bilities and the analysis time can take days for sufficient sensitivity.
Particle induced X-ray emission is an ion-beam spectroscopy (using
MeV protons for excitation) which allows an accurate measure-
ment of impurity concentrations in the sub-ppm range and imaging
of the distribution of impurities. Protons can penetrate deep into
the carbon material (50 mm) making PIXE a truly bulk-sensitive
technique. Commercially available HOPG from Momentive Perfor-
mance Materials, NT-MDT Spectrum Instruments and SPI Supplies
with three available structural grades designated as ZYA, ZYB and
ZYH were studied using PIXE [184]. The HOPG samples contained
Fe in the range of <0.23 mg/g up to 22.6 mg/g. Most of the samples
also contained Ti and V. The metallic impurities in the HOPG were
not distributed homogeneously within the sample but localized in
micrometer large grains (2e30 mm). The grains constituted flat
disks oriented parallel to the graphene planes. This shape was
caused by the high temperature (>2000  C) and pressure used in
the production of HOPG from pyrocarbons. The metallic phase in
the pyrocarbon melt spread out perpendicular to the c-axis of the
HOPG formed. Fe was present in the grains as cementite (Fe3C).
Direct solid sampling presents several advantages, such as
considerably shorter sample preparation time, higher sensitivity
owing to the absence of dilution, and reduced risk of contamination
or loss of analytes. As mentioned above, direct analysis of insoluble
carbon materials can be performed by a whole range of methods
(including NAA or XRF). However, if techniques such as NAA are
inaccessible there are still a number of little known yet cheap and
highly reliable methods for direct analysis of solid materials. While
ICP-based techniques require sample digestion, direct analysis of
solid carbon samples is an attractive alternative, which allows cir-
cumventing the problematic dissolution of refractory materials
[185]. Non-digestion sampling techniques which are often used in
combination with ICP-MS/AES quantification measurements
include electro-thermal-vaporization (ETV), laser-ablation (LA),
slurry nebulization (SN), or GF-AAS [185,186]. For instance, SN with
ICP-AES, solid sampling electrothermal vaporization-inductively
coupled mass spectrometry (ETV-ICP-MS) and ultrasonic slurry
sampling electrothermal vaporization inductively coupled plasma
mass spectrometry (USS-ETV-ICP-MS, which has the advantages of
multi-elemental capability and better detection power over the GF-
AAS method) were applied to study Fe content in MWCNTs [187],
rare earth elements in graphite [188] and Cd, Sb, Te, Hg, Tl and Pb in
medicinal activated charcoal capsules [189]. The study of heavy
metal content in medicinal activated charcoal capsules is especially
interesting as it shows that in certain applications the content of
transition metals must be rigorously monitored. Solid sampling
methods using ICP-MS with laser ablation have been proposed as a
convenient choice for analysis of metal and non-metallic contam-
inants in coals as well as of trace impurities in graphite powder and
activated charcoal [190]. Currently, ETV-ICP/AES is one of the
dominant methods for direct solid sampling of graphite powders.
However, a magnetically stabilized direct current arc AES was
recently proposed as a better alternative to ETV-ICP/AES for direct
solid sampling analysis of graphite powder [191]. In this approach,
halogenating gases (CCl2F2, SF6 or NF3) were used as chemical
modifiers that allow an effective release of the carbide-forming
trace elements. Halogenating modifiers (gaseous or solid, e.g.
CCl4, CaF2, AgCl or CsF) have been used to attain fast vaporization of
trace elements from refractory compounds such as B4C or SiC [192].
This is of high importance for accurate estimation of trace metal
content as some carbon-based refractories are thermally and
chemically resistant.
While there is indeed a variety of techniques that can provide
quantitative information directly from solid samples, the applica-
bility of these techniques can be limited by insufficient sensitivity.
An interesting technique to consider in such instances is the solid
sampling graphite furnace atomic absorption spectrometry (SS-GF-
AAS) which enables direct analysis of complex materials of various
natures (conducting or non-conducting samples) with no sample
preparation required [193]. As a young technique, SS-GF-AAS is not
yet well established in the field of Analytical Chemistry. During the
last 15 years the appearance of high-resolution continuum source
atomic absorption spectrometry (HR-CS-AAS) instrumentation has
brought new opportunities to this field. The use of a continuum
source device to perform AAS was commercialized in 2003 and HR-
CS-GF-AAS instrumentation became commercially available only in
2008 [193]. Even though it is a young analytical technique it may
merit further attention as this approach is suitable for samples that
are difficult to digest (e.g., graphite, chars, or glass-like carbon)
[194]. HR-CS-GF-AAS constitutes a faster alternative to conven-
tional time-consuming digestion and permits accurate values, even
if no appropriate standards are available for calibration, as required

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
for most of the other solid sampling techniques (i.e. using aqueous
standard solutions only is already sufficient in HR-CS-GF-AAS).
Despite the different concentrations and different thermal prop-
erties of metallic elements in the variant carbon materials, a fast
and simple methodology for the direct and simultaneous deter-
mination of TM impurities can be reached by means of HR-CS-GF-
AAS (or more generally by GF-AAS) [195e197]. Solid sampling
graphite furnace atomic absorption spectrometry has been suc-
cessfully applied for the determination of trace elements in acti-
vated charcoal, carbon black [195] and graphite samples [196].
Magnetic analysis (MAG; for instance, direct current magneti-
zation, alternating current susceptibility) of metallic impurities in
carbon-based materials has recently been reviewed by Vejpravova
et al. [154]. While MAG is less common, it is a truly powerful set of
techniques to study metallic impurities within carbonaceous
matrices [198,199]. Where other techniques may suggest that a
carbon material is metal-free, magnetometry can prove such
statement to be incorrect since the sensitivity of the standard
routes utilized for characterization of bulk material purity is often
insufficient [143,198]. Magnetization measurements allow deter-
mination of the exact state of the metallic impurities, and hence
monitoring of the chemical mechanisms of purification processes.
Determination of the distribution of magnetic moments (obtained
from measurements of magnetization isotherms) enables proper
interpretation of the efficiency and mechanism of an applied pu-
rification procedure. This distribution shows directly which fraction
of the metallic nanoparticles has been removed [200]. Vigolo et al.
studied the Ni catalyst content in arc-discharge SWCNTs purified by
two techniques, a Cl2 treatment at 800e1100  C and a standard
method including air oxidation at 350  C followed by HCl reflux and
an annealing under vacuum at 1100  C using MAG techniques [201].
Thanks to magnetic analysis, they proved that a particular purifi-
cation process can significantly alter the chemical state of a metallic
impurity. Cl2 purification preserves the structural quality of
SWCNTs and assures low Ni content. However, no effect of chlori-
nation temperature on nickel removal efficiency was observed.
Even though a higher chlorination temperature decreases the
metallic Ni0 content, it does not improve the overall purification
yield since Ni2þ remains trapped in the carbon samples as NiCl2.
This result does not resonate with results obtained for HiPco (high-
pressure carbon monoxide) SWCNTs, for which Cl2-based purifi-
cation yield improved with higher temperatures [202]. HCl acid
leaching does not attack the largest metal particles, whereas they
are easily removed by the Cl2 treatment. This selective reactivity
revealed a chemical differentiation of the metallic particles
depending on their size. This is because Ni particles are protected
either by carbon or NiO shells. HCl treatment preferentially attacks
NiO and carbon shells-free Ni particles, while chlorine preferen-
tially removes the particles inside the carbon shells whereas the
reaction with NiO is less favorable. As a result, both treatments are
complementary and should be combined to reach a better quanti-
tative purification efficiency. Chlorination was found to be more
efficient in terms of Ni-impurity content, yet this treatment leaves
some NiCl2 species which may be intercalated into graphitic carbon
forming an ordered magnetic phase.
Obviously, there is a range of other useful techniques for analysis
of transition metals/carbon systems. For instance, Mo €ssbauer
spectroscopy (e.g. transmission 57Fe Mo €ssbauer spectroscopy
(TMS)) has been utilized to study different forms of iron com-
pounds embedded in CNTs [203]. TMS allows study of the structure
of FexCy compounds within carbon matrices and differentiation
between iron carbides and iron oxides. This is of special importance
as cementite and iron oxides are the dominant forms of Fe-
impurities in carbon materials. TMS can be applied to monitor
the purification process of carbon materials by studying the
775
changes of iron phase state. TMS is also irreplaceable in studies
concerning the so-called pyrolyzed iron-nitrogen-carbon (FeeNeC
or FeN4/C) catalysts supported on porous carbonaceous scaffolds
[204]. Yet this example shows again that a specific technique must
be carefully and deliberately selected depending on what infor-
mation concerning metal impurities is required. The NMR tech-
nique is one of the most important characterization tools in organic
and analytical chemistry. SS NMR provides atomic-level charac-
terization, but it is difficult to apply for carbon materials that
contain magnetic impurities. As pointed out, measurements of the
13
C NMR spectra of carbon nanostructures are hindered due to
ferromagnetic and paramagnetic impurities [205e208]. Such im-
purities generate a very large broadening of the NMR signals pro-
ducing spectra which are difficult to deconvolute. Similarly,
application of electron spin resonance techniques is limited for
carbon samples containing catalyst residues [209].
Many researchers have limited access even to very common
analytical tools like ICP-MS/ICP-AES, not to mention advanced
techniques such as INAA. For this reason, easier yet precise methods
to quantify metallic impurities in carbonaceous materials are being
proposed, like for instance the colorimetric method to measure Fe
concentrations in CNTs by UVeVIS spectroscopy [210]. However,
this rather unconventional approach also requires reflux of CNTs in
a variety of oxidative acid mixtures (HClO4/HNO3 or H2SO4/HNO3)
for maximal Fe leaching. Another approach utilizing the optical
properties of CNTs to study their purity was proposed by Pingitore
et al. [211,212]. Their studies of cathodoluminescence spectra of
single- and MWCNTs bundles showed several common peaks
which disappeared after high-temperature annealing in a vacuum
[211]. As the authors elucidated, these transitions (i.e. the peaks
observed in the spectra) are extrinsic to nanotubes and originate
from TM oxide impurities. In follow-up studies, luminescence sig-
nals in the visible region of CNT bundles (with purity >95%) were
attributed to Zn and Al oxides. Annealing at 1200  C quenched the
luminescence due to the reduction of the metal oxides [212]. The
intrinsic luminescence emitted by CNTs is located in the infrared
region, and hence the origins of these visible transition lines were
extrinsic to the CNT structure. The authors propose the cathode-
luminescence analysis technique as a tool for qualitative and
quantitative analysis of impurities in CNT samples. This kind of
spectroscopy is able to detect the presence of impurities at a level of
ppm, which is equivalent to techniques such as ICP-MS [212]. There
also other reports presenting cheap alternatives to atomic/mass
spectrometry-based methods, which are based on electrochemical
measurements. While such methods cannot provide the total
amount of metallic impurities, they allow differentiation between
the total and the redox-active and hence bioavailable amount of
impurities in carbon nanostructures, which is important from the
toxicological point of view. The redox-active nickel impurity in
SWCNT samples can be characterized quantitatively as a nickel
hexacyanoferrate-SWCNT hybrid complex system by cyclic vol-
tammetric techniques [213]. This approach is based on a similar
electro-analytical method for quantification of the Ni impurity in
CNTs via electrochemical oxidation of Ni(OH)2 formed in alkaline
solutions when Ni impurities are exposed to the surrounding
environment [214]. Finally, commonly-known techniques often
associated with carbon nanomaterial qualifications and quantifi-
cations like Raman spectroscopy, near-infrared fluorescence spec-
troscopy (NIRF) or UV-VIS-NIR spectroscopy (used to determine the
abundance of semi-conducting, semi-metallic, and metallic
SWCNTs) are not applicable to detect trace metal impurities
[215,216]. Raman and NIRF spectroscopies are however sensitive
indicators of surface modifications of carbon-based materials. De-
tails concerning such analytical techniques can be found elsewhere
[15].
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In summary, there is no single universal technique to study the
purity of carbon-based materials and combinations of a few tech-
niques are almost always required to accurately determine the
content and type of metal impurities. Selection of an appropriate
analytical tool depends on the information pursued. While
improved digestion methods of carbonaceous materials are
constantly being developed worldwide, validation of the obtained
results remains challenging due to the lack of reference materials
for the diverse family of carbon (nano)structures. Most importantly,
while the range of possible analytical techniques is truly impres-
sive, one must be aware of the critical limitations of the tech-
nique(s) selected. To prove that a carbon sample is truly free of
metallic impurities is not as easy as it may seem.
5. Artifacts and deleterious effects of TM impurities
Due to their rich chemistry and specific physical properties,
transition metal impurities cause numerous deleterious effects and
artifacts during the examination and practical application of
carbon-based materials. Most transition metals exhibit multiple
oxidation states separated by a single electron. This is due to a
relatively small increase in the successive ionization energies.
Interestingly, for this very reason, most 3d TMs are essential for life
as they constitute a central part of the enzymes catalyzing vital
redox life processes. The multiple oxidation states separated by a
single electron give paramagnetism to most transition metal
compounds. TMs are efficient catalysts due to their ability to easily
donate/accept electrons to/from other molecules, which is due to
vacancies in d-orbitals. Herein below we track down some promi-
nent examples to substantiate that even ppt quantities of TMs can
turn seemingly carbon-only materials into surprising new sub-
stances of unforeseen properties.
5.1. TM impurities govern the electrocatalytic properties of carbon
(nano)structures: the groundbreaking discoveries of Compton and
Pumera
Carbon-based materials have a long and glorious history as
components of electrochemical systems. Not surprisingly, since
their first popularization, new carbon nanostructures have been
extensively scrutinized by electrochemists. Hopes were high that
new “outstanding” carbon nanostructures will reveal some un-
usual, intrinsic electrocatalytic properties. Electrodes based on
CNTs indeed offer enhanced electron transfer rates and decreased
overpotentials for a whole range of redox processes. This phe-
nomenon is known as the so-called “electrocatalytic effect”. How-
ever, in 2004 Compton and co-workers were the first to report that
in fact there is nothing distinctive and special about carbon nano-
tubes as they do not exhibit any electrochemical properties supe-
rior to those of simple graphite powders [217]. Just like for graphite
powder, the electrocatalytic responses of CNTs can be attributed to
the edge plane like-sites/defects occurring at their ends and along
their axes [217,218]. Consequently, carbon nanotubes have been
found to be no more catalytically active than edge plane pyrolytic
graphite and the activity originates from abundant defects. In fact,
ideal, defect-free CNTs (as presented on Fig. 1) are expected to be
poorly active in (electro)catalytic processes. However, raw CNT
samples contain up to 30e50 wt% of carbonaceous and metallic
impurities while CNT samples containing ca. 1.0 wt% of residual
metallic impurities are considered high purity materials. The trace
metallic impurities are often not listed in the purity certificates of
commercial CNT powders and some researchers may erroneously
assume that such materials are pure or even metal-free. Impor-
tantly, in 2006 Compton et al. discovered that metal-based impu-
rities within CNT samples are responsible for their outstanding
performance in electroanalysis observed for nanotube-modified
electrodes [219]. This observation is one of the turning points in
the science of carbon nanostructures as it started a gradual disen-
chantment with nanocarbons. From that point it also became clear
that the presence of residual metallic impurities within CNTs and
other carbon nanostructures can totally dominate their electro-
chemical properties. TM impurities are involved in the catalysis of
heterogeneous electron transfer and hence significantly enhance
the activity of carbon-based materials. As shown, MWCNTs leached
for 35 h in 2 M HNO3 still contained Fe2O3/Fe3O4 impurities. The Fe-
based residues were responsible for enhanced electrochemical
properties towards the oxidation of hydrazine (which is highly
sensitive to metallic impurities) [219]. In addition, the “electro-
catalytic” hydrogen peroxide detection reported at MWCNT-
modified electrodes was due to residual iron oxide particles origi-
nating from the catalysts used for nanotube production and not due
to the intrinsic, catalytical properties of CNTs arising from the edge
plane-like sites/defects [220]. Similarly, residues of iron in the form
of Fe3O4 dominate the electrochemical response of SWCNTs in the
electrochemical oxidation of hydrazine and reduction of H2O2
[221]. Detection of H2O2 is of the utmost importance inter alia for
studying the oxidative stress in biosystems, for fuel cells and
corrosion processes. Compton and co-workers further showed that
the reduction of halothane (a general anesthetic) [222] and
oxidation of glucose [223] is caused by the occluded copper oxide
impurities in MWCNTs. Soon after these important discoveries it
was also reported that different batches of commercial MWCNTs
produced via the CVD process contain significantly different
amounts of metallic impurities and to make matters worse the
amount as well as the type of metallic impurity can vary consid-
erably [224,225]. Since stirring CNT samples in 2 M nitric acid even
for a few days does not guarantee removal of all the Fe-based im-
purities, Compton and Banks strongly advocated special caution in
studying CNTs in electroanalysis, since the electrochemical or
“electrocatalytic” response may originate from residual metallic
impurities [226]. Eventually, they challenged the belief that carbon
nanotubes are electrocatalytic materials at all. While the truly
intrinsic electrochemical activity of carbon nanotubes is due to
edge plane like-sites/defects at the ends/along tube axes, Comp-
ton’s research group highlighted that even a small amount (ca.
1.0 wt%) of metallic particles randomly distributed within carbon
nanotubes predominate their electrochemical response. This effect
is due to overlapping diffusion layers - only a small proportion of
transition metal is enough to ensure that the electrochemical
response is dominated by them rather than by the edge plane sites/
defects of carbon materials. Consequently, an electrode exhibits
behavior analogous to that of the corresponding macroelectrode.
Therefore, Banks and co-workers encouraged the utilization of
carbon nanotubes completely free of metallic impurities to avoid
potential experimental misinterpretations. Commercial carbon
nanotubes usually possess diverse active sites towards target ana-
lytes (i.e. not only edge plane sites but also metallic impurities)
[227,228]. By utilizing MWCNT samples of high purity (99.99þ%;
the MWCNTs were obtained via a catalyst-free growth process
based on a solid-state production method) Banks et al. were able to
conduct a proper evaluation of carbon nanotube materials without
the need to de-convolute the contribution of metallic impurities
[228]. Eventually, they also demonstrated that the electrochemical
signatures of graphene screen-printed electrodes towards hydra-
zine are caused by metallic impurities [229]. Consequently, they
proved that all the observations made for metal-contaminated
CNTs also apply to graphene-based materials.
After the seminal work of Compton and Banks, Pumera and his
co-workers have become the leading debunkers of the “unlimited
versatility” of metal-free carbon-based nanostructures and their

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W. Kicin
application in the so-called carbocatalysis. In one of his many re-
ports Pumera stated that “It is clear that without proper detailed
characterization of carbon nanotube materials and any impurities
they might contain any data on the performance of CNTs would be
useless since the origin of the electrochemical/redox reaction is un-
known” [230]. This statement can be extended to graphene-based
structures and any other types of carbonaceous material that
might contain traces of TMs. It is indeed a profound statement as a
substantial part of the research concerning catalytic, electro-
chemical, toxicological, electronic, magnetic, optical and adsorption
properties of carbon-based materials can be misinterpreted/dis-
trusted if rigorous characterization of the materials’ purity is not
included. Because carbonaceous materials are usually highly het-
erogeneous systems consisting of different phases and impurities,
detailed characterization must be performed in order to correctly
establish the structure-to-performance relationship. As now
known, common purification procedures are not effective in
removing metallic nanoparticles from CNT samples. Even the most
thorough purification procedures yield CNTs that still containing up
to ca. 1.0 wt% of metallic-based phases [231,232]. For instance,
MWCNT and SWCNT samples were subjected to stirring in
concentrated nitric acid (6 M) for 36 h at 80  C yet even this
extensive purification removes only up to 88 wt% of the initial
metal catalyst nanoparticle content (e.g. Fe, Ni, Co and Mo) [232].
Metallic impurities exist within CNTs as capsules covered by
graphitic layers or as naked particles attached to the carbon surface.
However, even if washing at elevated temperature does not remove
the metal catalyst impurities, one cannot necessarily conclude that
these nanoparticles are protected by tight graphene sheets. In fact,
the kinetics of dissolution of many metal oxides, hydroxides, car-
bides, sulfides, multi-elemental alloys and mixed phases are much
slower than that of pure metals, even in concentrated and oxidative
acids. Many of the metallic impurities are binary or multinary
systems and the composition of the residual metallic catalyst im-
purities in a single batch of carbon nanotubes may vary drastically.
Pumera demonstrated that a single residual catalyst nanoparticle
exhibits a complex composition as it contained about 97% (at.) of Co
and 3% of Mo while the neighboring metallic particle impurity (a
few tens of nanometers away) contained 2% of Co and 98% of Mo
[232]. In fact, metallic catalyst nanoparticles used for the synthesis
of nanotubes might themselves contain other metallic impurities
[233]. TM impurities can consist of several components in various
atomic ratios. Interestingly, even minor impurities within known
TM impurities can totally dominate the catalysis of some redox
reactions. Trace iron impurities within residual Co/Mo catalyst
nanoparticles in CNTs (on the level as low as tens of atoms of Fe per
Co/Mo nanoparticle) were identified to be responsible for the
electrochemical reduction of H2O2 [230]. As little as 0.045 wt% Fe in
a CNT sample can be fully responsible for its electrochemical
properties. Multicomponent metallic impurities present within
carbon nanotubes are actually responsible for a whole range of
electrochemical processes [234e236]. In contrast to H2O2 reduc-
tion where only traces of iron within Co/Mo nanoparticle impurities
were responsible for the “electrocatalysis”, all metallic components
of multicomponent metallic impurities (Co, Mo, and Fe) dominate
the electrochemical response of CNTs toward N2H4 oxidation.
A variety of metallic particles have a strong toxic effect on living
organisms because they participate in the redox chemistry of
important biomarkers. Aside from the ubiquitous iron-based par-
ticles, Ni-based particles are also prevalent within CNTs and can
induce toxic action. Ambrosi and Pumera presented the first
example of the direct influence of metallic impurities in CNTs on
the oxidation of peptides [237]. The redox chemistry of regulatory
peptides was affected by the presence of NiO impurities within
SWCNTs. Binary nickel and iron residual catalyst impurities within
777
SWCNTs were found to be responsible for the electrochemical
oxidation of amino acids, showing that metallic impurities in CNTs
can cause damage to peptides and proteins in living organisms. The
chemical states of Ni in the SWCNTs were determined to be Ni0 and
Ni(OH)2 which suggests that there is interaction between the
external solution and residual metallic impurities [238]. Ni-based
impurities within CNTs were also found to be responsible for
electrocatalytic oxidation of sulfides [239].
Eventually, one may wonder how small the proportion of
metallic impurities in carbon-based materials must be in order not
to dominate their redox properties. By using CNTs as an example, it
was demonstrated that Fe-based impurities at concentrations as
low as 0.01% (100 ppm, which is significantly lower than the
detection limits of SEM/EDX and XPS methods) still affect their
redox properties towards hydrogen peroxide reduction [240]. Only
at levels of 10 ppm (0.001%) do the impurities cease to have visible
effect and CNTs can be considered electrochemically pure. The
borderline where Fe-based impurities no longer dominate the
redox properties of CNTs is somewhere between 100 and 10 ppm.
However, one must consider that the (electro)catalytically “invis-
ible” amount of TM impurities depends on the particular electro-
chemical process being considered. The maximal depth of metallic
impurity inclusion within carbon nanotubes at which they still
participate in electrochemical processes is also surprisingly large,
up to 12e13 nm [240]. Even if metal particles are covered by tight
graphitic shells they can still participate in redox processes. It has
been demonstrated that Fe particles encapsulated in non-doped
and nitrogen-doped CNTs exhibit both FeII/III and Fe0/II redox ac-
tivity, depending on the experimental conditions chosen for elec-
troanalysis [241]. Even though the Fe particles are tightly encased
by graphitic shells, they are still accessed via anion intercalation
into the CNTs’ graphitic lattice. Moreover, an increased FeII disso-
lution from N-doped CNTs was observed and attributed to more
easily accessible sites since there are more structural defects within
the N-doped CNT lattice in comparison to non-doped CNTs. Fe
contained within non-doped CNTs is better protected from elec-
trochemically induced oxidation while N-doped CNTs are much
more defective structures. This is an important observation, which
raises some doubts concerning the supposedly metal-free, N-doped
carbon-based catalysis.
While CNTs contain a variety of metallic impurities, the situation
is even more complicated for graphene-based materials. Generally,
methods for GBMs preparation can be divided into top-down
(exfoliation of graphite, e.g. via chemical oxidation-reduction)
and bottom-up (e.g. CVD or epitaxial growth). Exfoliation of
graphite is usually carried out by liquid-based oxidation to graphite
oxide (GiO) from which graphene oxide is produced followed by a
reduction yielding reduced graphene oxide. A large gamut of
methods is available for both the oxidation and reduction steps but
all the methods cause incidental contamination of the final mate-
rials by a whole range of metallic and nonmetallic impurities. The
impurities in the final GO and rGO samples originate not only from
the chemicals used for exfoliation and reduction process, but also
from the starting graphite and additional treatments. Solution-
based oxidation of graphite to GO can be classified into chlorate-
based (e.g. Staudenmaier or Hofmann) or permanganate-based
(Hummers) methods depending on the oxidant utilized (KClO3 or
KMnO4). In most experimental works concerning synthesis, prop-
erties and application of graphene, diverse derivatives of graphene-
like materials such as chemically/thermally reduced graphene ox-
ide are utilized instead of a single-layer ideal graphene. Such de-
rivatives are referred to as chemically modified graphene (CMG) or
graphene-based materials. The Hummers’ method and its modifi-
cations are by far the most popular way of preparing GiO and a
variety of CMGs. However, the Hummers’ method introduces a
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significant amount of Mn-based impurities (thousands of ppm) into

the resultant graphite oxide. As Pumera et al. substantiated,
contamination with metals is unavoidable during the oxidation of
graphite to GiO and GO and the subsequent reduction to rGO
[242e244]. Consequently, graphene-based materials prepared
from graphite oxide exhibit contrasting and inconsistent electro-
chemical properties [19]. Fabrication procedures that do not
involve the use of electrochemically active TMs could constitute an
efficient strategy to exclude the influence of metallic impurities on
graphene-based material properties. A low (ppm) level of impu-
rities can significantly alter the electrochemical properties of
carbon-based materials; however, lowering this level without
substantial modification/destruction of the carbon structure is
impossible [244]. The reduction of metallic content to levels where
they have no significant catalytic effects (far below 0.01 wt%) is
difficult and only methods utilizing extreme conditions (high
temperature annealing (2000e2500  C) under vacuum and/or
under halogen atmosphere) can efficiently remove TM impurities
[245]. Even if totally metal-free routes are utilized to obtain GO, the
final material is still contaminated by traces of TMs. This is because
both natural and synthetic graphite contain metallic impurities
(mostly Fe and Ni) which remain in the GO and rGO samples pre-
pared by top-down graphite exfoliation [145,246]. The Fe content in
rGO obtained from synthetic and natural graphites is still in the
range of 100e1000 ppm [246]. One of the most efficient ways to
remove metallic impurities from such graphene-based materials is
thermal treatment at 1000  C in a Cl2 atmosphere (after treating the
graphene in a H2 atmosphere at 1000  C to reduce metal oxides).
This treatment is more efficient than refluxing in a concentrated Fig. 32. Schematic synthesis of reduced graphene oxide by different oxidation-
hydrochloric/HNO3 acid mixture or in a mixture of hydrochloric reduction methods and contaminants found in the final products. Reproduced with
permission from Ref. [247]. (A colour version of this figure can be viewed online.)
acid/H2O2, since liquid-based purification methods resulted in
unaltered levels of Fe [246]. Even if ultrapure graphite (99.9995%;
2e15 mm, Alfa Aesar) was utilized to obtain rGO, the final product Pb (0.033) and Ni (0.014)). Overall, when one studies GBMs and
was still contaminated to varying extents by the chemical reagents their catalytic properties, the presence of metallic impurities must
used during the oxidation and reduction procedures [247]. While be considered. For instance, the origin of the catalytic activity of
incorporation of Mn in rGO obtained from ultrapure graphite was porous GO in an aerobic oxidative coupling of amines to imines was
expected because of the use of a permanganate oxidant, contami- investigated and it was highlighted that the purification process
nation with unexpected elements (e.g. As, Co, Cr, Cs, Cu, Fe, Sb, and and thorough characterization had excluded the role of any metallic
Sc) was also observed (Fig. 32). Contamination by the chemicals impurities in the process of catalysis [250]. Consequently, the
used during synthesis occurs at levels high enough to alter the intrinsic oxygen functional groups in GO were identified as catalytic
electrochemical behavior of the final rGO. centers in this case of a truly metal-free carbocatalysis.
Carbon-based (nano)materials have been widely used in the In summary, seminal papers presented by Compton’s and
design of advanced electrochemical sensors and energy storage Pumera’s research groups changed our view on the intrinsic elec-
devices [248]. However, the performance of graphene-based de- trochemical properties of carbon nanostructures. It became clear
vices is critically dependent on graphene purity as impurities that there is nothing particularly special about the electrochemical
hinder the utilization of graphene-based materials where surface properties of CNTs or reduced graphene oxides. A substantial part
area is of importance. It has been shown that silicon-based con- of the research concerning the (electro)catalytic properties of CNTs,
taminations originating from graphite utilized to obtain GO are graphene and a variety of carbon-based materials should be criti-
extremely persistent. Utilizing high purity graphite as a precursor cally examined for lack of rigorous characterization of the purity of
might be the only way to produce silicon-free graphene [20]. An the materials utilized. However, research prior to the awareness of
evaluation of various GO materials produced from natural and the influence of metal impurities on the electrochemistry of carbon
synthetic graphites (with purity ranging from 98% to 99.9999%) nanostructures still holds value, at least as a point of warning and
revealed that graphite with purity of at least 99.9% assures high reference and a great example of the ability of science to self-
quality and silicon-free GO. Capacitance values close to the theo- correct. Extensive research presented by Compton and Pumera is
retical capacitance for graphene were observed only when Si- also a good starting point to more deeply explore other possible
contaminant-free graphene was used to fabricate supercapacitor artifacts caused by TM impurities and ways to produce truly metal-
electrodes [20]. free carbons either via thorough purification (demetalation) or
While the Hummers’ method is the most common approach to truly metal-free synthetic procedures.
obtain GBMs, a range of other methods have also been proposed.
For instance, using the strong oxidant K2FeO4 an iron-based strat-
egy to produce single-layer GO was proposed as an alternative to 5.2. Traces of TMs in heterogeneous (electro)catalysis
chlorate- or permanganate-based methods [249]. Despite the use
of an iron-based reagent, a negligible iron content in the final GO Heterogeneous catalysis can be divided into three categories:
purified by centrifugation/water-washing was determined (ICP-MS thermocatalysis, electrocatalysis, and photocatalysis. Oxidation and
metal content in ppm: Fe (0.13), Mn (0.025), Co (0.073), Cu (0.017), hydrogenation reactions are typical examples of thermocatalysis,

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W. Kicin
while for electrocatalysis and photocatalysis, the oxygen reduction,
hydrogen oxidation, hydrogen evolution and oxygen evolution re-
actions (ORR, HOR, HER, OER, respectively) are of high importance.
By definition a “very small amount” of catalyst can significantly
alter the rate of reaction [251]. In consequence, catalytic reactions
are extremely sensitive to the presence of metal contaminants
which can either promote or poison activity and selectivity in a
variety of heterogeneous processes [252,253]. When an extremely
low metal level yields a strong catalytic effect, impurity artifacts
may play a dominant role in the reaction pathway. Such a low metal
content is often referred to as “homeopathic” [252]. TMs at con-
centrations of 1 ppm (0.0001%) or even at ppb levels can exhibit
drastic influence on chemical reactions and dominate the catalytic
pathway [252,253]. In the case of carbonaceous materials such
impurity concentrations are unavoidable in most cases.
The observation that reactions can be catalyzed by trace metal
impurities has a fascinating history with a prominent example
being the “nickel effect” discovery in the development of the Zie-
gler catalysts [253]. In 1953 Ziegler found that trace amounts of
nickel originating from steel autoclave were responsible for the
catalytic dimerization of ethylene. This discovery revolutionized
the chemistry of polymers. Another classic example of trace metal
impurity artifacts is the discovery of the antitumor activity of Pt(II)
amine complexes. The antitumor effect was unexpectedly observed
in an attempted electrolysis of tumor cells using Pt electrodes. The
activity was entirely due to the trace (ca. 10 ppm) of Pt that dis-
solved under experimental conditions and reacted with trace
components of the system to give cis-[PtCl2(NH3)2] [251]. This
eventually allowed introduction of a new medical treatment. The
homeopathic effect of noble metals was also observed for platinum
group metal (PGM)-free catalysts in ORR. The activity of the sup-
posedly Pt-free catalysts (sodium tungsten bronze) for electro-
chemical reduction of O2 was later ascribed to Pt as the non-noble
metal-based catalyst was incidentally contaminated during prep-
aration in a Pt crucible [254]. In another example, the intrinsic OER
activity of CoOOH was shown to be promoted by Fe impurities from
the electrolyte [255]. Traces of TM impurities are present even in
ultrapure electrolyte solutions and while they are very difficult to
remove they can have a major impact on the promotion/poisoning
of catalysts [256]. For instance, a 0.1 M KHCO3 solution prepared
with an ACS-grade KHCO3 (99.7% (assay)) and ultrapure water
(Milli-Q), still contained 0.02e0.05 ppm of heavy metals and up to
0.05 ppm of Fe, enough to deactivate a copper electrode in the
electrochemical CO2 reduction reaction (CO2RR) [257]. The pres-
ence of metal impurities in the electrolyte combined with the
possibility of incidental contamination from the counter electrode
creates challenges for studies of the inherent properties of “metal-
free” carbocatalysts. For instance, the electrochemical performance
of carbon nanohorns in HER was greatly affected by the Pt counter
electrode employed for their activation [258]. The improved per-
formance was caused by Pt transfer to the cathode. Experimental
evaluations of electrocatalytic activity are usually done in a three-
electrode cell configuration including the reference, working, and
counter electrodes. The sample that is studied as a new electro-
catalyst acts as the working electrode. Pt wire and Ag/AgCl are
usually used as counter and reference electrodes, respectively
[259]. Both electrochemical and chemical dissolution of Pt in acidic
or alkaline electrolyte causes re-deposition of Pt on the working
electrode of interest, which affects its activity. The counter elec-
trode must be both chemically and electrochemically stable. Glassy
carbon or high-purity graphite is recommended as a counter elec-
trode [260]. Utilization of Pt counter and Ag/AgCl reference elec-
trodes requires caution, even if they are separated by a proton-
conductive polymer membrane. Strong interferences from the Pt
counter and Ag/AgCl reference electrodes were reported for the
779
HER studies due to the formation of Pt and Ag particles on the
cathode, resulting in overestimation of the HER activity of the
cathode material [261]. Ag leaches out from an Ag/AgCl electrode in
spite of the negligible solubility of AgCl in aqueous electrolytes. The
dissolution of metals from the counter and reference electrodes is a
rather poorly controllable experimental parameter, and hence,
similar artifacts can also be produced in ORR, CO2RR and N2
reduction reactions catalyzed by non-precious metal/metal-free
catalysts.
It is well recognized that extremely low palladium loadings can
yield significant reactivity for coupling reactions in organic het-
erogeneous catalysis [252,253]. Consequently, positive results for a
number of apparently “metal-free” reaction mixtures were later
verified as metal-catalyzed. Even ppt amounts of residual Pd
remaining from glassware/equipment can be enough to catalyze
supposedly “Pd-free” reactions. For instance, the first iron-
catalyzed cross-coupling reaction was reported in 2008 [262].
However, attempts to repeat this experiment failed. Eventually it
was shown that ultra-low amounts of palladium compounds
(0.1 ppm), which could be present in the original catalyst, glassware
or utilized reagents, catalyzed the reaction. As a result, authors of
the original report retracted their article and apologized for the
claims they originally made [262]. In fact, many reports concerning
catalysis in organic chemistry has been retracted later because at-
tempts to reproduce the published results by independent labo-
ratories failed. If such a rule would be applied in the chemistry of
carbonaceous materials (CNTs, GBMs, etc.) not many reports on the
catalytic activity of carbon nanostructures would prove to be
replicable. In fact, contradictory results are still being published
when it comes to application of carbon nanomaterials in (electro)
catalysis. That is because each research group studies very different
types of carbons even if the studied samples have the same name
(e.g. graphene or SWCNTs). We will never know to what extent the
physicochemical properties of carbon nanostructures reported in
literature over the past few decades are attributable to trace
metallic (and also non-metallic) impurities. However, one can
conservatively assume that a large proportion of the reported re-
sults are tainted by such effects to various extents. For instance,
graphene derivatives obtained via wet chemistry routes exhibit
large surface areas, a profusion of functional groups and hence high
adsorption capacities towards metallic ions [263]. Such materials
are extremely prone to unintentional contamination. Metal ions are
coordinated in defective graphenes, but these metallic species are
difficult to remove once bonded.
5.2.1. Carbocatalysis: non-precious metal, single-atom and metal-
free carbon-based catalysts
Carbon-supported metal catalysts are one of the most important
catalytic systems in organic synthesis [264]. For example, Pd/C
catalysts were the first commercialized carbon-supported metal
catalysts used industrially to produce organic chemicals. Moreover,
nitrogen-doping in carbon materials effectively stabilizes metal
particles enabling high catalytic performance [265e267]. The his-
tory of N-doped carbon catalysts containing transition metals
started in 1924 with Warburg research on the catalytic properties
of pyrolyzed hemin [268]. This material showed catalytic activity in
the oxidation of organic acids by molecular O2 and was susceptible
to cyanide poisoning. Warburg proposed that the catalytically
active centers within the carbon material consist of iron-carbon-
nitrogen complexes (denoted as FeeCeN) since neither pure car-
bon nor carbon with iron but without nitrogen exhibited any visible
catalytic activity. Today the so-called pyrolyzed FeeNeC materials
are the most promising PGM-free catalysts for ORR. In 1926 Rideal
and Wright prepared carbon catalysts from a mixture of sugar, urea
and ferric chloride [269]. The activity of this material in the oxalic
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acid oxidation was ascribed to three possible active centers: the
FeeCeN site, which was designed to be the most active, and less
active FeeC and CeN sites. The N-sites of N-doped carbon nano-
materials act as nucleation centers for the deposit of transition
metals, enabling high metal dispersion and better anchoring in
comparison to N-free structures [270]. The stronger interaction
between metal NPs and the N-doped carbon supports has a pro-
motional effect on the formation of metallic sites and prevent the
transition metal oxidation upon contact with air, which is partic-
ularly important [271]. Metal free and PGM-free (electro)catalysts
including pyrolyzed TM-nitrogen-carbon (TMNeC) materials are
of huge interest as cheap catalysts for O2, CO2 or even N2 electro-
reduction as well as H2 evolution reactions and a variety of organic
processes (e.g. coupling reactions). Recently such catalysts are often
referred to as single atom catalysts since the most active catalytic
centers are supposedly a single metal atoms coordinated to nitro-
gen or carbon in the carbonaceous scaffold [272e274]. There is no
clear distinction between the so-called metal-free N-doped carbon
(CNx), TM-nitrogen-carbon materials containing metallic NPs
(TM@CNx) and TM-nitrogen-carbon structures containing single
TM atoms bonded via nitrogen moieties (e.g. TMN4eC) [275]. That
is because within the pyrolyzed TMNeC catalysts the active
centers are diversified in nature and constitute isolated, single
metal atoms, encapsulated metal NPs and metal-free N-defects. In
addition, synergistic interactions between different varieties of
catalytic centers have been reported. For instance, due to an elec-
tronic interaction between N-doped carbon shells and encapsu-
lated metals, encapsulated iron NPs promote the catalytic activity
of FeeN4 centers [276]. In fact, metal particles confined inside
hollow carbon nanostructures (e.g. inside CNTs) exhibit very
different catalytic activities with respect to the same metals
deposited on the outside of a carbon structure [277]. Due to TMs
confinement some catalytic reactions can be enhanced while
others are hindered. For instance, if TMs are strained/confined
within the CNT channels, a downshift of the d-band states is
observed, and hence the adsorption of molecules such as O2 can be
weakened [277]. Moreover, in the case of N-doping, N sites act as
active adsorption centers for the deposit of metal. To complicate the
issue even more, the amount of metal in the TMNeC catalysts is
usually low (in the range of 0.05e3.0 wt%) and as little as 0.05 wt%
of metal could be enough to obtain an efficient catalyst for the
above-mentioned reactions. It has been demonstrated that trace
levels of transition metals could actually be the desired amount to
obtain efficient multifunctional TMNeC electrocatalysts [278].
Even if a truly carbon-based metal-free catalyst is indeed achiev-
able it can still be easily contaminated by metallic impurities from
the electrolyte, metallic counter electrode (e.g. Pt) or other ele-
ments of the reactor/container, especially since defects in carbon
(e.g. N-sites, reconstructed vacancies, organic impurities, etc.) have
a strong affinity to selectively capture TM ions. It is possible that
metal-based catalytic sites are also formed in situ during the act of
experiment via instantaneous adsorption and coordination of
metallic species to nitrogen-containing functional groups on the
carbon matrix. This effect could be further amplified in the case of
nitrogen/sulfur co-doped carbon due to the even stronger affinity of
TMs to sulfur [279]. The presence of N or N/S dopants on the surface
of carbon materials can improve their wettability, thus further fa-
voring adsorption of metal ions from aqueous solutions. Some au-
thors argue that if metal residues are indeed the active sites for
ORR, CO2RR, OER or HER, then pure carbon materials should also be
active catalysts because they usually contain the same level of
metal impurities as heteroatom-doped carbon materials. In most
cases, pure and undoped carbon materials exhibit rather negligible
catalytic activity. Therefore, they prefer to consider non-metallic
heteroatom doping responsible for improved catalytic activity
instead of any metallic traces. However, as mentioned above, the
strong affinity of N and S functionalities to selectively capture
metals might turn metal-free catalysts into metal-based ones by
the very act of experimental study. It was recently reported that an
N-doped carbon-based electrocatalyst undergoes activation in the
presence of Fe impurities during the CO2 reduction reaction [280].
The catalyst selectively adsorbs Fe impurities from the electrolyte
on the electron-rich N-sites leading to in situ generation of highly
dispersed FeeN sites. The degree of activation observed was pro-
portional to the number of N-sites of certain types (such as the N4
moiety/N4V2 vacancy). As the CO2RR is performed at highly
reductive potentials, in situ formation of TMN centers from a trace
amount of metal impurities is indeed likely. Importantly, other sites
on the catalyst surface consisting of C or O are less active for Fe
adsorption than the N sites. To study this phenomenon in detail,
electrodes consisting of phthalocyanine (PC) and bipyridine-based
covalent triazine framework (BPY) were constructed. PC and BPY
were selected as they represent materials with different coordi-
nation centers of the N moiety (N4 vs N2). Catalyst inks were pre-
pared with CNTs added to ensure good conductivity. As depicted in
Fig. 33a the CNT-PPV sample (PPV stands for a nonionic poly-
phenylenevinylene binder) with and without Fe impurities does
not exhibit CO production activity. This is because this sample does
not contain N-functionalities. In contrast, the electrode with N4-
sites (Fig. 33b, the PC/CNT-PPV), which provides a center to bind
Fe(II), exhibited self-activation in the CO2RR. Interestingly, BPY/
CNT-PPV, which could provide only the N2 moiety to bind Fe(II),
did not exhibit CO production (Fig. 33c). Ni, Zn and Cu impurities
also significantly affected the activity of the studied N-doped car-
bon catalyst in the CO2RR (Fig. 33 d-f). This report is of special
importance as it is the first explicit proof that metal-free N-doped
carbons selectively capture trace metal impurities from the elec-
trolyte and gain activity via in situ formation of TMNx catalytic
centers [280].
Finally, it has been argued that the intrinsic defects of a pure,
undoped carbon scaffold (non-hexagonal rings, vacances, edges,
etc.) significantly contribute to the enhancement of metal-free
carbocatalyst activities [281,282]. As reported, highly porous, sup-
posedly pure carbon materials (containing only C, O and H) exhibit
good ORR activity in alkaline electrolytes, confirming the role of
defects for ORR enhancement. Since the role of intrinsic carbon
defects is usually neglected, this effect might be the source of the
apparent confusion and conflicting reports in the field of metal-free
carbocatalysis. However, both the reports on carbon-only ORR
electrocatalysis still lacked accurate purity analyses to exclude
involvement of TMs [281,282]. Even worse, the more defects in a
carbon material the higher its propensity to bind metallic ions. This
could be the reason why more defective nanocarbons constitute
more active “metal-free” catalysts. In fact, it has recently been
proven that undoped carbons (just like N-doped carbons) exhibit
extraordinary affinity to TM ions and hence undergo instantaneous
in situ metal deposition upon contact with a metal-containing
electrolyte [283,284]. The spontaneous reduction of noble TM
salts on sp2 carbon surfaces and deposition of metal NPs is a well-
documented phenomenon. Reduction of noble metal ions (e.g. Au3þ
or Pt2þ) occurs because of the redox potential difference between
metal ions and carbon based-materials and the conductivity of the
carbon [283]. Even carbons as inert as graphite, adsorb TM ions like
sponges [284]. As expected, noble metal NPs can easily deposit on
defective HOPG yet even non-precious metal ions (e.g. Fe and Ni)
can be spontaneously reduced and deposited on graphite by simple
immersion in a metal salt solution at room temperature. This is due
to the inherent reducing potential of graphite - a material that is
usually perceived as inert. Functional groups on graphite defects
have sufficient potential to reduce TM ions to metallic NPs. This

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W. Kicin 781

Fig. 33. (a) Catalytic activities of the CNT-PPV electrode before (closed symbols and solid lines) and after (open symbols and dotted line) the injection of Fe(II) impurities. Effect of
the N moiety on self-activation. (b) Changes in partial current densities of CO (blue) and H2 (red) after the injection of Fe(II) impurities during the CO2RR using the PC/CNT-PPV
electrode. The inset is the molecular structure of PC. The Y values of each red and blue symbol represent the changes in partial current densities of CO and H2 at certain
applied potentials, respectively. (c) Catalytic activities of the BPY/CNT-PPV electrode before (closed symbols and solid lines) and after (open symbols and dotted line) the injection of
Fe(II) impurities. Effects of other metal impurities on the CO2RR using the NC catalyst. (def) Changes in partial current densities of CO (blue) and H2 (red) before and after the
injections of Ni(II), Zn(II), and Cu(II) impurities, respectively. For all cases, the stock solutions of Ni(II), Zn(II), and Cu(II) were injected to adjust the target concentration of 2.5 ppm,
respectively. Error bars indicate a deviation among three different measurements. Reproduced with permission from Ref. [280]. Copyright 2019 American Chemical Society. (A
colour version of this figure can be viewed online.)

reduction can go via oxidation of hydroxyl groups to carbonyl
groups. More importantly, metal NPs are generated not only on the
surface, but also deep inside the bulk of graphite due to cracks and
imperfections of its structure (up to ~100 mm, Fig. 34). More defects
allow more metal ions to be reduced to NPs and hence this effect is
expected to be incomparably greater for carbons with nanofeatures
than for graphite powder. Finally, it has been shown that defective
carbons not only capture TM ions from solutions but are also able to
pull TM atoms out of their metallic crystal lattice [285]. Sonication
of GO with metallic foams of Fe, Co, Ni or Cu resulted in the transfer
of TM atoms from metallic phase to GO due to the trapping of metal
atoms by the oxygen-containing dangling bonds of GO. This
allowed preparation of SACs with metal loadings of up to 7 wt%
(Fig. 35). The amount of a trapped metal was proportional to the
amount of Oefunctional groups in GO. The TMeO bond is appar-
ently responsible for plucking the TM atoms out of the bulk metal
crystal.
Also, aqueous solution of KMnO4 undergoes spontaneous
reduction by SWCNTs [286]. The spontaneous formation of MnO2
on the surface of the SWCNTs is due to the difference in the redox
potential between the SWCNTs and MnO 4 ions. The Fermi level of a
SWCNT is ca. þ0.5 V above the potential of a standard hydrogen
electrode (SHE) and above the reduction potentials of MnO 4 strongly bound single-atom sites remain firmly anchored on the N-
(þ1.692 V vs SHE). The rate of MnO 4 reduction by CNTs increased
with decreasing pH of the aqueous KMnO4 solution. Hþ released
from the solution and the electrons donated from the SWCNTs are
responsible for the spontaneous reduction of MnO 4 . This phe-
nomenon is of importance as KMnO4 solution is often utilized to
process carbon-based materials (e.g. synthesis of GO, unzipping of
CNTs, etc.)
The influence of metallic impurities on “metal-free” carbon-
based (electro)catalysts is under heated debate for at least a
decade, since 2009 when the first publication on metal-free elec-
trocatalysts for oxygen reduction was published [287]. With around
4500 citations after only 10 years, this paper initiated the field of
non-metallic carbocatalysis (carbon-based metal-free electro-
catalysis). In this study, N-doped CNT arrays synthesized by py-
rolysis of iron(II) phthalocyanine exhibited better activity than
commercial Pt/C in the ORR in alkaline fuel cells. Fe was removed
from the vertically aligned N-doped CNT catalyst by electro-
chemical purification. The efficiency of electrochemical purification
was confirmed by voltammetric responses of the working electrode
before and after electrochemical oxidation. Fe removal was
confirmed by XPS, TG and CO poisoning tests (iron-based catalysts
would be poisoned by CO). An Ag/AgCl and a Pt wire were used as
reference and counter electrodes, respectively. While the authors
concluded that the iron phase was completely leached out during
electrochemical purification, neither XPS nor TG is capable of
detecting less than 0.1 wt% Fe in carbon matrixes, and such con-
centrations already strongly promote O2 electroreduction. It has
also been shown recently that theoretically, a large electrochemical
potential window may exist, within which any aggregate forms of a
target transition metal (e.g. Pt, Pd, and Ni) on the carbon substrate
are easily leached away by electrochemical oxidation, while the
doped carbon [132]. Even the poisoning studies could give mixed,
unclear results. Now it is recognized that the FeeNeC catalysts
exhibit much better resistance to chemical poisoning than noble
metal-based catalysts [288e290]. Accordingly, there is a possibility
that the first metal-free, N-doped carbon electrocatalyst was in
reality a type of FeNxC single-atom catalyst as such structures
show good poisoning resistance and outstanding performance in
alkaline conditions. Similarly, Wagberg and co-workers studied
CVD-derived (ferrocene was used as a catalyst) N-doped MWCNTs
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W. Kicin
Fig. 34. SEM images of metal NPs deposited after immersing a piece of graphite in a salt solution. The left column shows the surface of graphite (i.e., without peeling any layer off its
surface). The right column shows the bulk section of graphite (i.e., ~100 mm beneath the surface) after peeling a layer off its surface. Fe and Ni NPs deposited on the surface and in
the bulk of graphite. Adapted with permission from Ref. [284]. Copyright 2019 American Chemical Society.
Fig. 35. Schematic illustration for the construction and characterization of Fe SAC/GO.
a) Schematic illustration for the preparation of Fe SAC/GO. b) TEM and c) HAADF-STEM
images and the corresponding EDS elemental mapping, and d) aberration-corrected
HAADF-STEM image of Fe SAC/GO. e) Fe K-edge XANES spectra. f) k3-weighted c(k)
function of the EXAFS spectra and g) EXAFS fitting curve for Fe SAC/GO. Inset is the
proposed FeeO4 coordination environment. Reproduced with permission from
Ref. [285]. Copyright © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. (A
colour version of this figure can be viewed online.)
as ORR electrocatalysts (in KOH solution) [291]. They showed that
high temperature annealing transforms pyrrolic and pyridinic sites
into quaternary nitrogen, which improved the ORR catalytic ac-
tivity of the doped nanotubes. However, they did not even remove
Fe from the N-doped MWCNTs after synthesis. Taking the recent
results concerning immobilization of single metal atoms on N-
doped carbons and the extraordinary stability of metal-N4 atom
sites into account [129] it is likely that they also obtained some type
of single-atom FeNxC catalyst. Such catalysts contain, inter alia,
FeN4C10 motifs (Fig. 36), which are considered the most stable and
active sites of SAC FeeNeC catalysts in ORR electroreduction in the
whole range of pH (although much more active at pH ~13)
[131,292,293]. In fact, it has been shown that high-temperature
synthesis of CNT from precursors containing Fe and nitrogen
yields CNTs with single atom FeeN4 sites that exhibit excellent ORR
catalysis, outperforming the conventional PteC catalyst (0.1 M
KOH) [293]. If bulk Fe is available during pyrolysis, a single Fe atom
with the oxidation state of þII stabilizes the N4V2 vacancy by
lowering its formation energy, eventually yielding a FeeN4 com-
plex (Fig. 37).
There is a profusion of reports on metal-free carbon catalysts,
which might be questioned on this basis, especially since the purity
of the studied catalysts was not thoroughly assessed despite the
fact they contained transition metals [294e298]. To be fair, one
must consider that many of these reports were published before
awareness of the surprising thermo- and (electro)chemical stability
of carbon-embedded metal-N4 sites and before full development of
metal-based single-atom (electro)catalysis. An increasing number
of reports on metal-free carbon catalysts do include thorough pu-
rity assessments now, providing strong evidence for truly non-
metallic carbon-only catalysis [299,300]. This is of the utmost
importance because, as Masa et al. warned, it is important to un-
derstand how metallic impurities affect the ORR activity of N-
doped carbon catalysts to avoid misleading designations of “metal-

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
Fig. 36. Model of a carbon basal plane-infused FeeN4 site (FeN4C10 site with pyridinic
coordinating N), which can be formed by thermal mobilization of Fe atoms followed by
their entrapment at N4V2 vacancies. (A colour version of this figure can be viewed
online.)
free catalysis” [301,302]. As they reported, the ORR activity of Fe/N-
doped carbon catalysts increases with Fe loadings of up to about
1.0 wt% and then begins to decline. The addition of Fe to metal-free
N-doped carbon catalysts in concentrations as low as 0.05 wt% can
totally dominate their activity and significantly promote the ORR.
Similarly, Wang et al. found that the activity of FeeNeC catalysts
increases with Fe content ranging from 10 to 1000 ppm and then
Fig. 37. (a) Schematic illustration of the CNT with FeeN4 sites (the blue, magenta,
green, and gray spheres indicate the C, quaternary N (Nq), pyridinic N (NPyr), and Fe
atoms, respectively). (b) Calculated formation energies as a function of the N chemical
potential mN. The insets show the atomic structures of quaternary Nq, Pyr-N3, Por-N4,
and FeeN4. (c) Half-wave RDE voltammograms for ORR at the GC (black), PteC (pur-
ple), CNT (blue), Nq-CNT (green), and FeeN4CNT (red) electrodes in O2-saturated
0.1 M KOH. Adapted with permission from Ref. [293]. Copyright 2011, American
Physical Society. (A colour version of this figure can be viewed online.)
783
declines at higher Fe concentrations [303]. These examples
demonstrate that the designation of catalysts produced using metal
precursors as “metal-free” might be erroneous. In another report N-
doped carbon composites of N-doped graphene, N-doped CNTs and
carbon black were shown to catalyze O2 reduction as efficiently as
state-of-the-art FeeNeC catalysts [304]. While this work could
indeed indicate that N-doped carbon nanomaterials are efficient
metal-free catalysts for ORR even in acidic polymer electrolyte fuel
cells, both the CNTs and graphene were prepared using methods
involving transition metals. The N-doped CNTs are especially likely
to contain a high content of residual growth catalyst, because the
bamboo-like structure of N-modified CNTs may trap metal particles
in the tube compartments [241]. Consequently, the presence of
transition metals cannot be excluded. Investigations of the intrinsic
active sites of “metal-free” N-doped carbon materials that involved
metals in their preparation showed that metallic residues at the
ppm level are responsible for the catalysis of HER [305]. Further-
more, these residual metal sites are extremely stable against acid
washing lasting for one week. As a result, “metal free” N-doped
carbon materials are not truly free of metals if metals are present in
their synthesis, since residual metallic species are entrapped in the
form of metaleNx or metaleC(O)x coordinations. “Metal-free”
carbon-based catalysts obtained from biomass also cannot be
considered as metal-free as biomass is never free of metallic im-
purities. Considering the facts that: (i) it is impossible to totally
remove metallic impurities from CNTs by acid leaching, (ii) N-
doped (or N/S-co-doped) carbons bind/capture metals much more
strongly than their undoped counterparts, (iii) encapsulated metal
NPs might contribute to ORR and are resistant to the selective
poisoning test (by CO, CN, S 2 , etc.), and (iv) single atom metal-
NxC sites exhibit outstanding thermochemical stability and high
catalytic activity, the first report on metal-free ORR catalysis
(Ref. [287]) should be read with some skepticism. On the other
hand, a number of researchers claim that the presence of truly non-
metal active sites for ORR/OER/HER in N-doped carbons was un-
equivocally confirmed by a study based on HOPG model and N-
doped graphene nanosheet powder catalysts [306,307]. Neverthe-
less, while the catalytic properties of metal-free N/S-co-doped
carbons are explained by the rehybridization of CeN/CeS/NeS
configurations they can simply be caused by ppm (or even ppb)
levels of adsorbed metals strongly interacting with p-block het-
eroatom functionalities [265]. However, from a practical and
economical point of view, such catalysts can indeed be considered
metal-free, as they do not need intentional introduction of
expensive metal precursors during their synthesis.
Inherent metal impurities can occur in surprisingly high con-
centrations in commercial organic chemicals that are expected be
free of metallic compounds. Iron is a very common impurity in
commercial chemicals as it is introduced from stainless-steel re-
actors routinely used for syntheses. As a result, chemicals including
solvents are contaminated with transition metals. Iron for instance
was detected at levels as high as 0.15 wt% in an organic reagent
(perylene tetracarboxylic dianhydride (PTCDA)) utilized to produce
carbon supports supposedly devoid of Fe impurities [308]. The
source of Fe was traced to the stainless-steel vessels used to pro-
duce the organic reagents. PTCDA was leached several times in
concentrated HCl to decrease the Fe content to <35 ppm. However,
the Fe content in the carbon obtained by pyrolysis of this precursor
was still as high as 47 ppm. This is because metallic impurities
within organic precursors accumulate during pyrolysis. As a result,
a few ppm might be accumulated over a few consecutive carbon-
izations to hundreds of ppm. The equipment used for pyrolysis
processes to produce chars can also release TM impurities. Com-
mercial carbon blacks enriched in nitrogen used as supports also
contain metallic impurities, which accumulate after thermal
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annealing. For instance, N-doped carbon black (Sid Richardson
Carbon Corporation) contained 40 ppm of Fe after annealing [309].
The same problem concerns carbons templated on zeolites, metal
organic frameworks (MOFs) or other templates as they also contain
traces of transition metal impurities. When metal-organic frame-
works (e.g. ZIF-8) are used to obtain an N-doped carbonaceous
material the final material usually contains traces of Fe from the
utilized MOFs. During the synthesis of MOFs, iron from the
stainless-steel autoclaves can be easily incorporated into their
structure. For instance, the concentration of Fe in commercial ZIF-8
was detected to be 165 ppm and the Fe impurity was transferred to
the final carbonaceous material [310]. As suggested by Dodelet
et al., when the Fe concentration in N-doped carbon gets below a
certain threshold (for instance below ca. 50 ppm) then metal-free
CNx defects are the prevalent sites active in the catalysis of ORR,
however FeNx still exists, even if the carbon precursor has been
extensively purified by acid leaching [310].
N-doped carbon-based materials are usually obtained via high-
temperature processes which generate a variety of N-configura-
tions (e.g. pyrrolic, pyridinic, quaternary, metalNx sites, etc.).
Chemical fictionalization on the other hand allows better control
over N-functional groups grafted at the carbon surface. Surface N-
functionalities can mimic the well-defined edge-type N-defects in
carbon materials probed as metal-free catalysts. As reported, N-
functionalized CNMs with variable basicity can act as versatile
solid-base catalysts. For instance, aziridine (¼NH)-functionalized
MWCNTs with basic character typical of secondary amines exhibi-
ted high catalytic activity in the Knoevenagel condensation [311].
MWCNTs (metal residues below 2 wt% (based on TG)) were used to
obtain a variety of N-functionalized catalysts for ORR and CO2RR
[311,312]. In comparison to unfunctionalized MWCNTs, the
aziridine-functionalized counterparts demonstrated enhanced
catalytic activity for ORR (in alkaline conditions), ascribable solely
to the N-functionalization. When utilized as metal-free electro-
catalysts for CO2RR, aziridine functionalized CNTs demonstrated
performance that was among the best reported at that time for
similar metal-free carbocatalysts [312]. Similar, N-functionalized
CNT materials proved to be metal-free heterogeneous catalysts for
mild CO2 reduction to methanol [313]. Utilizing the aryldiazonium
salt (Tour) functionalization process, MWCNTs were functionalized
with a variety of pyridine- and pyrrole-containing dangling groups
[314,315]. The sample functionalized with 9-aminoacridine
Fig. 38. CNTs ex situ functionalization via aryl diazonium salt (Tour) conditions. (**) The Npy content (NPy%) is calculated for samples 2 and 4 via acidbase titration. (A)
Currentpotential curves for ORR in O2 saturated 0.1 M KOH solution for the disk electrode [0.196 cm2 GC rotating-disk electrode] and (A0 ) for the ring electrode [0.11 cm2 Pt
rotating-ring electrode]. (B) H2O2 production (%) for all N-doped and undoped samples. Adapted with permission from Ref. [314]. Copyright 2013 American Chemical Society. (A
colour version of this figure can be viewed online.)

ski, S. Dyjak / Carbon 168 (2020) 748e845
exhibited higher electrocatalytic activity in ORR than CNTs func-
tionalized with 4-aminopyridine and 3-aminocarbazole (Fig. 38).
Pyridinic nitrogen was identified to be the active site, whereas
neighboring carbon atoms play an essential role in the catalyst’s
ability to perform ORR under alkaline conditions. Eventually, strong
evidence of a truly metal-free action of N-doped CNTs in ORR was
provided utilizing the advantages of surface functionalization,
ruling out contribution from any metal contaminants [316]. In
addition to covalent functionalization, polymers were also used to
modify N-free carbon nanotubes by simple physical adsorption, and
such composites acted as metal-free electrocatalysts for ORR in an
alkaline solution, exhibiting properties similar to that of commer-
cial Pt/C catalysts [317]. Moreover, a co-catalytic effect has been
observed for CO2RR by an overlayer film of polyethylenimine
adsorbed on the surfaces of N-doped CNTs [318].
Carbon materials with N-functionalities attached via covalent
sp3 bonding are somewhat different to those where heteroatoms
are substitutionally infused into the conjugated sp2-carbon
network. In fact, they are similar to carbon-based solid acids (car-
bons functionalized with eSO3H groups), which indeed are truly
metal-free carbocatalysts for acid-catalyzed reactions. There are
various metal-free catalytic processes where the acido-basic (and
not redox) sites are active moieties in the catalytic conversion.
Acido-basic sites catalyze a variety of organic processes involving
cracking, polymerization or isomerization. Condensation, addition
and other carbon-carbon bond formation reactions in organic
synthesis are indeed catalyzed by truly metal-free carbon-based
catalysts. For instance, C60 functionalized with eOH groups proved
to be a competitive substitution for the traditional Lewis acid cat-
alysts in organic syntheses [319], while GO functionalized with
silanol, quaternary ammonium salt and amine groups was used as a
metal-free catalyst for cycloaddition of CO2 to epoxides [320]. In
contrast to acido-basic catalysts, redox sites which can catalyze
proton-coupled electron transfer reactions (e.g. ORR, CO2RR, N2
electroreduction, etc.) are extremely sensitive to traces of transition
metals. There are also the profound questions of why N-doped
carbons are not active ORR catalysts in acidic conditions, and what
is the nature of the active sites of carbon-based metal-free elec-
trocatalysts for an acidic ORR. As recently shown, removal of pyr-
idinic N atoms from an N-doped HOPG yields edge defects in the
form of carbon pentagons [321]. This carbon defect was identified
as the active site for the acidic ORR, superior to that of pyridinic

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W. Kicin
sites. Similarly, zigzag-edged graphene nanoribbons with a CNT
backbone obtained by partial unzipping of MWCNTs showed
enhanced ORR catalytic activity in an acid electrolyte [322]. In
comparison to its N-doped counterpart, the N-free carbocatalyst
was more active in acid because the pyridinic nitrogen of N-doped
carbons undergoes deactivation via protonation. Eventually, even in
CO2RR, N-free carbons were shown to be more active electro-
catalysts than their N-doped counterparts [323]. As postulated,
thermal desorption of nitrogen from N-doped carbons creates a
defect-rich, metal-free electrocatalyst for CO2RR. Consequently, it is
possible that carbon-only defects rather than the previously
considered N sites catalyze the CO2RR.
Many metal-free carbon-based structures are presented as
versatile multifunctional (electro)catalysts for a variety of reactions
(e.g. ORR, OER, HER, CO2RR) over a wide range of pH values with
even higher activities and stabilities than those of commercial
noble metal counterparts [324,325]. Some of the reports indicate
that heteroatom-free (carbon-only) materials are excellent multi-
functional catalysts. Other reports argue that N-doping is the
decisive factor while others still suggest that either B-, F-, P-, S- or
multielement-doped carbons perform better than N-doped ones
[326e328]. Which heteroatom yields the best performance? How
can one interpret such incoherent results? In theory, new carbon
(nano)materials offer many advantages over conventional activated
carbon and carbon black in heterogeneous catalysis. Yet difficulties
in controlling their physical and chemical properties severely limit
the potential of carbocatalysis (carbon-based metal-free catalysts).
As results concerning carbocatalysts are still poorly reproducible
and often contradictory, this field remains confined to a laboratory
scale. In a rather sarcastic article entitled: Will Any Crap We Put into
Graphene Increase Its Electrocatalytic Effect? Pumera and his co-
workers boldly questioned some aspects of the metal-free carbo-
catalysis [329]. As they pointed out, having 84 stable elements, one
can produce 84 articles of mono-elemental doping; but multi-
doping with 4 elements yields almost 2  106 possible combina-
tions. By using bird dropping-treated graphene they showed that a
multifunctional carbon-based electrocatalyst can be obtained
whatever “crap” one adds to a carbonaceous support. Since mixing
graphene even with guano can be utilized to enhance the (electro)
catalytic performance of carbon materials, why would anybody use
expensive chemicals and complex procedures when guano is so
abundant and cheap [330]? These are indeed difficult questions to
be addressed. This perspective from Pumera et al., albeit personal,
could be a good starting point for disenchanting “the wonder world
of carbon nanomaterials”, as the general perception of the utility of
at least some carbon (nano)structures might be somewhat
overoptimistic.
5.2.2. Stability of metallic species on N-doped carbon
electrocatalysts
In electrochemical test conditions, carbon nanostructures which
contain metallic impurities can undergo demetalation and corro-
sion of the carbon matrix causing further release of metal ions. Fe
metallic particles present in N-doped carbon are prone to disso-
lution into Fe2þ species at high potentials [331]. In addition, elec-
trooxidation of carbon according to the reaction: C þ 2H2O /
CO2 þ 4Hþ þ 4e is thermodynamically possible at potentials
>0.207 V vs SHE. Since the kinetics of this reaction are sluggish
(especially at lower overpotentials) the reaction is often presented
as: ReCH / ReCOH / ReC]O / ReCOOH / ReH þ CO2 [332].
Carbon oxidation can disintegrate carbon-metal coordination sites
causing release of previously bonded metallic ions and a decrease
in corrosion resistance of the material as a whole. Carbon oxidation
may also expose metal NPs that were protected by carbon layers. In
early studies on Fe-macrocycles supported on carbon materials (e.g.
785
porphyrins and phthalocyanines), their demetalation was assigned
to removal of the iron ion from the FeN4 macrocyclic core, where
the demetalation was accelerated at high potentials due to the
smaller ionic radius of FeIII in comparison to FeII. Demetalation of
the catalytic sites of FeeNeC catalysts can occur either directly (the
site loses the metal center from the coordinating Nx structure) or
indirectly by chemical or electrochemical corrosion of the coordi-
nating carbon scaffold supporting these sites (e.g. Fenton oxida-
tion) [333]. Recently, the thermodynamic stability in acid of two
types of sites: (i) a porphyrin-like FeIIN4C12 site and (ii) a FeN2þ2/C
site integrated into a graphene sheet was studied [334]. As an
example, the demetalation causes release of Fe2þ ions according to
the following schematic process: FeIIN4C12 þ 2Hþ /
Fe2þ þ H2N4C12. Both sites (FeN4C12 and FeN2þ2/C) showed ther-
modynamic stability against iron leaching by acids at pH ¼ 0
exhibiting the great resilience of these catalytic sites. However,
even though FeN4-like sites are thermodynamically stable in a
static condition, they are not stable when located in the open sys-
tem of a micropore network exposed to a fast flow of water [333]. In
stagnant acidic media the FeeN4eC structure is stable due to small
equilibrium constant of the demetalation process
(Fe2þN4Cx(s) þ 2Hþ(aq) # Fe2þ(aq) þ H2eN4Cx(s)). Nevertheless,
under dynamic conditions water would eventually leach the Fe2þ
ions out according to the Le Chatelier’s principle. The demetalation
of the FeN4 catalytic sites located in the micropores of a carbon
matrix was identified as being responsible for the fast decay of the
ORR current density of the FeeN4eC catalysts. To reveal the
fundamental function of iron in FeeNeC catalysts for O2 reduction,
a H2O2/H2SO4 mixture was utilized to oxidize the carbon scaffold
and selectively remove iron [335]. It was previously suggested that
Fe species protected from oxidation and dissolution by carbon
layers but close enough to the catalyst surface to remain catalyti-
cally active are vital for FeeNeC catalyst activity [336]. Selective
removal of Fe revealed that the maximum activity of FeeNeC car-
bon materials is reached for Fe contents between 0.2 and 0.5 wt%
and Fe is indispensable for achieving high ORR activity (in both
acidic and alkaline conditions) [335]. This observation is especially
significant given the number of examples of “metal-free” catalysts
in the literature. Catalysts without Fe or less than ca. 0.2 wt% Fe,
reduce O2 with larger overpotentials and only via the 2e pathway.
The selective removal of Fe by oxidation of the carbon matrix with
H2O2/H2SO4 can also be utilized as a good purification route for a
whole range of carbon nanomaterials.
5.2.3. Examples of metallic impurity artifacts in carbon-based
(electro)catalysis
In his extensive research presented over the last 10 years,
Pumera has questioned the validity of “metal-free” carbocatalysis
for a range of chemical reactions differentiating between studies in
which ICP-MS analysis was carried out to test for the presence of
trace metallic impurities and studies without such data [337,338].
As he noticed, less than 20% of reported studies on carbocatalysis
had included reliable spectroscopic techniques for detecting trace
metal impurities [337]. The lack of reliable and accurate impurity
assessments disqualifies the studied carbocatalysts as “metal-free”
(unless additional extensive control tests are performed). As
mentioned above, traces of metallic impurities may dominate the
catalytic properties of carbonaceous materials in both heteroge-
neous thermocatalysis and electrocatalysis [338]. This is true for
cases where carbon is used directly as an active catalyst or only as a
catalyst support. Numerous studies concern the effects of metallic
impurities in carbon nanostructures towards ORR, proving that
extensive metal removal decreases catalytic activity of the carbo-
catalyst, especially in acidic conditions [339]. If permanganate-
based oxidation techniques are used to prepare carbon
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W. Kicin
nanomaterials (e.g. rGO, graphene nanostripes by CNTs unzipping,
etc.) then the carbons obtained are contaminated with a large
amount of Mn (thousands of ppm) which totally dominates the
electrocatalytic response. Residual Mn impurities (0.83 wt%) in
graphene prepared by the Hummers’ method (from natural
graphite, Asbury Carbons) were proved to play a key role in the
electrocatalysis of the ORR on supposedly metal-free carbon elec-
trodes [340]. Even if graphene is prepared by the Mn-free Stau-
denmaier method (chlorate-based oxidation method) and despite
the Mn content being as low as 0.0018 wt% in the final material, this
metal still dominates the final catalytic properties. In the case of
rGO different methods of graphite exfoliation provide materials
with variant electrocatalytic properties [341]. It has been suggested
that the high ORR activity associated with trace Mn content reaches
the highest performance when Mn exists in the carbon scaffold as a
single atom-centered structure [342]. N-doped reduced graphene
oxide is able to coordinate Mn2þ ions in porphyrin-like structures
(MneN4) and such structures constitute exceptionally active sites
in ORR [343]. Purified graphene nanoribbons prepared by per-
manganate unzipping of carbon nanotubes were shown to contain
a low amount of metallic impurities (11.9 ppm of Mn-based im-
purities) yet the impurities still enhanced the electrocatalytic
properties of GNRs towards ORR [344]. As CNTs usually contain
native metallic impurities the unzipped tubes contained not only
Mn but also Fe (127.4 ppm), Mo (16.0 ppm), W (8.7 ppm), Ni
(5.0 ppm) and Co (4.5 ppm); ICP-MS. It was also shown that gra-
phene oxide nanoribbons synthesized through oxidative opening of
CNTs contained 13.0 ppm of residual Ni and that was enough to
alter the electrochemical behavior of the studied material [345].
These reports [344,345] challenged previous results presenting
nitrogen-doped GNRs prepared by CNT unzipping as “metal-free”
catalysts [346]. In another report the high electrocatalytic ORR
performance of hydrogenated graphenes prepared by chlorate- and
permanganate-based methods from synthetic graphite (99.9995%)
has been assigned not only to the hydrogenation of graphene, but
also to contamination with Mn and other metals present during
synthesis [347]. A significantly higher content of Mn (0.26 wt%,
XRF) in hydrogenated graphenes prepared from GO obtained via
the permanganate-based method was evident. Importantly, the
enhancement of catalytic activity was again tracked down to the
TM contaminants. It was also demonstrated that metallic impu-
rities introduced during the synthesis of graphene nanoribbons
including Mo (15.97 ppm), Fe (127.38 ppm), Mn (11.94 ppm), and W
(8.71 ppm, ICP-MS) acted as catalysts for the HER [348]. The elec-
trocatalytic activity of the GNRs towards HER was attributed mainly
to the W-based impurities. B/N co-doped rGOs prepared by the
Hummers and Hoffman methods from graphite (2e15 mm,
99.9995%, Alfa Aesar) also showed the synergy of B/N-co-doping
and metallic impurities in the enhancement of catalytic activity
for ORR [349].
Besides commonly studied ORR, many papers also suggested
that metal-free carbon-based materials are active catalysts for the
CO2RR. However, systematic comparison of the electrocatalytic
activity of pure graphite (which contained only ca. 4 ppm of Fe),
graphene oxide (which contained Mn (3800 ppm), Cu (120 ppm),
Fe (53 ppm) and Ni (4 ppm)), and carbon nanotubes containing Ni
(1200 ppm), Fe (90 ppm), Mn (11 ppm) and Cu (3 ppm) proved that
the observed activity was caused mainly by traces of Cu-based
impurities [350]. Thorough purification of the contaminated car-
bons in ultrapure nitric acid efficiently removed the impurities and
decreased the electrochemical activity. GO is often considered a
metal-free catalyst with intrinsic peroxidase-like activity attributed
to the inherent properties of oxygen functionalities and abundant
structural defects. However, in reality, due to the strong interaction
between TM ions and GO, trace levels of metals are present within
its structure. Fe contaminants in graphene and its derivatives are
responsible for the so-called “metal-free” peroxidase-like catalytic
activity [351]. Authors of this report recommended careful reas-
sessment of the real origin of activity in the peroxidase-like cata-
lytic reaction for all carbon nanostructures, since the catalytic
activity is not native to the carbon backbone but caused by TM
traces. Both SWCNTs and GO were once thought to possess intrinsic
peroxidase-like properties. Unfortunately, only EDX analysis was
used to prove lack of metallic impurities in the early reports
[352,353]. Eventually, irrefutable proof that metallic impurities at
trace level dominate graphene materials’ electrocatalytic proper-
ties was delivered by the electrochemical study of ultrapure gra-
phene materials [245]. An electrothermal vaporization was used to
obtain ultrapure graphene by heating rGO (produced from
99.9995% purity graphite by permanganate and chlorate methods)
to a temperature of 2500  C under dichlorodifluoromethane
(CCl2F2) acting as the halogen source and forming volatile metallic
halides. Importantly, trace concentrations of metallic impurities
like Mn and Fe in levels less than 1 mg/kg (1 ppm) were found by
NAA but could not be detected by ICP-AES. It was unequivocally
proved that manganese impurities are a key ingredient for the ORR
electrocatalytic activity of GBMs. At last, the key role of metallic
impurities in graphene-based electrocatalysis with significant in-
fluence observed for the ORR reaction was confirmed [245]. This
paper debunks the previous claims that metal-free graphene-based
materials exhibit some extraordinary intrinsic (electro)catalytic
activity. In fact, GBMs turned out to be pretty ordinary carbons. In
this regard, this report continues the legacy of Compton et al. [219].
When carbon materials are used as a support for noble metal
catalysts (Pd, Pt, etc.) the native metallic impurities within the
support can deactivate the noble metals. For instance, residual iron
present in N-doped CNTs at a level of only 40 ppm (ICP-AES)
significantly deactivated Pd catalysts in the process of nitrobenzene
hydrogenation [354]. A similar effect was observed for other com-
mon metallic impurities in carbon materials (Co, Ni, Mn, Cr, Cu, or
Zn). It was also shown that removing the residual growth catalyst
from N-functionalized CNTs is essential to achieve good reducibility
and high catalytic activity of the supported Pt nanoparticles in the
olefin hydrogenation catalysis [355]. Consequently, it is of the
utmost importance to carefully identify the composition and purity
of carbon materials if they are to be used as catalysts supports.
Otherwise the artifacts can totally dominate the obtained results
leading to false conclusions. This is especially important as N-
doped carbon constitutes an attractive support for metal NPs, yet
due to its affinity to metals, it is also prone to incidental
contamination.
In summary, carbon materials contain a variety of metallic im-
purities of various, often unforeseen, origins which may accumu-
late during the synthesis, post processing or in situ during
experimental studies (from solvents, glassware or metallic elec-
trodes/containers). A classic example is Mn contamination in rGO
(originating from KMnO4) which enhances the activity of
graphene-related materials in ORR. In hindsight, the artifacts
caused by Mn impurities in GBMs were in fact easy to predict as
parallel effects were observed earlier for SWCNTs. Metallic impu-
rities in N-doped CNTs prepared via metal-assisted catalysis
constitute another interesting example. Claims of metal-free
(electro)catalysis on heteroatom-doped and co-doped carbon
nanostructures should be revisited if these structures were pre-
pared using metal catalysts [356]. CNT samples purified by harsh
chlorination at 1000  C still contain as much as 140 ppm of Mn and
200 ppm of Co impurities (XRF), which are responsible for their
activity in the ORR [357]. Pure carbon nanotubes (without any
traces of transition metals) on the other hand do not exhibit a
noticeable catalytic effect towards the ORR. The problem of TM

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W. Kicin
artifacts in assumed metal-free carbon-based catalysis remains
relevant as a large number of new reports claiming metal-free
catalysis on carbons obtained via TM catalyst-assisted routes are
still being published [358]. Metallic impurities have recently been
identified in commercial carbon-based devices/materials, such as
graphene/polylactic acid (PLA) 3D-printing filaments [359]. The
graphene component of this commercial filament contains Al, Fe
and Ti impurities. This example visualizes that TM impurities can
easily slip through to final market products and seriously affect the
performance and lifetime of carbon-based devices.
5.3. Influence of TM impurities on the toxicity of engineered
carbonaceous materials
Commercial or prototypic nanomaterials that are near
commercialization are produced mainly as freely dispersible
nanoparticles [360,361]. The public has started to view nanotech-
nology as a potential hazard only recently. While nanoparticles
used in sunscreens (e.g. ZnO) and as bioimaging probes (e.g.
superparamagnetic iron oxides [362]) are considered non-toxic to
humans, they do have adverse effects on the environment. On the
other hand, the hazard caused by particles released from diesel
exhausts brought the issue of airborne nanoparticle toxicity to an
international crisis level [363]. Carbon-based materials such as
activated carbons have generally been considered benign to
humans and animals. Toxicity studies of carbonaceous materials are
currently focused on carbon nanostructures including carbon black,
carbon nanotubes, fullerenes, graphene-based materials and car-
bon dots [364,365]. CNTs or graphene-based materials are consid-
ered promising candidates for bioimaging, biosensing, drug
transport and bone tissue engineering [366]. Consequently, the
potential toxicity of such structures must be thoroughly examined.
Experimental data concerning carbon nanomaterial toxicity to
humans, animals and bacteria is truly extensive, yet the results are
often conflicting (e.g. toxic vs therapeutic effect of CNTs [367]). This
can be explained by the variety, complexity and heterogeneous
nature of these materials. For instance, the mechanism for inducing
toxicity for larger agglomerates of CNTs may be different from that
for individual tubes. The biological impact of carbon (nano)mate-
rials is governed not only by their native characteristics (structure,
size, morphology and chemistry), but also by their extrinsic prop-
erties (e.g. metallic impurities). Residual TM catalysts used during
the production of carbon materials significantly contribute to their
toxicity [368]. The toxicity of TM nanopowders is well-documented
and can be attributed in part to their diverse redox chemistry.
Similarly, metallic catalyst residues in carbon nanotubes/nanofibers
cause metal-induced toxicity, but only if the metal is included in the
carbon matrix in its bioavailable form. There are plenty of reviews
on the toxicity of carbon nanomaterials, mainly SWCNTs, and all of
them indicate residual metal impurities as one of the main sources
of toxicity [369e372]. CNTs can induce toxicity through oxidative
and non-oxidative processes. Oxidative processes cause imbalance
between the production of free radicals and the antioxidant de-
fense of cells, while non-oxidative toxicity relies inter alia on me-
chanical damage of the cell membrane. While the presence of
metals in CNTs contributes to their toxicity, it is not the only
responsible factor, as even “bioavailable metal-free” carbon nano-
tubes can induce deleterious effects [371]. In addition, discrep-
ancies between studies of carbon (nano)materials toxicity are
partly due to an overlap of the two main effects of purification on
the final material structure: removal of catalytic impurities with
simultaneous introduction of surface functional groups. As several
parameters of carbon materials change after metal removal, it is
difficult to determine which factor contributes most to the possible
toxic effects. Depending on the properties of the external biological
787
environment (pH, ionic strength, complexing agents, etc.) and the
properties of the metal present in the carbon matrix, either negli-
gible or significant quantities of metal ions can be mobilized from
the material into the surrounding fluids. Contradicting results of
toxicological studies are also caused by the differing bioavailability
of metals within different batches of CNT samples, so certified CNT
standards are required to obtain comparable results. In fact, due to
significant batch-to-batch variability of carbon nanostructures, re-
ports on their toxicity are irreproducible. The content of metallic
impurities in commercial samples of CNT soot varies significantly,
yet the degree of metal catalyst contamination of a sample is often a
determining factor for the magnitude of its toxicity [373]. For
instance, early research on the pulmonary toxicity of SWCNTs
showed that they induce dose-dependent lung lesions (in mice)
regardless of the type and content of metal impurities, although
SWCNTs containing Ni yielded a higher mortality rate [374]. Papers
exploring single- and MWCNT toxicity reported redox imbalances
in exposed cells and metallic impurities-induced oxidative stress is
regarded as the most likely mechanism. Fe impurities have been
extensively linked to oxidative stress enhancement due to the
Fenton reaction. TM ions released from CNTs transform cellular
oxygen metabolic products such as H2O2 into highly reactive radi-
cals [375]. They catalyze overproduction of reactive oxygen species
(ROS) such as superoxide anion (O 
2 ) and hydroxyl radical (HO ), as
well as reactive nitrogen species. Excessive levels of ROS may
overwhelm the protective effects of endogenous antioxidants and
result in total cell damage [370]. For instance, nickel oxide in
SWCNTs affected the redox properties of the regulatory peptide L-
glutathione, which is an antioxidant protecting cells from oxidative
stress [237]. CNTs containing Fe impurities alter the iron meta-
bolism of biological systems in a similar manner as observed earlier
for asbestos. The presence of transition metals (ferrous and ferric
forms of iron (Fe2þ/Fe3þ)) is responsible for the carcinogenic
properties of asbestos [376]. Similarly, the presence of iron impu-
rities and fiber morphology are the main reasons behind the
asbestos-like toxicity of CNTs [377]. As observed, asbestos and raw
(unpurified) SWCNTs caused a similar Fe-related response in a
human cell model [378]. While iron can act as both an essential and
a toxic element for biological systems, its presence as an impurity in
CNTs has been identified as a main cause of oxidative stress. To
clarify the mechanisms underlying MWCNT-induced toxicity cor-
relation to Fe contamination, two MWCNT samples differing only in
the presence or absence of iron were utilized [379]. Only the Fe-rich
MWCNT samples induced strong cellular oxidative stress in
exposed murine alveolar macrophages, while Fe-free MWCNTs did
not exert any visible toxic effects. However other reports still
document contradictory observations. As purification changes the
physicochemical properties of CNTs, methods that do not alter CNT
structure and chemistry are urgently sought to decouple the native
toxicity of CNTs from the removal of metallic impurities. As recently
shown, purification by Cl2 treatment at 800  C allows selective
removal of metallic impurities from MWCNTs, while the purified
nanotubes (with purity of about 98.5 wt%) remained untouched
[380]. This approach demonstrated that metallic impurities were
not involved in the cytotoxicity of this particular type of MWCNTs,
since the toxicity was basically the same for CNTs before and after
the Cl2 purification. Interestingly, a study of similar type where
MWCNTs are purified through traditional liquid-based purification
(KOH/HNO3 leaching method) showed that purified MWCNTs had a
greater toxicity than raw MWCNTs [381]. This might be due to the
harsh purification conditions, which considerably altered CNT
structure and surface properties. Metal impurities within MWCNTs
have direct and indirect effects on cells. For instance, the Mo-based
contaminations in raw MWCNTs affect their agglomeration degree
and therefore determine the toxicity mechanism in human cells
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W. Kicin
[382]. The chemical state of the metal is also important, as MWCNTs
containing MoS2 impurities caused higher toxicity as compared to
nanotubes containing only Mo phase.
Importantly, it has recently been observed that the biological
identity of the CNTs is indeed determined by their metal impurities
[383]. By using SWCNTs containing Fe impurities (HiPco, Nano-
Integris), it was demonstrated that oxidation of cellular proteins
by CNTs is mediated by metal ions originating from the residual
catalysts. Ge et al. tried to quantify the contribution of metal resi-
dues and the fiber structure to the toxicity of SWCNTs [384].
Nanotubes with a total metal content between 2.1 and 15.3 wt% (as
determined by ICP-MS) were studied. It was found that the metal
residues had a dominant role in cytotoxicity while the effect of the
fibrous morphology of SWCNTs on cell viability was limited. In
contrast to other metal species (Ni or Y), iron played a major role in
promoting intracellular ROS production. As noted, the concentra-
tion of Fe in SWCNT determines the extent of extracellular oxida-
tive stress as well as intracellular depletion of antioxidant reserves
and accumulation of lipid peroxidation products in macrophages.
This is in line with former reports which showed that non-purified,
Fe-rich SWCNTs (26 wt% of Fe) were more effective in generating
hydroxyl radicals than purified ones (0.23 wt% of Fe) [385]. Corre-
lations between a dose- and time-dependent increase in intracel-
lular ROS and a decrease in the mitochondrial membrane potential
with metal containing CNTs were repeatedly confirmed by an
extensive experimental data [386,387]. When lung cells were
incubated with commercial single- and MWCNTs as well as an acid-
treated SWCNT with reduced metal catalyst content (1.3 wt% of Co
and 1.2 wt% of Ni) it was observed that the purified SWCNTs had no
toxic effect [386]. To elucidate the role of iron in SWCNT toxicity to
human cells at different metal concentrations, raw (Fe < 30 wt%),
purified (Fe < 15 wt%) and highly purified SWCNTs (Fe < 2 wt%)
SWCNTs were considered [387]. Cells treated with raw SWCNTs
showed a severe alteration of iron distribution/content while
highly purified nanotubes did not alter cellular iron metabolism.
The effect was attributed to the iron impurities in SWCNTs in a
dose-dependent manner. This observation was later confirmed as it
was shown that raw SWCNTs alter the iron metabolism of the
studied cell model similarly to crocidolite, while exposure to pu-
rified SWCNTs induces marginal alterations [378]. It was also
shown that exposure of neuronal cells to even moderate concen-
trations of MWCNTs with a high iron catalyst content (of ca. 12 wt%
vs 4.2 wt%) adversely affects cell viability [388]. Studies of in vitro
effects of MWCNTs with different content of metallic impurities
(0.16 vs 2.4 wt% of Fe) on the status of immune cells in healthy
volunteers delivered similar conclusions [389]. In comparison to
purified materials, unpurified MWCNTs induced significant mito-
chondrial dysfunction. Such results show that efficient purification
procedures can reduce the toxic effect of carbon-based materials.
MWCNTs with impurities did indeed induce immunological
toxicity when implanted in mice, whereas extremely clean tubes
purified via annealing at 2800  C (Fe content < 20 ppm) showed
excellent biocompatibility [390]. High-temperature annealing is
indeed one of the most effective ways to improve carbon material
biocompatibility and reduce transition metal-induced toxicity
[390,391]. However, a question remains: how much metallic im-
purity is enough to induce a toxic effect? Basically, questions like
this do not apply to the field of carbon nanostructures as their
toxicity is simultaneously affected by a whole range of factors. For
instance, for MWCNTs thermally treated at 1800  C as little as
80 ppm of Fe present on the tubes’ surface already caused gener-
ation of toxic ROS, whereas the origin of the toxicities for the as-
grown tubes (containing as much as 12000 ppm of Fe) was
attributed to the carbon-based impurities and functional groups
instead of metallic impurities [390].
Hurt et al. introduced the concept of bioavailability of metallic
impurities despite their seemingly impermeable encapsulation
inside the CNT structure [392,393]. As now known, the carbon
shells encasing metallic particles are never totally leak-proof and
metal ions can diffuse through the graphitic shells especially since
additional post-processing causes shell damage. As demonstrated,
commercial raw and purified CNTs with Fe content ranging from
1.21 to 22.2 wt% and Ni content from 3.15% to 24.1 wt% released as
much as up to 7% of Fe and up to 9% of Ni upon interaction with the
surrounding physical fluid [392,393]. What is worse, Fe and Ni
bioavailability varies greatly from sample to sample and cannot
easily be deduced from the initial metal content. In another
experiment two samples of MWCNTs with Fe impurity of 9 ppm
and 4206 ppm (XRF) were used to measure iron leakage in a culture
medium and under two different conditions: one mimicking the
lysosomal environment (pH ¼ 4.5) and the other the cellular
cytoplasmic environment (pH ¼ 7.2); both at 37  C [394]. For
MWCNTs containing 4206 ppm of initial Fe, significant metal
release in the acidic condition and no release in the neutral con-
dition and the culture medium were observed. In contrast, the
sample with only 9 ppm of Fe (ICP-MS) did not release a measur-
able amount of iron under either condition. Consequently, the iron-
mediated MWCNT cytotoxicity was correlated with the intracel-
lular accumulation of iron released from the nanotubes in an acidic
lysosomal environment. It must also be noted that metal bioavail-
ability is sensitive to sample age and additional post-processing
(sonication, mechanical grinding, etc.) that may expose fresh
metal phase. Ultrasonication is a common procedure used to purify
carbon nanomaterials and obtain homogeneous dispersions, but it
also promotes the mobilization of metallic impurities. As observed,
even if most of the iron or nickel was indeed encapsulated in CNTs
and not mobilized by ultrasound (93e99%), a small fraction was
fluid-accessible and sufficient to induce toxicity [395]. A study of
the fate of SWCNT after their internalization by macrophages
showed that although Fe residues are initially isolated from bio-
logical media by their carbon shells, they become accessible to the
biological environment via a pH-dependent mechanism as low pH
facilitates metal mobilization [394,396]. Targeted removal of the
bioavailable fraction of TM impurities indeed allows some degree of
carbon material detoxification [393,397]. Interestingly, studies of
biological responses to MWCNTs devoid of bioavailable iron hinted
that increases in redox-active iron could be related to the release of
endogenous iron [398]. Most studies of the metal-induced toxicity
of carbon nanomaterials concern CNTs [372]. However residual
metallic phases can also be found in chemically modified graphene
materials. Toxicological studies of graphene-based materials also
yield conflicting data, e.g. such materials can either inhibit or
enhance bacterial proliferation. GO usually contains high levels of
mutagenic Mn and Fe residues [399]. It has been confirmed that the
bactericidal properties of GO are critically dependent on its purity
and the method of preparation [400]. However, it was also
observed that the metallic elements detected in GO samples were
not responsible for the antibacterial properties of both unwashed
and thoroughly washed GO samples (containing respectively the
following amounts of metals (in ppm) for unwashed vs washed GO:
Cr 15.51 vs 14.71, Mn 7871.50 vs 1734.83, Fe 240.41 vs 137.05, Co
0.99 vs 1.63, Ni 3.57 vs 3.76), since the concentration of each metal
was below the inhibitory level to have a detrimental effect on
bacteria [400]. Poor control of the purity of the GO hinders its
biomedical applications [401]. Generally, GO of a certain purity
does not induce significant cytotoxic responses. But once again,
“certain purity” remains elusive as chemically modified graphene
samples are in reality an extremely diverse group of entities.
While the direct toxicity of carbon nanomaterials in humans and
animals is of critical importance, the long-term consequences of

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environmental pollution by carbon-based materials may cause
serious health-related repercussions. CNT or fullerene soot can
release toxic metals into aquatic environments [402,403]. The
levels of metal impurities that may leak out from carbon nano-
materials into natural waters over a long period of time must be
closely monitored and quantified. For instance, nickel can be
leached out from high-purity commercial CNTs (<2% dry weight
ash) at levels that are toxic to amphipods [404]. Studies of five
different commercial CNT samples representing three different
common manufacturing processes (HiPCo, electric arc-discharge
and a CoMoCAT) both purified and raw were performed to esti-
mate the extent and kinetics of metal leaching [405]. As could be
expected, metals leach out even from the purified commercial CNTs
and the leaching is higher in lower pH conditions. Long-term (90
days) leaching of metals from SWCNTs containing either Ni, Y, Fe,
Co, Mo or combinations of these metals was also studied in fresh-
water, seawater, wastewater and groundwater [406]. The dynamics
of leaching vary between the different CNT sets and their respective
metal impurities (e.g. Fe is released much quicker than Ni). To
complicate matters further, once metals are released from CNTs
they can be re-adsorbed on their surface. To investigate this issue,
the impact of four different single- and multi-wall CNTs and hy-
droxylated and carboxylated MWCNTs on Cd toxicity to aquatic
organisms was examined [407]. The toxicity-increasing effect of all
CNTs was caused by inherent catalyst impurities from the pristine
CNTs, whereas enhanced adsorption of Cd onto functionalized CNTs
was the key factor contributing to the enhancement of their
toxicity.
To conclude, metallic impurities within carbon (nano)materials
significantly contribute to their toxicity. Fe residues in particular
have been repeatedly associated with the geno- and cytotoxicity of
CNTs. However, the extent of TM contribution to carbon-based
material toxicity is difficult to assess due to their diversifity and
the complexity of carbon/metal systems. As a result, there is no
certain type and amount of metallic impurities that can be labeled
as toxic. In some cases, materials with only tens of ppm of TM
impurities can be toxic if the metal is bioavailable; in other cases,
materials with several percent of TM impurities may still not show
any toxic effects. It is ironic that purification of carbon-based ma-
terials is so difficult due to their tight carbon shells protecting
metallic NPs, yet in biological or electrochemical applications such
carbon-encased metals do leak out from the seemingly imperme-
able graphitic cases. Nevertheless, thorough metal purification
decreases the risk of carbon (nano)materials to health. Finally, one
must consider that the contrasting results concerning carbon ma-
terials toxicity can also be attributed to the variability of the applied
specific experimental procedures. Results concerning the toxicity of
carbon engineered materials will remain conflicting and for now
there is no reason to believe that this situation will be clarified
anytime soon. It is also interesting to note that unlike its effect on
animals, the catalyst residue present in CNTs has rather little effect
on plant growth [408].
5.4. Metallic impurities and the intrinsic magnetism of graphenic
carbon structures
The magnetic materials currently utilized employ elements of
either the d- or f-block of the periodic table. Magnetic ordering in
TMs, e.g. in Fe, Co and Ni (which are ferromagnets at room tem-
perature) stems from their partially filled d-electron bands. Yet the
field of magnetism of light elements, especially carbon-based ma-
terials, has been under scientific scrutiny for decades [409]. It is
now commonly accepted that despite the absence of d or f elec-
trons, magnetism in carbonaceous materials can exist under a va-
riety of experimental conditions. In fact, experimental evidence
789
obtained within the last 20 years practically eliminated all doubt
that ferro/ferrimagnetism is indeed intrinsic to graphite structures
containing certain kinds of defects (defect-induced magnetism
(DIM)) and not induced by extrinsic magnetic impurities [184]. As
CNTs and GNRs may exhibit a magnetic ground state, utilization of
the magnetic response of low-dimensional carbon structures in
spintronics will allow construction of a carbon-only spin logic
system [410,411]. Defect-free CNTs and graphene are considered
non-magnetic, but the presence of defects might induce magnetism
even in undoped graphenic structures. Nevertheless, experimental
observations of inherent carbon magnetism are seriously hindered
by the presence of magnetic impurities (transition or rare earth
elements) which usually dominate the magnetic response [154].
Despite numerous theoretical predictions of interesting magnetic
properties of carbon nanostructures, there are only a few reports on
the direct experimental measurements of the magnetic suscepti-
bility of structures like SWCNTs. This is because nearly all available
SWCNT samples contain ferromagnetic particles. Even after
extensive purification, a tiny fraction of remaining impurities still
overshadows the low intrinsic magnetic susceptibility of SWCNTs
(which is in the order of ~106 emu/g) [412]. To correctly interpret
the magnetic behavior of carbon-based materials, the exact content
and nature of magnetically active elements (e.g. Fe, Co, Ni or Mn)
must be precisely determined. In contrast to SWCNTs, there are
more reports on the magnetic susceptibility of MWCNTs, as they
can be produced without magnetic catalysts. Since the magnetic
response of SWCNTs is predicted to be in the order of units to tenths
of mB (Bohr magneton), its measurement is disrupted by the
response of randomly dispersed magnetic atoms (single mB) or
larger magnetic clusters (tens of mB) [154,412,413]. As little as
50 ppm of Fe can induce significant extrinsic ferromagnetic mo-
ments in carbonaceous materials. Consequently, before attributing
the ferromagnetic signal observed in graphite, CNTs and related
materials to intrinsic defects, it is necessary to reduce the iron
impurity content to low ppm or even ppb levels [414]. A truly
metal-free carbon sample must be obtained to unequivocally assess
the magnetic properties of carbon materials, yet such materials are
rarely available [415].
Various kinds of defects (e.g. vacancies, strains, hydrogen or
other heteroatom-doping) can induce magnetic order in carbon-
based solids. DIM has been studied mostly in graphite and gra-
phene [409,416]. Sepioni et al. pointed out that studies of magne-
tism in graphene and graphite require careful consideration of the
interference of ferromagnetic inclusions (e.g. Fe, Fe3C) [417,418]. By
applying particle-induced X-ray emission, it was shown that sub-
stantial contamination with magnetic elements can be found at the
side-faces of a range of commercial HOPG samples provided by
different producers [184,419]. These impurities (mainly Fe and Ni)
originate from the cutting of the HOPG samples (prior to shipping)
using stainless-steel tools. The amount of such incidental impu-
rities can significantly surpass the impurity concentration in the
bulk of HOPG and hence prevents correct measurement of the
magnetic contribution from defect-induced magnetism in appar-
ently pure HOPG. The main impurity that can contribute to the
magnetic response of commercial HOPG samples is Fe with a
maximum concentration of ~23 mg/g determined for ZYH grade
samples provided by Advanced Ceramics (Momentive Performance
Materials) [184,419]. This example proves presence of metallic
impurities in most commercially available carbon samples, even
those of the seemingly highest purity. Thorough purification is
mandatory prior to using HOPG samples in contamination-critical
studies and applications. However, even precise determination of
the metallic impurity content in carbonaceous materials is still not
enough to correctly study their magnetic properties. It is also
equally important to characterize the form in which metals occur. If
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the metallic impurity is in the form of nanoparticles and not just
single atoms or evenly distributed small clusters, metal-induced
magnetism usually exceeds the signal from pure CNTs in several
orders of magnitude [200,420]. This is true even if the overall
amount of the impurity in the sample is low. For instance, it was
proved that commercially available super-purified SWCNTs (HiPco,
Unidym Inc.) are not suitable for reliable studies of nanotube
magnetism because they still contain Fe3C impurities [420]. Even if
a whole range of macroscopic analytical methods indicate high
SWCNT purity, a non-negligible amount of metallic phase may still
be present and dominate their magnetic properties. In fact,
magnetization studies can be utilized as a very sensitive tool to
measure the amount of magnetic impurities in carbon matrixes;
the value of the saturation magnetization allows estimation of the
amount of the magnetic phase present in a sample [200]. However,
to determine extremely low metal contents within carbon-based
structures, local and element-sensitive probes such as the
extended X-ray absorption fine structure must be utilized [144].
Utilization of non-magnetic metallic catalysts to prepare CNTs
or purification via high temperature annealing can yield truly
diamagnetic samples - as expected for a pure, metal-free carbon
structure [421]. Single-, double-, and multi-wall carbon nanotubes
have been obtained without magnetic impurities utilizing the Re
catalyst-based CVD technique. This approach yielded non-magnetic
nanotubes with diamagnetic Re particles [422]. In addition, CNTs
prepared with a Fe catalyst were purified via annealing at 2500  C
under Ar for 2h, which allowed virtually complete vaporization of
the catalyst. ICP-MS and AES analyses proved that after the high-
temperature treatment, Fe concentration decreased below
10 ppm. Detailed magnetic studies showed that both approaches
yield materials with a clear diamagnetic behavior typical for pure
carbon nanotubes with no interference from ferromagnetic or
paramagnetic materials [422]. Utilization of non-magnetic catalysts
(e.g. PtRhRe) is indeed a convenient way to obtain magnetic
impurity-free SWCNTs [205,423]. Such SWCNT samples are
attractive for fundamental studies of their superconductivity or
NMR analysis since many spectroscopic techniques require
magnetically pure carbon samples [424]. Magnetic measurement
methods are very sensitive to para- and ferromagnetic impurities,
yet they are unable to discriminate between the impurity and the
material’s intrinsic properties. This problem was well documented
with EPR studies conducted on SWCNTs containing traces of
metallic impurities. However, even though ferromagnetic catalysts
can be replaced by nonmagnetic PtRhRe catalysts, other carbon
properties (thermal, electrical, etc.) can still be dominated by the
difficult-to-remove metallic phase. Microwave digestion using aqua
regia was employed for the removal of the PtRhRe catalyst from
CNTs yet the catalyst content was still as high as 2.8 wt% after
multiple purification treatments [423]. Ultracentrifugation of raw
SWCNTs obtained with a PtRhRe catalyst was proven to be an
effective method to eventually obtain catalyst-free SWCNTs [425].
Truly metal-free SWCNTs showed negligible EPR signals at the X-
band. EPR signals were only detected in samples containing catalyst
particles, indicating that it was the interactions between the metal
catalyst and the surrounding carbon which contributed to the EPR
signal [425]. Para- and ferromagnetic impurities (for instance Mn
and Fe) are also common in rGO and other graphene-based mate-
rials, prohibiting studies of their fundamental properties. To
circumvent this issue, a method to prepare paramagnetic metal-
free graphene nanosheets based on SnCl2 as a reducing agent of
GO was proposed [426]. Sn compounds are diamagnetic. Compared
to the chemical reduction of GO using hydrazine or iron, the ob-
tained rGO did not contain any paramagnetic metallic impurities.
SnCl2 and its reduction products are easily soluble in hydrochloric
acid which assured high purity of the obtained rGO.
Numerous research groups utilized magnetic filtration to pre-
pare magnetic phase-free SWCNTs [412,427]. For instance, Kim
et al. obtained a diamagnetic response from a purified SWCNT
sample, where the SWCNT material with ferromagnetic impurities
reduced below 0.013 emu/g was obtained by chemical treatment
and magnetic gradient filtration [427]. Yet the magnetic suscepti-
bility of 5  106 emu/g they observed was an order of magnitude
higher than the theoretical prediction. This discrepancy between
theory and experiment was attributed to contributions from ferro-
or paramagnetic impurities. Similarly, superconductivity observed
in ropes of CNTs has been attributed to the presence of TM impu-
rities [428]. Traces of magnetic impurities can dramatically influ-
ence nanotube electrical properties. As little as 10 ppm of magnetic
impurities imposes a drastic effect on the electrical transport
properties of SWCNTs. It was shown that the interaction between
the magnetic moment of the metal atom and the spin of the con-
duction p-electrons of the nanotubes affect the transport behavior
due to the Kondo effect [429]. However, the presence of magnetic
impurities within graphenic carbon matrixes can also yield coun-
terintuitive results. For instance, as deduced by DFT calculations,
interactions of iron impurities with the electronic structure of
defected graphene systems could result in decreased magnetic
signals instead of enhancing any possible intrinsic carbon magne-
tism, due to the occurrence of spin pairing between carbon and iron
[430]. It was also reported that graphane nanostripes (hydroge-
nated graphene) prepared by unzipping CNTs exhibited ferromag-
netism significantly exceeding the concentration of all possible
magnetic impurities (Co (2200 ppm) and Fe (110.6 ppm), ICP-AES)
[431]. As elucidated, the interplay of metallic nanoparticles and
defects in the nanostripes can lead to a spin polarization and in-
duction of the ferromagnetic moment. Eventually, other basic
physical properties of carbon structures, e.g. the heat capacity of
bundles of SWCNTs, can also be affected by metallic impurities. For
instance, specific heat measurement was obscured at low temper-
atures because of nuclear hyperfine interactions in metallic impu-
rities (Ni, Co) [432].
5.5. Influence of metal impurities on the adsorption capacity of
carbon nanostructures
Activated carbons are one of the most common adsorbents used
for water and air purification over decades. High-surface-area
microporous carbons and their composites are also considered
promising media for gas storage. Adsorption of heavy metals and
pharmaceuticals from water and hydrogen storage are the main
applications of interest. Recently, more advanced forms of carbons
such as graphene and CNTs have been extensively studied for such
applications. Even though CNTs have been advertised as promising
adsorbents for the removal of heavy metals from water, the influ-
ence of residual metallic catalysts within the tubes was rarely
studied. And yet it was shown that metallic impurities present in
commercial CNT samples can dominate their capacity for metal ion
sorption [433]. CNTs containing up to 10 wt% of ash (mainly Co and
Mo) were studied as adsorbents of lead. Metallic impurities
released from the commercial CNTs reacted with Pb(II) and caused
its precipitation. Release of MoO2
4 caused precipitation of PbMoO4,
which was the dominant mechanism for the CNTs’ apparent lead
adsorption. The negative influence of metallic impurities on sorp-
tion properties was also observed for graphene oxide. GO has a
strong affinity to metallic ions, which quickly occupy available
active sites. As shown, metallic ions adsorbed on the surface of GOs
not only had a negative influence on the maximum adsorption
capacities of methylene blue, but also adversely impacted its
adsorption rates [434]. Purified GO exhibited enhanced equilibrium
capacities and improved adsorption rates.

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Graphitic nanofibers and CNTs were once considered attractive
materials for hydrogen storage [435]. In 1997, it was announced
that CNTs are capable of absorbing up to 10 wt% of hydrogen and
soon after this work other very optimistic conclusions on the
hydrogen storage capacity of CNTs at room temperature were re-
ported [436,437]. However, it was soon realized that carbon
nanostructures cannot store the amount of hydrogen required for
any practical application at moderate pressures and room tem-
peratures. A comprehensive study of several carbon structures
proved that claims of more than 1 wt% of H2 adsorption capacity at
room temperature for carbon nanotubes are erroneous [438]. In
fact, the sorption capacity of CNTs for H2 is so low that one must pay
special attention to calibration procedures to get reliable results
[439]. The value of 10 wt% reported in 1997 [436] was the result of
an erroneous extrapolation because the examined sample of
SWCNTs contained only 0.1e0.2 wt% of carbon nanotubes and the
rest of the powder was carbon soot and cobalt particles. It was
incorrectly assumed that H2 was stored only in the nanotubes, but
the tubes constituted only a fraction of the entire sample and
contribution from the Co particles was not considered. Nowadays
these overoptimistic reports on the H2 storage capacity of CNTs are
considered the most controversial episode in carbon nanotube
science [439]. Besides errors in measurements and calculations,
metallic impurities have been identified as the main contributors to
the erroneous conclusions concerning the H2 adsorption capacity of
SWCNTs [440e442]. For instance, post-treatment can contaminate
the single-wall carbon nanotubes with metal particles which may
then dominate H2 adsorption capacity at room temperature and
ambient pressure [440]. SWCNT samples were sonicated in HNO3
using an ultrasonic TieAleV alloy horn. The goal of this treatment
was to open the carbon nanotubes to increase their H2 storage
capacity. And indeed, the storage capacity increased with the
sonication time. However, this treatment incorporated metal par-
ticles from the ultrasonic probe material into the carbon material
and the hydrogen uptake was caused solely by the Ti-alloy particles
and not by opening access to the interior of CNTs. Similar results
were obtained for as-produced (containing 25 wt% of Ni) and pu-
rified SWCNT samples [441]. The increase in H2 sorption was pro-
portional to the increase in Ni concentration. As a result, the
presence of metal particles in CNT samples introduced during post-
treatment or as residual catalyst particles enhanced H2 adsorption
capacity and led to false claims concerning the hydrogen storage
capacity of carbon nanostructures.
5.6. Metallic impurities govern the reactivity of carbon (nano)
structures, their mechanical strength and the stability of their
composites
The surface of perfect graphene or a large-diameter carbon
nanotube is chemically inert. In fact, unlike in electronic applica-
tions where defect-free CNTs are of interest, defective and func-
tionalized carbon nanostructures are more attractive for (electro)
chemical applications. However, defects and functionalization must
be precisely controlled to achieve the desired material perfor-
mance. For this reason, when the chemical properties of carbon
(nano)structures are studied, their purity and composition must be
determined since impurities affect the materials’ reactivity. For
instance, a combination of group 6 transition metals (e.g. Cr, Mo, W)
with SWCNT or graphene is a promising strategy to build
SWCNTSWCNT or graphene-graphene junctions through the
formation of TM(SWCNT)2 or TM(graphene)2 complexes, analogous
to Cr(C6H6)2. Two nanotubes (or graphene sheets) act as ligands in
such structures and they can be connected by a single transition
metal atom (Fig. 6). However, this type of functionalization is
difficult to control in practice, as formation of such single atom
791
junctions is extremely sensitive to oxidation (of the zerovalent
group 6 metal species) by a residual metal catalyst (especially iron
oxide catalyst used for the growth of the SWCNTs) [443]. As a result,
only exceptionally pure carbon nanomaterials should be selected to
synthesize TM(SWCNT)2 or TM(graphene)2 complexes. Similar side
reactions are also possible in the case of Li/NH3 reductive mixtures.
Li metal/liquid ammonia can be used for the Birch reduction as a
way to covalently functionalize SWCNTs without damaging their
walls [444]. However, Fe residues in SWCNT cause quenching of the
reduced SWCNT species and eventually lead to poor
functionalization.
Another interesting example of the detrimental effect of
metallic impurities present in carbon materials is the production of
polymer composites. Carbon fibrous nanostructures are frequently
studied as fillers to produce reinforced nanocomposites. CNTs and
CNFs are being used in a variety of organic and inorganic polymer
matrices. Epoxy resins/carbon nanostructure composites in
particular are considered attractive for electronics and aeronautic
applications. However, results regarding the effect of carbon
nanotube fillers on the cure process of epoxy resin are contradic-
tory [445]. It was shown that raw CNTs accelerated the formation of
branched polymeric chains during the epoxy/CNT nanocomposite
formation. Metallic residues in the CNT samples act as hydrogen
donor catalysts and induce the cure process at its early stages [446].
In the case of epoxy matrix composites reinforced with SWCNTs,
purification of the nanotubes from metallic and carbonaceous
residues was shown to have critical impact on the thermal prop-
erties of the final composite [447]. Purification yielded a twofold
increase in composite thermal conductivity but at the expense of
electrical conductivity, which decreased by at least two orders of
magnitude. As a result, metallic impurities within CNTs affect not
only the composite’s formation, but also its final properties such as
stability, conductivity, flame retardancy and mechanical strength.
Fe impurities of as-prepared CNTs play a catalytic role in both the
polymer’s degradation process and its flammability [448]. Another
interesting example is the Lyocell composite. Dissolution of cellu-
lose in N-methylmorpholine-N-oxide monohydrate (NMMO),
known as the Lyocell process, is utilized for wet processing of cel-
lulose to produce fibers for textiles. NMMO dissolves cellulose
without its derivatization owing to its strong NeO dipole. The
Lyocell fibers have a high strength and their properties can be
additionally enhanced by carbon-based additives. A variety of
Lyocell/CNT composites have been proposed [449]. Reactivity of the
carbon additives influences the complexity of reactions in the cel-
lulose/NMMO system, yet the influence of metallic impurities on
the process and the final composites has rarely been reported.
Heavy metals interfere with the hydrogen bond system of cellulose
and NMMO, initiating side redox reactions [195]. Consequently,
evaluation of metal content in carbon additives for the Lyocell
process is required, as such impurities affect reaction paths in the
cellulose/NMMO system leading to composites of unpredictable
properties (for instance with lower thermal and mechanical
stability).
Metallic particles also have detrimental effect on the mechanical
stability of carbon nanotubes and their inorganic composites.
Thorough acid purification of commercial CNTs has been shown to
prevent strength degradation of a sintered CNT/Al2O3 composite.
Otherwise TM catalyst particles in CNTs weaken such compositions
[450]. Impurities in raw MWCNTs might evolve into micro-defects,
producing stress concentration and cracks propagation in com-
posites [451]. However, TM residues affect not only the mechanical
strength of CNT/polymer composites but also the mechanical
properties of the tubes themselves. The interactions between
defect-free single-wall CNTs and Ni or Fe nanoparticles depend on
the metal type and its chemical state [452]. Pure metals bond more
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strongly to CNTs than their oxides and hence zero-valent metal NPs
significantly reduce the strength of the CNTs, whereas oxidized NPs
have only limited detrimental effects. The mechanical failure of a
tube is due to a chemical weakening of the CeC bonds via a charge
transfer between the CNT and the metal NP. The Fe NPs weaken the
mechanical strength of the tubes to a larger extent than the Ni
particles. As known, carbon fiber-reinforced composites are
commonly used in the automotive and aerospace industries. Yet,
such composites can be additionally reinforced by adding carbon
nanotubes. Direct growth of CNTs on the carbon fiber surface
catalyzed by metal nanoparticles is a promising approach to as-
suage the stress concentration around the fibers but strong bonds
between the tubes and the fiber surface are required. The catalyst
particles present at the CNT/fiber junctions lower the stress value at
failure and worsen the mechanical properties of CNT/fiber com-
posites [453]. Fe or Ni nanoparticles weaken the CeC bonds at the
junction which leads to a reduction of fracture strength. The pres-
ence of oxygen atoms prevents the formation of NieC bonds due to
preferential formation of more stable NieO bonds and hence limit
the weakening effect of the Ni nanoparticle. The chemical weak-
ening of CeC bonds and crack-tip stress reduction have also been
observed in Liegraphene composites [454].
Another aspect of carbon nanostructures’ reactivity is their
pyrophoricity induced by metallic impurities. Transition metal
nanopowders (Fe, Ni, Co, etc.) are pyrophoric. Since iron is widely
used as a catalyst in the synthesis of CNFs and CNTs, safety pro-
cedures in manufacturing must consider material flammability. It
was demonstrated that exposure of as-produced HiPco SWCNTs to
a camera flash causes their ignition, while purified SWCNTs do not
respond to such stimuli [455]. This effect was assigned to the py-
rophoric oxidation of Fe particles. It was later proved that pyro-
phoric iron NPs even in small quantities (below 1 wt%) can trigger
the ignition of carbon nanofibers and facilitate propagation of their
combustion [456]. Tests of commercially available carbon nano-
fibers produced via CVD on iron catalysts (Pyrograf Products, Inc.)
were conducted for the as-received and purified CNF samples. Fe
nanoparticles exhibited a promotional effect on CNF explosibility.
However, the explosion risk was lowered when CNF samples were
purified by vacuum annealing, due to the reduction in Fe content.
While the raw CNFs contained 1.4 wt% of Fe, annealing at 1500  C
and 3000  C reduced the Fe content to 1.2 wt% and 100 ppm,
respectively [456].
6. Purification of carbon-based materials from TM impurities
6.1. Removal of TM impurities from CNTs: a review of the main
achievements in 30 years of research
Most of the research devoted to carbon material purification
from metallic impurities concerns carbon nanotubes, especially
single-wall carbon nanotubes. Since the first globally-recognized
report on CNTs published in 1991, it was obvious that effective
purification, refining and separation methodologies (and not an
efficient synthesis method) would determine the future of these
materials. Even though the volume of research concerning CNT
purification is overwhelming, widely used purification methods
still need further improvement. Applications of carbon nano-
structures in advanced technologies remain challenging or even
precluded due to, inter alia, residual metallic impurities. Even if
metallic particles are tightly covered by graphitic shells they can
still interfere during electronic, electrochemical and medical ap-
plications, and hence techniques for their complete removal are
constantly pursued. While some scientists may consider purifica-
tion of carbon nanotubes as an already solved and outdated sci-
entific problem, the reality is very different. Despite nearly 30 years
of research pursuing CNT purification, there are no universal
methods to provide high-quality CNT materials of certain proper-
ties and the proposed refinement methods are poorly reproducible.
This is because carbon nanotubes constitute a diversified group of
materials. By erroneous analogy to buckminsterfullerene C60,
SWCNTs are often (and incorrectly) considered as molecular spe-
cies. As a compound (i.e. a molecule) of well-defined structure, C60
of purity 99.99% is easily available via sublimation or liquid-based
extraction. Yet graphical representations of SWCNTs routinely
shown in research papers are nowhere near the real SWCNT sam-
ples, which are usually comprised of carbon soot containing a
certain fraction of defective nanotubes of different lengths, thick-
nesses and chiralities (Fig. 1). There is no synthetic method to date
(with some unique exceptions discussed elsewhere in this paper)
that could provide a material defined as “the SWCNT” in terms of
nanotube length, diameter, chirality, and number of carbon atoms.
Moreover, carbon materials (especially in nanosized form) are
susceptible to oxidation, hence the concentration of oxygen func-
tional groups on SWCNTs can be as high as one oxygen per ca. 100
carbon atoms [457]. In extreme cases of heavy functionalization,
CNTs could even imitate GO, where up to 45e50 wt% of oxygen
atoms is attached to carbon sheets in the form of epoxy, hydroxyl
and carboxyl groups. As the critical difference between graphene
and graphene oxide in commonly accepted, one should bear in
mind that a similar difference occurs between non-functionalized
and functionalized carbon nanotubes, even if the functionaliza-
tion is unintended. In addition, CNTs occur as tight bundles or ropes
and not as independent objects. The metal impurities, which usu-
ally occur as carbon encapsulated nanoparticles (metal@C NPs),
have wide size distributions and hence different corrosion resis-
tance. As a result, it is impossible to establish a standard purifica-
tion and characterization protocol to evaluate the purity of different
types of CNT samples. While there is a profusion of reviews con-
cerning purification of single- and multi-wall CNTs [154,458e469],
the paper published in 2008 by Hou et al. is still considered the
most comprehensive [460]. All these reviews discuss various kinds
of impurities, the so-called “nanojunk” (carbonaceous, organic,
inorganic, etc.), and do not focus exclusively on metallic impurities,
hence they lack details concerning demetalization of carbonaceous
materials. However, Vejpravova et al. have recently published a
review discussing magnetic impurities in SWCNTs and graphene in
more detail [154]. High quality commercial CNT samples are usually
characterized by carbon content in the range of 70e90 wt% for
SWCNTs and ca. 95 wt% for MWCNTs [468]. In certain applications,
such as lightweight polymer composites, the problem of metal
catalyst residues is not critical and nanotubes containing some
metallic residues can be directly mixed with polymer matrixes.
However, in most cases, especially in medical or electronic appli-
cations, metal residues must be removed. For instance, CNTs
applied as conductive additives for Li-ion batteries should exhibit
Fe content as low as 10 ppm, while a content of amorphous carbon
and metal catalyst particles up to 1000 ppm or more can be toler-
ated if used as a filler in tires [464]. Besides, there is always a risk of
incidental contamination during additional processing, packing,
and distribution even if ultra-pure carbon nanostructures could be
obtained. Furthermore, in numerous cases, the amount of metallic
impurities within studied carbon nanotubes is analyzed utilizing
techniques not suitable for quantitative assessment of trace level of
metals. One of the biggest problems in research concerning carbon-
based materials’ purification and demetalation is in fact the vo-
cabulary and terminology used to describe their purity. Equivocal
expressions like “very low content” or “high-purity” instead of
precise analysis results brought much confusion into this field of
research. Using expressions like “complete elimination of metal
catalysts from single-wall carbon nanotubes” when energy-

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dispersive X-ray analysis is used as a detection technique is simply
erroneous [470].
CNTs can be produced in large quantities by three predominant
techniques: (i) chemical vapor deposition (the primary mode of
high-yield CNT production), (ii) arc discharge, and (iii) laser abla-
tion. As each method produces CNTs of very different characteris-
tics with different kinds of impurities, it is not possible to define a
general purification protocol. Production techniques strongly
determine the efficiency of CNT soot purification. All known large-
scale methods for producing SWCNTs require a metal catalyst. As a
result, metal-free SWCNT samples cannot be produced by metal
catalyst-mediated methods. The CVD approach for CNM production
(e.g. CNTs, CNFs, graphene) utilizes typical transition metal cata-
lysts including Ni, Co, Fe and Cu (in case of graphene); however a
whole range of “atypical” catalysts is also possible (including Al, In,
Pt, Ti, Mg, Pd, K, W, Mn, Mo or Ir) [47]. Although metal-free syn-
thesis of MWCNTs is possible, metal catalysts are indispensable in
large-scale production of high-quality nanotubes. As a result,
commercial CNT samples always contain metallic impurities.
Generally, the SWCNT content in as-prepared samples by CVD is of
ca. 50 wt%, while the content of MWCNTs can exceed 90 wt%. There
are two common CVD techniques utilized to produce SWCNTs: (i)
the high pressure CO disproportionation process (the so-called
HiPco process) using Fe(CO)5 as a catalyst source and (ii) the so-
called CoMoCAT process utilizing CoeMo dual oxide as a catalyst
and CO as the carbon source. The HiPco process was designed by
Smalley et al. [471], while the CoMoCAT method was proposed by
Resasco et al. [472]. It is very important to remember that these
methods do not yield pure SWCNTs but only soots containing some
fraction of nanotube bundles. Currently the method of choice for
high-quality SWCNT production is the HiPco process and the as-
produced HiPco materials typically show a metal content of
20e35 wt% [473,474]. Yet there are reports proposing production of
SWCNTs via the CVD method with purity (in respect to carbon
content) above 99.98%. Such purity has been obtainable via water-
assisted growth of vertically aligned CNTs on catalyst-coated sub-
strates [475].
Many purification routes are known for single- and multi-wall
CNTs. Considering that metal particles are present not only at the
base or tips of nanotubes but also intercalated within their walls at
various depths, it is virtually impossible to demetalate such mate-
rials without disruption of their structure. Purification of MWCNTs
is generally easier and more effective, whereas purification of
SWCNTs always results in low yield and serious structural degra-
dation. SWCNTs are more delicate structures and hence extensive
purification leads to high nanotube consumption (often >90 wt%).
Purification methods are usually divided into two categories:
physical and chemical. A combination of both techniques can be
considered as a third category (i.e. a multi-step purification). A high
yield of purified CNTs cannot be obtained using only the physical or
chemical method alone; hence all known purification protocols
almost always combine several steps. Chemical purification of CNTs
is classified into gas phase (e.g. dry oxidation), liquid phase (e.g.
acid etching), and electrochemical oxidation, while physical puri-
fication involves various separation techniques or high-
temperature annealing. Chemical purification via gasification of
carbon relies on the differences in resistance of a well-crystallized
graphitic phase and of a less ordered carbon impurities to a re-
agent. Unlike physical purification methods, the chemical methods
always distort the structure of CNTs and introduce functional
groups and heteroatoms. A typical purification procedure of
SWCNTs usually follows three steps: (i) exposure of metal particles
via oxidation of amorphous carbon impurities and weakening
carbon shells encapsulating the metallic phase (thermal treatment
in an oxidative atmosphere), (ii) subsequent leaching of the
793
exposed metallic phase and (iii) final high-temperature annealing
to restore the sp2 structure of the purified tubes [154,460]. The first
step is tricky since transition metals are known to catalyze the
gasification of carbon [476]. Therefore, preliminary removal of
metal particles (before the oxidation step) makes SWCNTs more
resistant to burn off [477]. The oxidation rate of HiPco-SWCNTs in
air at elevated temperatures is correlated to the metal content of
the samples [478]. Therefore, the process is usually carried out at
successively higher temperatures steps to prevent SWCNT loss
during purification via gas-phase oxidation, with each step fol-
lowed by non-oxidative acid leaching of metals. As metal particles
efficiently catalyze the parasitic oxidation of carbon nanotubes at
around 350e400  C, the first oxidation should be performed at
temperatures ca. 200e250  C, followed by leaching of the exposed
catalyst particles. Encapsulated metal particles can be exposed
using for example wet air or Ar/O2 mixture oxidation, which con-
verts the metal particles to oxides. The expansion of the metal
particle due to the lower density of the oxide causes mechanical
cracking of the carbon’s protective shells [479]. This multi-stage
procedure yields 99.9% pure single-wall nanotubes with respect
to metal content. However, it was also reported that metal-
catalyzed oxidation of carbon phase at low temperatures could be
of advantage, as it allows selective removal of non-SWCNT carbo-
naceous impurities [480]. In the case of gas-phase oxidation, the
problem of homogeneous contact between carbon-based phases
and the oxidant must be considered. To enhance the uniformity of
the oxidizing gas flow, a rotating furnace tube or a fluidized bed
setup were proposed. In another original approach, raw SWCNT
soot was mixed with zirconia beads used as inert packing materials
and placed inside a vertical quartz tube [481]. Yet the most ho-
mogeneous oxidation takes place in liquid solutions where the
CNTs can be dispersed, and for this reason wet oxidation is often
preferred over gas-phase oxidation.
With the use of corrosive/oxidizing chemical agents, purifica-
tion can be conducted in one step without prior gas-phase oxida-
tion, but this approach is more destructive than sequential multi-
step treatment. When it comes to liquid-based oxidative purifica-
tion of CNTs, Pumera in his report entitled “Carbon nanotubes
contain residual metal catalyst nanoparticles even after washing with
nitric acid at elevated temperature because these metal nanoparticles
are sheathed by several graphene sheets” proved that even harsh and
prolonged oxidative acid treatment cannot provide metal-free CNTs
[232]. As metal impurities are scattered throughout the whole
graphitic tube structure, the only way to totally extract them from
CNTs by chemical means would be complete oxidation of the
graphitic carbon phase. And indeed, in the case of SWCNTs, puri-
fication is often accompanied by low yield due to extensive
oxidative consumption of nanotubes. The commonly used oxidants
for liquid-phase oxidation include aqueous solutions of HNO3,
mixtures of HNO3/HCl, HNO3/H2SO4, H2O2/HCl, H2SO4/KMnO4,
HClO4, HF, NaOH or KOH. In fact, these same chemicals are used to
produce graphene via graphite oxidation or nanotube unzipping.
This kind of purification relies not only on the affinity of carbon to
oxygen (CO2 formation), but also on the ability of graphitic domains
to form graphite intercalation compounds [482]. This in turn re-
flects the layer structure of graphite with strong covalent bonds
within the layers and weak dispersive interactions between layers.
Due to van der Waals forces, carbon nanostructures self-organize
into larger structures (fullerites, SWCNT bundles, graphitic crys-
tals, etc.). For this reason, dispersion and dissolution of carbon
nanostructures into individual entities is difficult. To attain good
dispersion or full dissolution of carbon nanoobjects, the dispersive-
attracting forces must be overcome. Exposure of graphite to an
acidic oxidizing medium could yield GICs. For instance, treatment
with H2SO4 results in graphiteeH2SO4 intercalate (known as
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graphite-bisulfate). H2SO4 also allows debundling of SWCNTs due
to intercalation between nanotubes bundled in ropes. The liquid-
based oxidation of graphitic carbons can be further enhanced by
microwaves or sonication. Concentrated acids can absorb micro-
waves rapidly and quickly dissolve the metal particles, thus pre-
venting (to some extent) damage to the carbon structure of
nanotubes. Amorphous carbon or SWCNTs can be easily gasified by
KMnO4 in a reaction catalyzed by H2SO4:
3C(s) þ 4KMnO4(aq) þ 2H2SO4(aq) / 4MnO2(s) þ 2K2SO4(aq)
þ 2H2O(l) þ 3CO2(g)
The oxidizing agent here is either the manganese heptaoxide
(Mn2O7) or the permanganyl (MnOþ 3 ) cation, which is associated
with hydrogen sulfate (HSO 2
4 ) and sulfate (SO4 ) ions in the form of
MnO3HSO4, or (MnO3)2SO4 [482]. However, oxidation by Mn(VII)
ions introduces large quantities of manganese into the purified
material. The most common liquid phase oxidation by far is based
on HNO3. It is non-toxic, cheap and allows simultaneous removal of
metal catalysts and amorphous carbon without the introduction of
secondary impurities. HNO3 can efficiently remove the carbon
shells encapsulating TM particles, however at the cost of damage to
CNTs (especially SWCNTs), as it can unzip the tube walls and
eventually entirely oxidize them to CO2 and the metallic particles to
nitrates:
C(s) þ 4HNO3(aq) / CO2(g) þ 4NO2(g) þ 2H2O(l)
Indeed, purification by oxidative acid treatment relies on the
same principles as digestion methods for ICP-based quantitative/
qualitative analyses. Nevertheless, purification of SWCNTs by HNO3
is inefficient as it leaves behind amorphous carbon, yet it cannot
totally remove metallic phases [232]. As a result, more benign ox-
idants such as H2O2/HCl mixtures were pursued. Oxidative purifi-
cation also introduces a profusion of Oefunctional groups, which
may cause the re-deposition of metal nanoparticles and ions on the
surface of the purified carbon. In addition, newly created defects
and under-coordinated sites such as graphene edges may perma-
nently trap metal ions/atoms due to the enhanced stability of the
in-plane covalent bonding.
Charron et al. presented a systematic study of commonly uti-
lized multi-step, gas-phase purification procedures of HiPco
SWCNTs (air oxidation in a temperature range of 200e510  C in
successive cycles followed by hydrochloric acid leaching) [483].
They aimed to depict the nature and amount of remaining impu-
rities. Since the catalyst particles are diverse in size, structure and
morphology (bare or encapsulated within multiple-layered carbon
shells), there is a wide distribution of reactivity towards oxidation
determined by the carbon shell’s thickness and curvature e the
particles with low curvature and thick shells are more difficult to
oxidize. The mechanism for purification via carbon oxidation in-
volves diffusion of oxygen (through pores/defects in graphitic
shells) in the particle’s metal-rich core as the limiting step. Thus,
the larger the particle, the higher temperature is required to create
an oxygen diffusion pathway [483]. Once a pathway is open for the
oxygen to diffuse to the metal/carbon interface, the metal core
undergoes oxididation prior to the carbon shell and then the
oxidized core catalyzes oxidation of the graphitic capsule. Unfor-
tunately, high temperatures lead to faster combustion of the
nanotubes, decreasing the yield of the overall purification process.
Thus after the steps where most of the iron is removed, it is rec-
ommended to use a complementary method (such as magnetic
segregation) to get rid of the large oxidation-resistant particles
[483]. It was concluded that the treatment of these Fe-based
nanoparticles by a multi-step purification procedure with gas
phase oxidation and HCl(aq) leaching was indeed inadequate to
remove all impurities and resulted in large material losses (up to
85%).
In summary, purification via gas-phase oxidation relies on the
exposure of encapsulated metal particles due to carbon etching and
mechanical cracking of the shells since metals expand upon
oxidation. Once exposed, metallic phase is chemically leached out.
After purification, high-temperature annealing is usually utilized to
remove surface oxygen functionalities and to restore the original
structure of the purified carbon material. However, it is important
to realize that only a fraction of the initial carbon nanostructure’s
properties can be reclaimed via high-temperature annealing. This
process is in fact very much like attempts to obtain graphene via the
reduction of graphene oxide. Reduction of GO obviously cannot
provide graphene, and that is why we refer to such materials as
reduced graphene oxide (unlike graphene, rGO is an amorphous
material). The same rule applies to SWCNTs and other carbon
nanostructures. Once disrupted, their structure cannot be fully
restored by high-temperature annealing.
6.1.1. Diversity of commercial carbon nanotubes: Content and type
of metallic impurities
Unlike molecular compounds, which if pure can be considered
identical regardless of their origin, CNT powders/arrays may differ
significantly in composition, structure and morphology, even if
they originate from this same production cycle. For these reasons,
results concerning studies of carbon nanomaterials are poorly
reproducible even within one batch, not to mention results ob-
tained by different laboratories. Heterogeneity of carbon nanotube
samples caused by different structural characteristics (diameter,
length, chirality, and aggregation state) yields different, often
contrasting results in the same experiments conducted on different
sample batches. According to their agglomeration state, CNTs are
divided into randomly entangled aggregates and arrays in which
nanotubes are parallel to each other (i.e. vertically or horizontally
aligned CNTs (VACNTs or HACNTs, respectively). As-synthesized
SWCNTs typically form bundles made of up to hundreds of indi-
vidual tubes (the so-called nanoropes of up to ca. 50 nm in diam-
eter). Due to high curvature, the minimum inter-tube distance in
the ropes can be smaller than the distance between layers in a
planar graphite (ca. 3.1 Å vs 3.35 Å) [484]. Therefore, when we study
commercial CNT samples we do not examine single nanotubes but
poorly defined bundles of tubes.
Residual metal catalyst, amorphous carbon, graphitic nano-
particles, organic residues and other minor impurities can account
for up to 70% of bulk commercial SWCNT material. Moreover, a
particular metal can exist in CNT soot in many different forms/
phases. For raw HiPco SWCNT (NanoIntegris Inc., 37.2 wt% of
inorganic impurities) at least six iron-based phases were identified
by the 57Fe Mo €ssbauer analysis (i.e. a-Fe2O3, Fe3O4, Fe3C, Fe5C2, a-Fe
and g-Fe) [202]. The content of individual phases also differs
significantly as the studied SWCNTs contained 20.4 wt% of iron
carbide, 14.9 wt% of iron oxides and only 1.9 wt% of metallic iron.
There is a wide selection of papers presenting purity and metal
content analysis of the most common commercially available car-
bon nanotubes and nanofibers produced by the kilogram/ton
[485e489]. For instance, to show the complexity of metallic im-
purities present within carbon nanomaterials, a set of commercial
CNTs produced by different manufacturers was analyzed by NAA
and ICP-MS [485]. More than 20 metals/metalloids were detected
in the studied samples. Despite vendor claims of providing a
catalyst-free product, up to 3 wt% of catalyst residues remained in
the seemingly pure materials. In addition, besides the expected
catalyst residues (Fe, Ni, Mo, Y, Co and Cr), a variety of unexpected
impurity elements were detected (Ce, Gd, Ho, Nd, Sm, Tb, Th, W, Yb,

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Zn, Zr). Dozens of suppliers of multi-wall carbon nanotubes (grown
mainly by CVD in a fluidized bed reactor) can be found worldwide;
for instance Bayer (Germany), Nanocyl (Belgium), Arkema (France),
Hyperion and CHASM Advanced Materials (USA), Iljin Nanotech
(South Korea), OCSiAl (Luxembourg) and Shenzhen Nanotech Port
(China). A collection of MWCNT samples from Nanocyl, Arkema and
Bayer suppliers were subjected to metal-content analysis by EDS,
XPS and TG [488]. A whole range of elements was identified by EDS,
including dominant amounts of Al (the catalyst supports), Fe and
Co. It should indeed be considered that transition metal catalyst
supports (Al2O3, SiO2, Si, etc.) may constitute a large fraction of non-
carbon impurities in CNT soot. TG analysis showed a higher thermal
stability of Nanocyl grades when compared to Arkema or Bayer and
this was attributed to the lower level of residual transition metal
catalyst. TG and EDS analyses also confirmed that purified grades
from Nanocyl (NC3100) and Bayer (C150HP) contain lower levels of
residual catalyst and that the purification process appears more
effective for removal of the catalyst supports than the transition
metals. Studies of twenty four samples of as-received, commer-
cially available MWCNT supplied by Cheap Tubes, Inc., Helix Ma-
terial Solutions, Inc., M.K. Impex Canada, Nanostructured and
Amorphous Materials, Inc., Nanolab, Inc., Sigma-Aldrich, and Sun
Innovations showed that TG purity of the examined samples varies
from 86.1 to 98.9 wt% [489]. Using energy dispersive XRF, Fe was
found in all analyzed samples (with concentrations ranging from
0.007% to 7.16%), Ni in 20 samples and Co and Mo in 16 samples.
Importantly, some of the samples exhibited significant differences
in purity from their nominal values.
By analogy to CNTs, the market of carbon materials was flooded
by a surge of commercial products named “graphene” when gra-
phene became a popular scientific topic. However, nearly all com-
mercial graphene samples are not real graphene as defined by
chemistry and physics (a single layer of carbon atoms organized in a
hexagonal lattice (lattice symmetry p3m1, point group D3)). More
than 1000 graphene-related products are available commercially
worldwide; most of them as powders/slurries mainly for bulk ap-
plications [13,490]. The quality of commercial graphene today is
poor, and most companies produce not graphene, but graphite
microplatelets. In addition, a number of products on the market
labelled as graphene are actually GOs and rGOs. Neto et al. analyzed
graphene samples from 60 companies from the Americas, Asia, and
Europe [13]. They found that most companies offer material with
graphene content below 10% and no company is currently pro-
ducing >50% graphene content. Furthermore, many companies
produce material with low carbon content, which indicates sub-
stantial contamination and functionalization. They concluded that
there is almost no high-quality graphene available on the market as
yet [13]. Presently sold graphene-related materials are mainly in
the form of powder graphene nanoplates (more than ten layers)
and they can find less demanding, low-end applications as addi-
tives in composites, coatings, conductive inks, lubricants, or to
lesser extent in more demanding applications, e.g. batteries
(conductive additive) and supercapacitors.
In summary, it is necessary to thoroughly analyze commercial
carbon-based materials before any studies are undertaken.
Providing their source and vendor characterization is not enough.
Certificates of analysis provided by the vendor are often revised
after additional analyses. Samples may differ significantly from
batch to batch. Besides additional analysis, secondary purification
of samples previously purified by manufactures is almost always
necessary to further remove residual metallic impurities. As CNTs
are being used in battery additives or lightweight composite fillers
at a scale of hundreds of tones, their proper purification is still
worth further pursuit. Many of the problems encountered with
commercial CNT products are now reappearing in the graphene
795
market.
6.1.2. Specific examples of CNT purification procedures
6.1.2.1. Purification by gas-phase treatment (oxidation or reduction).
Purification by gas-phase treatment usually utilizes oxidizing
agents including air, O2/Ar, O3, H2O, CO2 or NO2 to remove some
fraction of carbon which enables following acid leaching of the
exposed metallic particles. However, carbon phase can be also
gasified to CH4 utilizing reducing gases (H2 or NH3). Other ap-
proaches are based on direct metal oxidation and volatilization by
halogenation to corresponding halides (utilizing e.g. Cl2, Br2 or
halogenated hydrocarbons) without carbon gasification. A typical
example of gas-phase purification by oxidizing the carbon shells of
CNTs, involves transformation of encapsulated catalytic iron parti-
cles to Fe2O3 by air oxidation at a low temperature of ca. 400  C
followed by gasification of the graphitic shells by the encapsulated
iron oxide according to the reaction: 2Fe2O3 þ 3C / 4Fe þ 3CO2
(annealing at temperature of 800e900  C) and final elimination of
the exposed Fe/Fe2O3 by hydrochloric acid leaching (Fig. 39) [479].
Using this approach, the amount of Fe in a SWCNT sample was
lowered from the initial 27 wt% to about 3 wt% (TG). However,
further studies of a commonly used three-step purification pro-
cedure of arc-discharged SWCNTs proved that the first dry oxida-
tion step (usually performed in air at 300e400  C) has poor
selectivity for the removal of weakly organized graphitic species
and hence results in substantial consumption of SWCNTs [491].
This is because dioxygen O2 is a surprisingly stable molecule yet the
combustion of carbon in oxygen is highly exothermic once initiated
[492]. For this reason, highly selective combustion of less-
organized carbon phases is very difficult to attain. To avoid para-
sitic oxidation of carbon nanotubes by catalytic action of metallic
residues, the catalytic activity of the exposed metal can be selec-
tively suppressed e.g. by turning Fe into inert iron fluoride (Fig. 40)
[493]. Fe content as low as 1 wt% (assessed by TG) with 70% SWCNT
yield was achieved by fluoride deactivation of iron oxide catalyst
particles during purification of a HiPco SWCNT sample.
Metal purification of CNTs via oxidation can be performed by
two approaches: a gas phase treatment followed by acid leaching,
or in reverse order. It has been demonstrated that the sequence of
treatments determines the final purity and structure of carbon
nanotubes. This is true for both singe- and multi-wall CNTs
[494,495]. If the order of the two treatments is reversed (acidic
leaching is performed in the first stage followed by a thermal
oxidation in the second stage) the initial removal of the metallic
particles limits the catalytic graphitization of amorphous carbon
during a subsequent thermal oxidation step. As a result, a much
milder thermal oxidation condition can be applied to remove non-
graphitized carbonaceous impurities [494].
As milder oxidizing agents than oxygen (or air), CO2 and steam
(H2O) allow better control over selective removal of less organized
carbon phases. For this reason, CO2 and steam are routinely used to
prepare activated carbons through the so-called gas-phase physical
activation, which is usually performed at a temperature range of
800e1000  C [496]. The direct reaction between carbon and oxy-
gen is highly exothermic and hence not selective, while oxidation
by CO2 or H2O is an endothermic, more controllable process:
C(s) þ O2(g) / CO2(g), DHof ¼ 393.5 kJ/mol
C(s) þ CO2(g) / 2CO(g), DHof ¼ þ172.4 kJ/mol
C(s) þ H2O(g) / CO(g) þ H2(g), DHof ¼ þ131.3 kJ/mol
Additionally, carbon monoxide can be further oxidized to carbon
dioxide by steam: CO þ H2O / CO2 þ H2, but the equilibrium of
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Fig. 39. Schematic illustration of graphitic shell removal by air oxidation and high-temperature reaction between Fe2O3 and carbon phase. TEM images of purified SWCNTs. First, a
pristine CVD-grown SWCNT sample was heated in air at 400  C for 45 min to oxidize Fe NPs. After air oxidation, the sample was treated by different processes: (a) the sample was
refluxed in 12 M HCl at 100  C for 4 h, (b) the sample was refluxed in 14 M HNO3 at 100  C for 4 h, (c, d) the sample was further heat-treated at 800 or 900  C for 60 min under Ar
and then refluxed in 12 M HCl at 100  C for 4 h. Adapted with permission from Ref. [479]. Copyright 2008 American Chemical Society.

this process is shifted toward the formation of CO2 only at tem-
peratures above 1200  C. For a given activation temperature, steam
is more reactive to the oxidation of carbon. Sulfur belongs to the
oxygen family (chalcogens) in the periodic table but is generally
less reactive than oxygen. Consequently, elemental sulfur S8 and
H2S (by analogy to O2 and H2O) can be utilized as even more se-
lective oxidant agents to remove amorphous carbon from
nanotube-containing soot (sulfidative purification of CNTs)
[497,498]. Note that in reality the C þ H2S reaction is complex and
does not result simply in CS2 or CS and H2 [499]. Furthermore,
purification methods utilizing sulfur as an oxidant of carbon,
introduce sulfur into the carbon materials, resulting in S-doped
carbon. Yet carbon can be easily desulfurized (chemisorbed sulfur
can be thermally desorbed) by annealing under H2 at ca. 800  C
(according to the following process: C(Sasdorbed) þ H2 / C þ H2S).
Similarly, nitrogen (and other heteroatoms) can by removed from
N-doped carbon via H2-treatment.
Transition metal nanoparticles encapsulated in graphitic shells
(TM@C NPs) are a common by-product of SWCNT synthesis. It was
shown that CO2 oxidation of the graphenic layers surrounding
metal nanoparticles (Fe@C NPs) and SWCNTs occurs at distinct
temperature ranges [500], which allows selective oxidation of the
graphenic shells without destroying the SWCNTs. At 850  C Fe@C
NPs can be oxidized at a rapid rate, while the SWCNTs are well
preserved since they are thermally more stable during the CO2
treatment. Removal of the Fe through subsequent acid treatment
resulted in SWCNTs with purity of 99.5 wt%. In this same research it
was also shown that during CVD synthesis the growth of SWCNTs
and Fe@C NPs can be distinguished by controlling growth duration.
The CVD growth of SWCNTs stops after the first 2 min, thus high
purity SWCNTs (98.5 wt%) with a low proportion of metal@C NPs
are available by limiting growth time. Like CO2 or sulfur, steam
allows better control of the purification of CNTs since selective
oxidation by H2O can last for several hours without destroying CNT
structures. Steam treatment of both SW- and MWCNTs at 900  C
has been reported [199,501]. Such oxidation removes the graphitic
shells allowing acid dissolution of exposed metals. While the metal
content of SWCNTs was decreased from 2.2 to 0.77 wt% (TG and
magnetic measurements), no damage to the carbon nanotube
structure was observed, even after prolonged steam treatment
[199]. In the case of MWCNTs, the amount of metal impurities was
reduced below 0.01 wt% and after a prolonged 10 h steam treat-
ment as little as 0.007 wt% of Fe was determined by magnetic
measurements. However, while the authors claimed that samples
with a metal content below 0.01 wt% have been achieved by steam
purification followed by an HCl wash, the TG still revealed as much
as 0.4 wt% of mineral residue [501]. Finally, NO2 is an interesting
oxidizing agent to consider for gas-phase purification of carbon

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin 797

Fig. 40. Scheme of a multi-step purification method to remove metal catalysts from raw HiPco SWCNTs. The metal phase expands upon oxidation and cracks carbon shell. The
metallic phase catalyzes carbon oxidation, but it can be deactivated by fluorine. TEM images of (a) raw material and (b) a purified HiPco SWCNT sample treated with 20% O2 and 5%
SF6. The iron fluorides were removed by extraction with a 6 M HCl solution. Adapted with permission from Ref. [493]. Copyright 2005 American Chemical Society.

materials as it seems to give much better combustion selectivity of
different carbonaceous phases than O2 [502].
6.1.2.2. Gas-phase reductive treatment of carbon materials.
Carbon-based phases are usually gasified by oxidative treatment to
CO and CO2, but gasification by reductive gases (H2, NH3) could
allow much better control of the final structure and provide a clean,
oxygen-free carbon surface. As known, nanostructured carbon
(regardless of its form - 0D particles or 3D nanoporous structures) is
susceptible to air oxidation and spontaneous oxygen functionali-
zation. High temperature hydrogen treatment of carbonaceous
materials can be considered as a method to passivate (deactivate)
the carbon surface. Hydrogenation removes oxygen- (and other
heteroatom-) containing groups and deactivates unsaturated sites
[503]. Consequently, if carbon is free of metals, H2 treatment can
provide truly heteroatom-free carbon materials containing only
hydrogen as a foreign atom. In fact, a substantial amount of
hydrogen can be covalently bonded to carbon structures during H2
treatment [504]. However, by increasing the temperature above ca.
700  C, gasification of carbon becomes efficient in selectively
removing reactive surface carbon atoms according to the following
process: C þ 2H2 / CH4 (DHof ¼ 74.9 kJ/mol). The carbon
methanation reaction is catalyzed by metallic particles (including
metal oxides) which can significantly reduce the temperature of
carbon gasification. This reductive gasification allows simultaneous
exposure of metallic particles and their reduction to metallic phase,
which is much easier to remove by acid leaching. If NH3 is used as a
hydrogenation agent, simultaneous carbon gasification to CH4 and
N-doping of the carbon scaffold is possible (3C þ 4NH3 /
2N2 þ 3CH4). In fact, exposure of carbon material to NH3 at higher
annealing temperatures gives similar results as H2 treatment, since
NH3 decomposes to N2/H2 (forming gas) [505]. Thermal cracking of
ammonia is catalyzed by the metallic particles. As reported,
annealing SWCNTs in a H2 atmosphere allows selective removal of
amorphous carbon and exposure of the encapsulated metallic
particles [506]. H2 treatment at 1200  C followed by acid washing
allowed removal of amorphous carbon and metal nanoparticles
from SWCNTs of various origins. Compared with other purification
processes, H2 treatment yields SWCNTs with fewer defects and
with purity over 99 wt% with respect to carbon content [507].
While oxidation is the most common method to unzip SWCNTs,
unzipping of SWCNTs into graphene nanoribbons was also realized
via annealing in H2 at 400e550  C under high pressure (50 bar) for
a prolonged time (72 h) [508]. This treatment resulted in removal of
carbon coatings from Fe catalyst particles, which allowed their
elimination by acid leaching (hydrogenation is additionally pro-
moted by Fe impurities which act as a catalyst in this process). This
is an efficient method of SWCNTs purification and production of, as
the authors stated, catalyst-free CNT samples [508].
In summary, purification by reductive hydrogenation has three
main and important advantages over purification by gas-phase
oxidation. It does not introduce new functional groups on the
carbon surface and by removing existing non-metal heteroatoms
(oxygen, sulfur, nitrogen, halogens, etc.), it increases surface ho-
mogeneity and decreases surface reactivity; it reduces most of
oxidized metallic impurities of complex stoichiometry (oxides,
hydroxides, sulfides, etc.) to their elemental state [509,510] making
such impurities easily soluble in hydrochloric acid; and finally
reduction by H2 unifies the variety of impurities into more coherent
groups of phases which become much easier to manage and
remove. Indeed, H2 annealing may allow production of truly pure
carbon-only materials free of not only metal atoms but also
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heteroatoms. Interestingly, selective removal of p-block hetero-
atoms (N, S, P, etc.) by high-temperature H2 treatment may help to
elucidate the nature of catalytic centers in the so-called metal-free,
carbon-based catalysts.
6.1.2.3. Direct metal removal by halogenation.
Temperature-induced halogenation has been successfully used for
purification of carbonaceous materials for more than 60 years
[511e513]. The great advantage of the halogen treatment is that
while it efficiently volatilizes metallic impurities, the purified car-
bon material remains almost intact. This is because halogens
oxidize metals/metalloids more easily than the carbon phase. In
principle, all the common halogens (iodine, bromine, chlorine and
fluorine) can be used to remove metal or metalloid impurities from
carbon materials. Nonetheless, gas-phase chlorination is the most
widely used halogenation purification method. This is because
fluorine is too reactive towards carbon (C þ 2F2 / CF4
(DHof ¼ 933 kJ/mol)), extremely toxic and hence difficult to
handle, and yields non-volatile fluorides, while the reactivity of
heavier halogens (Br2 or I2) is much lower than that of Cl2 [514]. In
fact, chlorination is so effective at carbon demetalization that it is
used on industrial scale to produce microporous carbon materials
from metal and metalloid carbides (for instance from SiC and TiC)
yielding the so-called carbide-derived carbons [515]. However,
high-temperature bromination of metal carbides has also been
realized recently to yield pure microporous carbon materials [514].
Halogenation of carbides is referred to as thermochemical metal
extraction. The oxidation and volatilization of metals at elevated
temperatures also occurs in other halogen containing atmospheres,
like for instance HCl, CCl2F2, COCl2, CHCl3, CCl4, etc. [245,516]. The
general reaction of metal carbide extraction by chlorination can be
presented as follows:
MCx(s) þ (y/2)Cl2(g) / xC(s) þ [MCly(g)
Formation of volatile metal chlorides allows production of high-
purity carbonaceous materials. For instance, thermochemical
extraction of iron from iron carbide by Cl2 yielded well-ordered
graphite at temperatures as low as 600  C [517]:
2Fe3C(s) þ 9Cl2(g) / 6FeCl3(g) þ 2C(graphite).
As such, halogenation of transition metal carbides allows syn-
thesis of high-purity and high-quality graphite at moderate tem-
peratures. Importantly, a substantial amount of chlorine atoms
remains bonded to the carbon surface if chlorination is performed
at temperatures below 900  C. Additional high-temperature
annealing (>1000  C) or hydrogenation at temperatures 600  C
is necessary to completely remove the residual chlorine. Chlori-
nation can also be applied to direct demetalation of organometallic
transition metal complexes, which constitute common substrates
in the synthesis of carbon nanomaterials [518]. One of the most
prominent examples of a stable complex with direct transition
metalecarbon bonds routinely utilized for synthesis of nano-
carbons is ferrocene (Fe(C5H5)2). Chlorination of ferrocene, and
more generally of any metallocene occurs according to the
following equation:
M(C5H5)x(s) þ (yþ5x)/2Cl2(g) / MCly(g) þ 5xHCl(g) þ 5xC(s)
The chlorination of different organometallic complexes yields
carbon nanostructures with different morphology and structure
depending on temperature and time of treatment [519,520]. Com-
plexes other than metallocenes can also be demetallized using
chlorine. For instance, the reaction between bis(benzene)
chromium (Cr(C6H6)2) [521] and chlorine yields a whole range of
carbon structures depending on the reaction temperature:
Cr(C6H6)2(s) þ 7Cl2(g) / 12C(s) þ CrCl2(g) þ 12HCl(g)
In the case of carbides, the final structure of carbide-derived
carbons is dictated by the crystal structure of the starting metal/
metalloid carbide and not by the halogen utilized or halides formed
during the synthesis [514]. In contrast, in the case of organometallic
complexes, the final carbon structure and morphology depend on
the nature and chemical structure of the halides formed during
synthesis rather than on the crystal structure of the organometallic
precursor [521].
Thermochemical extraction by chlorine has been successfully
used to purify coal, char and graphite from mineral impurities (e.g.
Si, Al, Ti, Mg, Ca and Fe) and as a method of desulfurization. It offers
an efficient means to prepare nuclear-grade graphite, high-purity
carbon substrates for electrodes or high-purity activated carbon.
As known, graphite purification can be realized via high-
temperature heat treatment where mineral impurities are first
carburized and then vaporized. However, this process is expensive
and temperatures >2000  C can significantly alter the original
carbon structure. Graphite purification by gas-phase chlorination
can be realized at a much lower temperature of ca. 800  C. Cl2 with
added CCl4 or NaCl (which acts as catalysts) is usually used as a
graphite chlorination agent. Addition of catalysts can increase the
purity of graphite from 97% (after purification with Cl2 only) to
99.6% (after purification with Cl2/CCl4 or Cl2/NaCl mixture) [513].
Interestingly, purification by chlorination can be accompanied by
iron removal as volatile carbonyls [513]. For instance, if carbon is
contaminated by FeS2 this impurity can first be oxidized to FeO and
then reduced to a metallic state. Metallic Fe can be removed from
graphite as a volatile carbonyl by heating graphite at 200  C under
CO (Fe þ 5CO / Fe(CO)5). At low temperatures of ca. 150e200  C
and high partial pressures of CO, the thermodynamic tendency to
produce carbonyls increases sharply.
More recently, Cl2 treatment has become a common method for
purification of CNTs and graphene. In one of the first experiments
concerning CNT purification by Cl2, chlorine in a mixture with HCl
and H2O vapor was applied for gas-phase treatment of SWCNTs;
however, the focus of that research was to remove carbon impu-
rities via mild oxidation [522]. 96 wt% loss of the starting HiPco
SWCNT sample was reported. Later, Vigolo et al. presented exten-
sive research concerning purification of a variety of single-, double-
and MWCNTs by chlorination at ca. 900e1000  C [202,523e526].
Analysis of the results revealed many advantages but also some
serious limitations of Cl2-based purification of carbon nano-
structures. Generally, accessibility of the metallic particles within
CNTs is the limiting factor to remove them by any chemical treat-
ment, including Cl2 annealing. The efficiency of SWCNT purification
by chlorination at 1000  C was compared with purification by
standard oxidation treatment (including air oxidation at 350  C
followed by HCl acid reflux) [523]. Samples of two types, i.e. arc-
discharge and HiPco SWCNT, were studied. One of the most
important advantages of chlorination over air oxidation is preser-
vation of the structural quality of the final carbon material. In the
initial stage of the chlorination process, chlorine diffuses through
the defective carbon layers to the metallic particles. The formed
chlorides are less dense than the metals, resulting in dilation, which
causes fracturing of the protecting carbon shells by mechanical
stress. Interestingly, after air oxidation, the mechanical breaking of
the surrounding carbon shells due to particle dilation is not very
efficient because, for instance for nickel the density (r) ratio of
metal to corresponding oxide is relatively low (r(Ni)/r(NiO) ¼ 1.34).
For chlorination, the dilation phenomenon is more powerful for

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both Ni and Fe since r(Ni)/r(NiCl2) ¼ 2.51 and r(Fe)/r(FeCl3) ¼ 2.72
[523]. Chlorination guarantees SWCNTs of high structural quality,
but the remaining metal content can still be between 2.0 and 4.0 wt
% after treatment for 2h at 950  C (as determined by TGA and direct
current magnetization analyses) [523]. It has also been noticed that
chlorination by a Cl2/O2 mixture improves the efficiency of metal
removal and the stability of the purified SWCNTs [524]. The pres-
ence of oxygen enhances the formation of metal chlorides as it
attacks the carbon shells and improves the accessibility of chlorine
to metal. The metal content (Ni and Y) in arc-discharge SWCNT
samples was decreased to 1.6 wt% by this approach [524]. Chlorine
used in large excess acts as a combustion inhibitor and protects
SWCNTs from oxygen attack; hence SWCNTs can sustain a tem-
perature of 950  C under an oxidative atmosphere. By applying
chlorine-oxygen environment, high-purity and high-quality dou-
ble-wall carbon nanotubes (DWCNTs) were obtained using a one-
pot and entirely gas-phase purification method [525]. A compari-
son of the removal of the metallic impurity by pure Cl2
(900e1100  C, 2h) and by Cl2/O2 mixture (950  C, 2h) proved that
the addition of oxygen leads to an enhancement in the removal
yield hence producing CNTs containing only 0.1 wt% of metallic
residues. A one-pot gas-phase treatment combining chlorine and
oxygen for simultaneous removal of metal and carbon impurities
from CNTs assures selective elimination of carbon impurities, with
acceptable carbon consumption (<50%) and limited damage to
CNTs. For instance, CNT samples maintained in a Cl2 stream were
submitted to small injections of O2 at moderate temperatures
(350  C for HiPco SWCNTs and 500  C for CVD-grown DWCNTs),
and then thermal treatment at 900e1000  C under pure Cl2 was
applied [526]. Only 19 and 11 wt% of carbon phases (mainly the
undesirable carbon impurities) were lost for DWCNTs and SWCNTs,
respectively. The raw and purified CNT samples are presented in
Fig. 41. Grafting of chlorine to larger (>5 nm in diameter) graphitic
carbon impurities is less favorable than the formation of covalent
CeCl bonds on SWCNTs and DWCNTs with a small curvature (radius
<3 nm). Cl grafted onto CNTs acts as a flame retardant, which allows
Fig. 41. TEM bright-field micrographs of the raw and treated DWCNT and SWCNT samples: raw DWCNT (rD), Cl2-purified DWCNT (D3), Cl2/O2-purified DWCNT (D1), raw SWCNT
(rS1), Cl2-purified SWCNT (S5), Cl2/O2-purified SWCNT (S1) [526]. Reproduced with permission from Ref. [526]. Copyright 2019 American Chemical Society.
799
selective combustion of carbonaceous impurities by O2 while the
CNTs are protected (Fig. 42).
It was also observed that Cl2 is less efficient for purification of
DWCNTs than for SWCNTs and the extent of metal removal depends
on the production mode used to prepare CNTs. This is caused (as is
the case for all purification techniques) by the different nature of
the impurities encountered in various types of SWCNT and DWCNT
samples. In SWCNTs synthesized either by the HiPco or arc
discharge method, metal impurities occur as particles of several
tens of nm surrounded by multi-layer carbon shells. Their easy
removal by chlorine was explained by a mechanical fracture of the
shells due to the dilation process. For arc discharge-produced
SWCNTs, chlorine-based purification conducted at 950  C for 2h
leads to a purification yield of metallic impurities of ca. 65% [524].
Under the same conditions, with HiPco SWCNTs which have a
thinner carbon layer covering the metallic particles, the purification
yield reached 87.5% [523]. The catalyst particles in DWCNT samples
are smaller (a few nm) yet embedded in large carbon impurity
aggregates. Their accessibility to chlorine is reduced and the me-
chanical effect observed in SWCNT samples is less pronounced. The
metal impurity removal yield for DWCNTs whose impurities are
embedded in large carbonaceous particles was as low as 67% under
the same experimental conditions [525].
As emphasized by Pumera et al. the reduction of metallic con-
tent in carbon materials to levels below 100 ppm (0.01 wt%) where
they have presumably only weak catalytic effects is rather difficult
[245]. To overcome this challenge, they purified MWCNTs [527] and
graphene [246] by Cl2 treatment at 1000  C. A dramatic decrease in
the metal content and significantly reduced electrocatalytic activity
of chlorine-purified CNTs and graphene were observed [246,528].
Interestingly, chlorination of a variety of carbon-based catalysts
containing TMs showed drastic reduction of catalytic activity upon
Cl2 treatment, which was attributed to oxidation of metals to cat-
alytic inactive chlorides [336]. After only 10 min of Cl2 treatment,
the removal of Ni- and Fe-based impurities from MWCNTs yielded a
final content of less than 10 ppm, while the concentrations of Co-,
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W. Kicin

Fig. 42. (a) Proposed mechanism for the selective removal of carbon impurities from CNTs utilizing protective action of Cl2, and typical Raman spectra (632.8 nm) of DWCNTs in the
raw state (b), DWCNTs collected just after the Cl2/O2 step (c), and DWCNTs at the end of the purification procedure (at the end of the Cl2/O2-process) (d). Reproduced with
permission from Ref. [526]. Copyright 2019 American Chemical Society. (A colour version of this figure can be viewed online.)

Al-, Mg-, and Mn-based impurities were reduced from ~5000 ppm
to tens or hundreds of ppm [527]. Cl2 treatment of graphene is more
efficient than soaking and refluxing in concentrated acids [246].
The thermal Cl2 treatment at 1000  C was able to reduce the
amount of Fe in graphene-based materials by 90 ppm (from
930 ppm to 840 ppm) whereas wet chemistry purification methods
resulted in unaltered levels of Fe. Liquid-phase purifications in
HCleHNO3 or H2O2eHCl mixtures usually reach levels of purity in
the order of 1e5 wt% (10000e50000 ppm), two orders of magni-
tude higher than the content measured in graphene materials pu-
rified by Cl2. While traces of transition metals can dominate the
electrochemical activity of carbonaceous materials, the purity of
carbon materials is of even bigger importance in the case of medical
applications. Chlorination at 1000  C was used to purify SWCNTs
(HiPco) in order to utilize them as a platform to deliver therapeutics
to pancreatic cancer cells. The amount of residual catalyst was
reduced to 1.8 wt% (TG) [528]. However, some of the encapsulated
iron was not removed. The efficiency of CNTs purification by Cl2 can
be improved by utilizing a two-step cleaning process involving
microwave oxidation in air (to expose the metallic particles) fol-
lowed by Cl2 treatment [529].
As mentioned above not only Cl2 but also chloroform (CHCl3)
and tetrachloromethane (CCl4) have been used to remove iron from
CNTs [530,531]. CCl4 purification decreased the metal content in
CVD-grown CNTs from 3.0 to 1.0 wt% (EDX). CCl4 decomposes to
chlorine radicals at 700  C, which react with Fe to produce FeCl3:
CCl4 / C þ 4Cl and then Fe þ 3Cl / FeCl3. Fig. 43 depicts a
schematic representation of MWCNT purification by CHCl3.

Fig. 43. Schematic diagram of the purification mechanism of MWCNTs by CHCl3. During CHCl3 treatment, Cl radicals and HCl gas diffuse through defective or etched graphitic
carbon layers and react with the metallic particles to form metal chlorides. The metal chlorides sublime, leaving the graphitic shell empty. Reproduced with permission from
Ref. [531]. Copyright 2019 Elsevier.

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W. Kicin
Purification of as-prepared CVD-grown MWCNTs (JEIO (South Ko-
rea) and Nanocyl (Belgium)) was realized through two-step gas-
phase treatments at a temperature range of 800e1150  C to remove
catalyst particles (Fe and Co) and the support material (Al and Mg)
[531]. After CH3Cl annealing, residual chlorine was removed from
the carbon samples by H2O vapor treatment at 1050  C. Compared
to Fe and Co, Al and Mg were not completely eliminated at 800  C,
but pure MWCNTs could be obtained at 1050  C. The optimal
conditions for complete removal of the metals were 1050  C and
15 min; during this period the metal impurities were reduced from
5133 ppm to 12 ppm (ICP-AES), corresponding to a purification
efficiency of 99.8%. CHCl3 also proved to a better purification agent
than CH2Cl2 and CCl4.
Phosgene (COCl2) was also applied as a chlorinating agent for
recovery of fly ash carbon [532]. Minerals in fly ash exist in the form
of metal oxides. The general chlorination reaction by phosgene can
be written as: MxOy(s) þ yC(s) þ yCOCl2(g) / xMCl2y/x(g) þ 2yCO(g).
The reactivity of minerals with phosgene depends strongly on the
reaction temperature. Within 10 min, 80% of the minerals can be
extracted from the fly ash at 1050  C. Chlorination is also effective
in removing phosphorus. At 1000  C, the content of phosphorus can
be reduced from 2100 to 24 ppm in 10 min.
Carbonaceous materials can be also purified by treatment with
liquid bromine but this approach is much less efficient in metal
removal than high-temperature thermochemical extraction.
Bromination in liquid Br2 and subsequent selective oxidation with
oxygen was originally a dedicated purification method for removal
of carbonaceous impurities from CNTs. This approach is based on
the graphite intercalation process as small intercalated graphitic
nanoparticles can be removed by subsequent heating in air
resulting in preferential destruction of the intercalated carbon
[467,533]. Intercalation of bromine into graphite or CNTs (especially
at the tip of the nanotubes) takes place at room temperature,
producing C8Br and causing an expansion of the carbon interlayers.
The oxidation resistance of the intercalated graphite decreases and
eventually the metal catalyst particle is exposed [534]. Liquid
bromine at room temperature was used as an oxidant to remove
iron catalyst impurities from HiPco SWCNTs [535]. Fe was oxidized
to its bromide salt and removed by aqueous washing. The iron
content (ICP-AES) for the purified SWCNT material was ca. 3 wt% for
a single purification step but could be lowered to 1.7 wt% with an
additional purification cycle. After this treatment, the SWCNT
sample contained up to 30 wt% of intercalated bromine which was
removed by heating the sample at 400  C.
In summary, chlorination is one of the most effective methods
for demetallization of carbonaceous materials. Importantly, besides
F2, halogenation does not affect the carbon phase and allows se-
lective removal of the metallic phase only. Thermochemical
extraction has been used for industrial processing of graphite and
commercial production of carbide-derived carbons. As a result, the
infrastructure for halogen annealing of carbon materials already
exists and the procedures are well-optimized. Therefore, purifica-
tion by chlorination next to or complemented by high-temperature
heat treatment is one of the most feasible ways to obtain carbon
materials with low metal content on an industrial scale. However,
while thermochemical extraction produces carbon materials with
metal content at the level of several ppms, it still does not yield
truly metal-free materials since carbon-encapsulated metals can
withstand even such harsh treatment.
6.1.2.4. Wet purification by mineral acids, their mixtures with oxi-
dants or by hydroxide solutions. Digestion by mineral acids is the
most common method to remove large amounts of metallic im-
purities from carbon-based (nano)materials. However, the effi-
ciency of this method varies significantly depending on the utilized
801
acids or their mixture (e.g. oxidizing vs non-oxidizing). Additional,
external energy sources (e.g. sonication or microwave irradiation)
allow shorter treatment periods. As in all purification techniques,
also the specific type of purified carbon material determines the
purification efficiency. For instance, the impact of CNTs’ structural
characteristics (crystallinity, tube diameter, and bundling state)
was studied in a two-stage oxidative purification of commercially-
available single- and multi-wall CNT samples synthesized by
different processes [536]. Purification included reflux in 3 M HNO3
for 16 h followed by air oxidation at 833 K for 30 min. Highly
graphitized MWCNTs retained their structural integrity while small
diameter MWCNTs were prone to damage due to their high cur-
vature. The bundling of SWCNTs prevents the destruction of this
type of small diameter tubes to some extent [536]. A two-step CNT
purification and/or functionalization process involving HNO3
treatment is indeed very common. Concentrated nitric acid exhibits
high oxidation efficiency towards metallic and carbon phases,
especially at boiling point. However, one must consider that direct
treatment by concentrated oxidizing acids (HNO3 or H2SO4) may
not allow complete metal removal, since such acids at high con-
centrations can cause specific passivation of transition metals
[537e539]. For this reason, non-oxidative treatment with diluted
HCl followed by oxidation with concentrated HNO3 can be more
efficient for the removal of metallic impurities [540]. For instance,
when MWCNTs were subjected to non-oxidative (using concen-
trated HCl with sonication) and oxidative purification treatments
(using concentrated HNO3 or a H2SO4/HNO3 mixture) the highest
degree of purity (>98% (TG)) was achieved with the non-oxidative
treatment [541]. This result is surprising as HNO3 treatment could
be expected to be more efficient. However, the studied MWCNT did
not possess a highly ordered crystalline structure. The combination
of non-oxidative acid with ultrasound facilitated ion permeation
through the abundant defects of the tubes’ walls to dissolve iron. In
that case, it was the tubes’ structure that determined the efficiency
of oxidative vs non-oxidative acid purification. The effect of
oxidation on the structural integrity of CVD-grown MWCNTs (80%
as-received raw purity, Nanocyl) through acidic oxidative (HNO3
and H2SO4/H2O2 mixture (piranha)) and a non-oxidative (HClaq)
treatments as well as basic oxidative treatment (ammonium hy-
droxide/H2O2) was also systematically studied [542]. The HNO3-
treated material suffered the highest degree of degradation under
reflux conditions (nanotube shortening). Basic oxidative treatment
provided efficient removal of amorphous carbon and metal impu-
rities while leaving the structural integrity of nanotubes intact. The
increasing power of the oxidation agents also resulted in higher
oxygen functionalization of the treated CNT samples, which fol-
lowed the trend: hydrochloric acid < ammonium hydroxide/
H2O2 < piranha < refluxed nitric acid; where HNO3 resulted in the
highest degree of oxygen functionalization [542]. Treatment with
oxidative agents (e.g. HNO3, KMnO4, (NH4)2S2O8, H2O2, etc.), always
brings a profusion of Oefunctionalities to the carbon surface.
Weaker oxidants (e.g. (NH4)2S2O8 or H2O2) yield a higher content of
carbonyl and hydroxyl groups, while potent oxidants (e.g.
H2SO4 þ HNO3 or KMnO4) result in a profusion of carboxyl groups
(Fig. 44) [543]. Extensive surface oxidation is always accompanied
by severe structure disruption (Fig. 44, TEM pictures) which is
difficult or impossible to reverse later.
Ultrasonication or microwave-assisted acid digestion (and their
combination) yields significant efficiency improvement over
traditional acid leaching. Residual metal catalyst on the tips of CNTs
strongly absorbs microwave radiation, which leads to rupture of the
carbon shells [544]. Similar removal degrees were achieved using
HNO3 reflux for 24 h and microwave heating for only 15 min,
regardless of the kind of metal catalysts removed [545].
Microwave-assisted acid purification allows rapid unzipping and
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W. Kicin

Fig. 44. (a) Influence of the oxidant on the distribution of oxygen-containing functional groups, measured on MWCNTs that exhibit similar total oxygen concentrations. (b) Average
and standard deviation for the percentage of eCOOH groups measured for the six studied oxidants. At the bottom there are representative TEM micrographs of MWCNTs (left to
right): pristine MWCNTs (0.9 at% Oecontent), H2O2 treated (4.5 at% Oecontent), H2SO4/HNO3 treated (5.1 at% Oecontent), KMnO4 treated (5.3 at% Oecontent). Amorphous carbon is
indicated with arrows, sidewall defects highlighted by circles. Adapted with permission from Ref. [543]. Copyright 2011 Elsevier. (A colour version of this figure can be viewed
online.)

cutting of MWCNTs and hence removal of metal catalyst residues
[546]. While methods utilizing oxidizing acids may be appropriate
for robust, highly-crystalline MWCNTs, they usually destroy
SWCNTs leading to low purification yield, heavy functionalization
and production of amorphous carbon. Therefore, purifying CNTs
using milder oxidizing agents such as a HCl/H2O2 mixture (which
allows higher purification efficiency from metal particles than only
HCl solution) was also investigated. Oxidation of carbon phase by
H2O2 is a convenient purification treatment since the only final by-
product is water: C þ 2H2O2 / CO2 þ 2H2O. A one example of
utilizing H2O2 to purify SWCNTs from ferromagnetic impurities
involves a multistage process including air oxidation at 300  C
followed by reflux in 15% H2O2, then another air oxidation at
400e470  C followed by reflux in concentrated HCl acid and then in
HNO3 with a final annealing of the purified SWCNTs at 1200  C in
vacuum for 10 h to restore their structure [547]. As evaluated by
magnetic analysis, SWCNTs with 99% purity were obtained this
way. Refluxing in H2O2 was in that instance critical for efficient
purification since it partially exposed metal particles, which
selectively catalyzed burning of the graphitic particles during the
second air oxidation. A selective removal of the carbon-coated iron
NPs from HiPco SWCNTs containing 35 wt% of metallic impurities
was also achieved by treatment in an aqueous H2O2/HCl mixture at
40e70  C for up to 8 h [548]. The Fe content dropped below 5 wt%
after purification, with no loss of SWCNTs or significant damage to
their structure. Combining oxidation of raw CNT materials by H2O2
and removal of metals by HCl into a single pot improved the yield
and purity. The metals that are present in pristine CNTs act as
catalysts to produce hydroxyl radicals via the Fenton reaction. The
cleavage of one H2O2 molecule with Fe2þ produces one radical
according to the following reaction: Fe2þ þ H2O2 þ Hþ /
Fe3þ þ OH þ H2O [549]. The highly oxidizing hydroxyl radicals
etch away the high-curvature carbons in a less damaging manner
than oxidizing acids, allowing HCl to dissolve the exposed catalysts.
Eventually, amorphous carbon is converted into carbon dioxide
(4OH þ C / CO2 þ 2H2O). By confining the catalytic effect of iron
to the production of hydroxyl radicals in the vicinity of carbon-
coated iron NPs, both high selectivity in metal removal and a low
consumption rate of SWCNTs were accomplished [548]. While
purification of nanotubes using a mixture of HCl/H2O2 focuses
mainly on SWCNTs [550], this method has also been adopted for
MWCNT purification [551]. H2O2 was also utilized in a conventional
three-step purification process. Quick hydrochloric acid purifica-
tion followed by slow, selective oxidation (stirring in 30 wt% H2O2

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W. Kicin
solution assisted by sonication at room temperature for 7 days
followed by one more HClaq treatment) resulted in high-quality
few-wall carbon nanotubes (fWCNTs) with mineral residues of
only 0.16 wt% (TG) [552]. OH radicals can also be generated in
aqueous solutions from ozone via the so-called ozonation process
(2O3 þ H2O / OH þ OOH þ 2O2). The mechanism and efficiency
of O3 decomposition in water depends on pH. Carbon nano-
materials can in fact catalyze the production of OH from O3 in
water [549]. This catalytic activity of O3 decomposition increases
with the content of basic oxygen functional groups and the specific
surface area of the carbon material utilized [553]. However, one
may ask here: was it really the pure carbon material that catalyzed
the O3 decomposition reported in Refs. [553] (and numerous
similar reports) or were trace iron impurities responsible for this
phenomenon?
Acid wash is also utilized for purification of carbon nanotube
fibers. While loose powders and dispersions of CNTs can be purified
efficiently, purification of long CNT fibers is more challenging.
Metal particles increase fibers’ weight and cause performance
degradation in mechanical or electrical applications so they must
be removed. However, in the case of fibers, the major challenge is to
access the inner regions of the fibers enclosed by tightly-twisted
CNTs. Consequently, a highly efficient method to purify twist-
spun SWCNT fibers based on instantaneous Joule heating of a fi-
ber to more than 1000  C was proposed [554]. The heat burns away
the amorphous carbon species instantly and exposes Fe particles
that can be reached by hydrochloric acid. In another approach, CNT
fibers directly spun from the floating catalyst method were first
oxidized in air to burn out carbonaceous impurities and then
immersed in HCl acid [555]. This process was repeated several
times until the iron impurity content was reduced from 12 to 4 wt%
(TG).
The majority of acid-based CNT purification techniques cannot
be directly applied to fluidized bed-produced nanotubes since they
are unable to remove the substrate material (i.e. catalyst supports
including zeolites, silica, alumina, magnesia, etc.). The solubility of
commonly-used supports in alkalis implies that hydroxide treat-
ment can remove such impurities. For instance, silica-supported
SWCNTs were purified using a concentrated NaOH aqueous solu-
tion and minimal CNT structural damage was reported [556].
Obviously, unlike aqueous NaOH solution washing, rousting of CNTs
with NaOH at temperatures of ca. 700  C resulted in serious damage
to the structure of MWCNTs [557]. In the case of hydroxide treat-
ment, formation of insoluble metal hydroxides/oxides may occur
and subsequent acid treatment is always necessary. In this regard,
microwave-assisted acid digestion of alumina constitutes a very
attractive alternative to remove catalyst supports from as-received
CNT samples. As reported, microwave-assisted purification at
230  C for 30 min using H2SO4 was the most effective method to
remove alumina supports and metal catalysts from MWCNTs syn-
thesized by fluidized-bed CVD [558]. CNT purity increased from
2.6 wt% in the as-synthesized samples to 67.9 wt% in the purified
samples. This digestion caused little damage to the CNT structure.
Surprisingly, alumina-based supports which are insoluble in acids
can be quickly removed from as-obtained CNT samples by micro-
wave irradiation in H2SO4. Indeed, microwave assisted acid purifi-
cation of as-synthesized CNTs is postulated to be one of the most
promising technologies for large-scale, single-step purification of
alumina-supported CNTs avoiding time-consuming processing,
utilizing minimal acid volumes, and inducing negligible damage to
the CNTs [462].
In summary, since the beginning of research on carbon nano-
materials it has been clear that their structure determines their
purification performance and hence a universal purification
method yielding high purity and quality CNMs does not exist.
803
Conditions must be optimized based on the characteristics of pro-
cessed materials and the impurity type and level. While conven-
tional acid digestion cannot assure complete demetallization of
carbon materials, this method is still worth further optimization
due to its simplicity and low-cost. The use of HCl/H2O2 mixtures
overcomes the drawbacks of CNT purification by more corrosive
and strongly oxidizing acids. While concentrated oxidizing acids
seriously damage the carbon structure, they may not remove all
transition metal impurities due to the specific passivation of TMs.
Furthermore, in the cases of HNO3 and H2SO4, extensive interca-
lation between graphene sheets or between SWCNT bundles must
be considered. Once intercalated, H2SO4 is difficult to completely
remove. Acid leaching introduces functional groups, heteroatoms
(e.g. oxygen, nitrogen, sulfur) and incidental contaminants from
water or the utilized acids. Another important disadvantage of
liquid-based purification is the time-consuming filtration of highly
viscous and gel-like suspensions of carbon nanomaterials. How-
ever, treatment with acids in gas phase (e.g. HCl or HNO3 vapours)
is also being exercised [559]. While wet purification allows high
homogeneity, the ions released by acid dissolution can be easily and
permanently re-adsorbed on the in situ created defects in the car-
bon surface. Consequently, further high-temperature annealing in
vacuum or in a halogen/hydrogen atmosphere is necessary to get
closer to truly metal-free carbon materials.
6.1.2.5. High-temperature heat treatment (purification via graphiti-
zation). Purification of carbon-based materials through high-
temperature heat treatment is possible due to a combination of
three characteristics of graphitic carbon: (i) extremely high melting
point of ca. 3500  C, (ii) low vapor pressure and (iii) reductive
properties towards mineral phases (e.g. carbothermal reduction
and carburization of oxides and sulfides) [4,24]. High-temperature
annealing under reduced pressures (also referred to as graphitiza-
tion) is the most efficient method to remove metal/metalloid im-
purities from graphite, carbon fibers, CNTs and other carbon-based
materials. The graphitic structure is simultaneously improved but
some specific defects such as bending in CNTs are not healed even
upon high-temperature graphitization. While high-temperature
annealing does not heal all structural defects, it can cause adverse
structural effects [560]. Nevertheless, this purification method is
easily scalable, economically viable and is being extensively used to
purify graphite and carbon fibrous structures. For instance,
annealing of vapor-grown carbon fibers in up to 2800  C allowed
reduction of the mineral impurity content from 1.5 to 0.03 wt%
[561]. High-temperature thermal treatment has also been adopted
on an industrial scale to improve structural integrity and remove
metal catalysts entrapped in CNTs. Lambert et al. were the first to
show that cobalt catalyst NPs can be removed from SWCNTs by
vacuum annealing above the evaporation temperature of the metal
[562]. Unlike vacuum annealing, heat treatment at standard pres-
sure may not permit complete removal of the metal catalysts even
at temperatures exceeding 2000  C. For instance, raw MWCNTs
with an initial Fe content of 1200 ppm (ICP-MS) treated at 1800  C
in argon for 30 min still contained 80 ppm of iron on their outer
surface [390]. The Fe content decreased below 20 ppm only after
annealing at 2800  C. As a result, metal evaporation under a high
dynamic vacuum is necessary to obtain truly metal-free carbon
materials. A vacuum-based heat treatment assures complete
elimination of the metal catalysts from CNTs at approximately
2000  C if the operating pressure is sufficiently low. For example,
the purity of 99.9 wt% were achieved by annealing MWCNTs (with
raw purity of 89 wt%) at temperature of 2000  C for 5h under
pressure below 10 Pa [563]. In addition, high-temperature
annealing under vacuum is an efficient method for removing not
only residual metals (even if the metal is embedded within graphite
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W. Kicin
shells) but also residual metal oxides, like Al2O3 that cannot be
easily removed by post-annealing acid treatment. High-
temperature annealing under vacuum allows reduction of the
metal concentration to low ppm levels which are not detectable by
common analytical techniques. However, total removal of metal
traces may still be challenging even using such extreme treatments.
As proved, even if macroscopic methods indicated an absence of
any metallic impurities in HiPco SWCNT samples purified by
annealing at 2200  C for 3 h under a dynamic vacuum, a non-
negligible amount of metal was still present and the metal con-
tent must have been examined using exceptionally sensitive probes
such as extended X-ray absorption fine structure [144]. While
magnetic measurements showed that the annealed sample did not
contain any iron, the EXAFS technique revealed the presence of iron
oxide.
As hypothesized, to remove metallic impurities from graphic
structures, the metal nanoparticles must exhibit thermal mobility
to diffuse through the graphitic walls without destroying CeC
bonds [564]. Due to some defects, cracks and also the spacing be-
tween CeC bonds and the high thermal mobility of TMs during
high-temperature annealing, the metal atoms can diffuse through
graphitic walls and then evaporate. However, high-temperature
annealing can significantly change or even totally reorganize the
original structure of carbon nanomaterials especially if they are
sensitive to high temperatures. Changes such as transition of
SWCNTs to MWCNTs and tube coalescence were observed [565].
For example, high vacuum (104 Pa) heat treatment of HiPco
SWCNTs for 5h at 1800e2000  C reduced Fe content from 30 to 2%
but the diameter of the tubes increased substantially [566]. At
temperature of 2000  C SWCNTs start to transform to MWCNTs and
complete transformation is observed at ca. 2400  C [567]. Even
more thermally stable MWCNTs start to evolve into graphite
polyhedral crystals if annealed at ca. 2000  C under vacuum [568].
In his pioneering work Andrews et al. showed that high purity
MWCNTs can be obtained by annealing at temperature between
Fig. 45. TEM images of the tips of (a) as-synthesized and (b) 2000  C annealed MWCNTs for 20 min in argon. At the bottom: changes in the relative amount of iron-related
compounds as a function of temperature (900e2800  C) for total Fe content (ppm, XRF) in CVD-grown MWCNTs. Adapted with permission from Ref. [570]. Copyright 2008 Elsevier.
(A colour ver sion of this fig ure can be viewed on line.)

ski, S. Dyjak / Carbon 168 (2020) 748e845
1600 and 3000  C under a nitrogen flow [569]. Treatment at tem-
perature above 1800  C was proven to be an efficient method for
removing residual metal particles, even those encapsulated within
the core of a MWCNT. The Fe content dropped from 7.1 wt% in the
raw CNT sample to <0.01 wt% (ICPeAES) after graphitization at
3000  C for 45 min. No depletion of iron content occurred below its
vaporization temperature but all iron was essentially removed from
the nanotubes once this temperature was exceeded (>1800  C).
Nevertheless, the reported Fe content could be doubted because it
is not clear if the encapsulated Fe was indeed completely dissolved
by nitric acid during sample preparation for the ICPeAES assess-
ment [569]. Complete dissolution (digestion via oxidation) of CNT
samples is required to accurately assess the metal content by
spectroscopic methods. For this reason, such results must always be
considered with caution as full digestion of graphitic carbon is
difficult to achieve.
Extensive research is available presenting the influence of
temperature and annealing time on the purity and structure of
carbon nanomaterials, mainly nanotubes. For instance, the
composition and amount of remaining Fe-based catalyst were
investigated for isothermally treated CVD-grown MWCNTs at
temperatures ranging from 900 to 2800  C (under an Ar atmo-
sphere) for different durations ranging from 2 to 60 min (Fig. 45)
[570]. The amount and composition of the residual Fe was evalu-
ated by XRF (measurable limit for Fe of ca. 30 ppm) and 57Fe
Mo € ssbauer spectroscopy. A significant decrease in the total residual
Fe content occurred between 1800 and 2500  C while there was
little change in Fe content above 2500  C. The amount of Fe3C phase
decreased in the temperature range of 1500e2400  C and vanished
above 2400  C where the residual iron consisted only of pure metal
phases. Most of the residual iron could be efficiently eliminated by
annealing at 2400  C (for 20 min at least). However, several hun-
dred ppm of pure Fe phase was still found even after treatment at
2800  C for 20 min (Fig. 45). [570].
By examining the structural changes in MWCNTs annealed at

ski, S. Dyjak / Carbon 168 (2020) 748e845
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various temperatures and different durations (under Ar, no vac-
uum), it was confirmed that the effect of annealing temperature is
much greater than that of duration [571]. Significant structural
enhancement of the graphitic phase was observed in the temper-
ature range of 1800e2200  C. When annealed above 2500  C, no
further depletion in iron content was observed. From the
economical point of view, the optimal annealing temperature for
production of high purity and high crystallinity MWCNTs was
found to be around 2400  C [571]. The effect of high-temperature
heat treatment on the purity and structural changes of MWCNTs
was also studied by annealing pristine MWCNTs at 2600  C for 60
and 120 min under atmospheric pressure [572]. Interestingly,
60 min of heat treatment yielded nanotubes of high purity and
significantly decreased structural defects, while 120 min of such
treatment caused structural degradation with collapse of the
innermost shells. High-temperature annealing is also a convenient
approach to purify vertically aligned MWCNTs. A temperature of
1900  C (4h under Ar flow) was sufficient to evaporate most of the
residual iron from the CNT sample. ICP-AES showed a Fe content of
0.02 wt% in the purified MWCNT sample, hence arrays with purity
of 99.98 wt% were obtained [573].
While more examples of high-temperature annealing to obtain
pure CNTs can be given, the reported results concerning treatment
temperature/time and final purity are highly inconsistent. This is
due to the variety of carbon nanotube materials studied. As shown,
purification of MWCNTs of different average diameters performed
at 2200e2800  C for 1h in an Ar flow yields variant results
depending on nanotube dimeter/number of walls [574]. Annealing
at 2800  C leads to removal of almost all impurities but while in
nanotube samples with smaller diameter (8e10 nm) only traces of
Fe were observed (impurity content <1 ppm, XRF), samples with
bigger outer diameters (20e22 nm) still contained 10 ppm of Fe. It
was concluded that in the case of thicker tube walls, the applied
heating time was not sufficient for complete iron diffusion through
the walls. This observation explains why Andrews et al. [569] ob-
tained an iron content of 0.04 wt% and of <0.01 wt% for MWCNT
samples with average outer diameters of 30e60 nm treated at
2250  C and 3000  C. Other results showed that MWCNTs annealed
at 1800  C for 2h under vacuum of 400 Pa exhibited purity higher
than 99.7 wt% (TG) [564]. It can be concluded that the number of
graphitic walls and the structure of the carbon nanomaterial
determine the efficiency of metal removal by high-temperature
annealing. If the graphitic walls are thick more time and higher
temperature are required to allow the metal to diffuse through and
evaporate. Unfortunately, annealing time and temperature must
always be initially optimized depending on the type of sample
being purified.
Since very high temperatures (usually >2500  C) and vacuum
are required to remove metals with high boiling points, the use of
metal catalysts with lower boiling temperatures allows preparation
of metal-free CNTs under milder purification conditions. CNTs of
ultrahigh purity were fabricated by heat treatment of disordered
CNT-encapsulated IneSn alloy nanowires at a temperature of
1800  C in a H2 atmosphere and under vacuum (pressure of ca. 1 Pa)
[575]. Nearly 100% of the encapsulated IneSn alloy was removed at
1800  C (as determined by TG). The IneSn alloy melts at 117  C, and
the vapor pressure of its constituent metals is higher than that of
the transition metals usually utilized for CNT synthesis. Addition-
ally, H2 as the carrier gas suppresses the oxidation of the metals
during the annealing process, thus allowing for the complete
removal of the reduced metals at lower temperatures (while iron
oxide is not eliminated even with thermal annealing at 1800  C
under vacuum). Efficient removal of iron oxide requires comple-
mentary treatments in a H2 atmosphere or post-annealing acidic
washing. A different type of thermal annealing of CNTs to improve
805
their purity utilized thermal plasma processing based on extremely
high heating rates in order to shorten processing times [576]. CNTs
were subjected to an instantaneous heat treatment approaching
the temperature of carbon sublimation. Such processing of
MWCNTs and SWCNTs allows rapid removal of metal-based im-
purities via their rapid vaporization. In addition, plasma-generated
activated hydrogen species reduce metal oxides to elemental
metals of lower boiling point. However, as in the case of traditional
furnace-based annealing, the plasma method also yields different
results for different types of CNTs. In MWCNT samples the metal
encapsulations are mechanically weaker, hence the shells break
more easily, whereas strong multilayer encapsulations of impu-
rities in SWCNT samples can withstand higher internal pressures of
vaporizing catalysts making the purification process less efficient.
CNTs purified via high-temperature annealing (with improved
thermal stability and degree of graphitization) showed improved
performance in various applications. For example, heat treatment
(2200  C in an N2 atmosphere) proved to be an efficient method for
improving the electrochemical activity of a MWCNT/Pt catalyst as it
exhibited high performance in the ORR [577]. In addition, the
electrical and mechanical properties of the polymer composite
prepared with heat-treated MWCNTs (2500  C, the residual content
of Fe decreased from 14.8 to 2.08 wt%) showed improved properties
over the one prepared using as-produced MWCNTs [578].
In summary, high-temperature annealing under vacuum is the
most efficient method to remove traces of metal impurities from
carbon materials (including impurities trapped inside graphitic
shells) and to improve carbon crystallinity. However, its efficiency
differs significantly for different types of graphitic structures and
the temperature and time must be optimized for a specific sample
type. In fact, annealing at temperature as high as 2800  C may still
not be sufficient to obtain metal-free carbon structures if the
graphitic walls are thick and the time of treatment short. Purifi-
cation by high-temperature annealing can be enhanced by
reducing metal oxide/sulfide phases in a H2 atmosphere or by
additional post-processing acid dissolution of the metal phases that
diffused to the surface of the graphitic structure. In addition, some
defects like curvatures are resistant to high-temperature annealing
while at the same time adverse reengagements of the original
structure may occur. It should also be noted that graphitization is
often performed under a nitrogen flow. However, N2 reacts with
carbon at temperatures above ca. 1500  C to produce C2N2((CN)2).
Such phenomena should also be taken into consideration when the
high-temperature purification procedure is performed. Regardless
of the number of variations concerning purification techniques of
carbon (nano)materials, high-temperature annealing under (dy-
namic) vacuum remains one of the most efficient treatments to
reduce the metal impurity content to values below 0.01 wt%
without significant structural damage.
6.1.2.6. Examples of less common purification methods (electro-
oxidation, magnetic filtration, supercritical extraction, reductive pu-
rification). Purification of carbon-based materials aims to
maximize metal removal with minimal modification of the mate-
rial’s original structure. A particular type of purification must take
the specific delicate architecture of the material to be purified into
consideration. For instance, vertically-aligned carbon nanotube
arrays offer many advantages in comparison to disorganized
powders. The harsh conditions of wet purification, cause collapse of
the aligned architecture when applied to free-standing CNT arrays.
In such cases electrochemical oxidation of carbon and exposure of
metallic particles are considered superior to gas-phase or liquid-
based oxidation allowing avoidance of damage to the arrays.
However, electrochemical oxidation is usually only considered
adequate for small-scale purification. Removal of metallic
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W. Kicin
impurities from VACNT arrays is essential to eliminate their
poisonous effect if such structures are to be applied in fuel cell
electrodes, sensors, batteries, and similar high-end applications.
From a range of examples, ultrafast removal of Ni from the ends of
vertically-aligned MWCNT arrays via the CNT opening was achieved
through electrooxidation performed in an H2SO4 aqueous solution
at room temperature; 98.8% of the initial Ni was removed (ICP-MS)
[579]. Electrochemical oxidation coupled with acid washing was
able to remove more than 95% of the initial iron phase from a
SWCNT/PET electrode [580]. Electrooxidation in H2SO4 removed Fe
without inducing damage to either the assembly structure or the
tube walls of few-wall CNTs. The Fe content was reduced from >20
to ca. 1 wt% (EDS) [581]. Electrochemical purification was also
utilized for partial removal of redox-available iron impurities from
chemically-reduced graphene oxide. Partial purification was per-
formed through cyclic voltammetric scans in HNO3 [582]. This
purification method allowed a more efficient removal of iron im-
purities from rGO prepared by the Hummers than by the Stau-
denmaier method, despite a lower initial content in the second
material (860 vs 1690 ppm). This phenomenon was attributed to
the use of a strong oxidant (i.e. KMnO4) in the Hummers’ method,
which is more potent than the KClO3 used in the Staudenmaier
oxidation method and hence leads to more defects and eventually
more efficient electrochemical purification. Electrochemical puri-
fication is strongly recommended as a routine cleaning method for
graphene-based materials before any electrochemical analyses/
measurements are undertaken [582]. Finally, electrochemical pu-
rification may seem difficult to implement on an industrial scale.
Yet electrochemical processing of metals is indeed a well-
established industrial method for their purification. Consequently,
it is a feasible method to produce metal-free carbon materials in
large quantities.
Magnetically-assisted filtration (purification methods that use
permanent magnets to remove residual metallic catalyst from
aqueous suspensions of surfactant-coated CNTs) combined with
chemical purification yields purified CNTs with low loss of the
nanotube phase. Importantly, utilization of the inherent magnetic
nature of the catalyst particles enables production of undamaged
SWCNTs of high purity. However, this method cannot deliver truly
metal-free SWCNTs. For instance, using this method the mass
fraction of iron in SWCNT samples was reduced from 36 to only ca.
12 wt% [583]. In other studies, the catalyst content in SWCNTs was
lowered from 11.7 to 3.7 wt% by only applying magnetic filtration.
Still, the metal content was further reduced to 0.3 wt % (TG) by
combining magnetic filtration with air oxidation followed by HCl
treatment [584]. Magnetophoretic purification of HiPco SWCNTs
from Fe catalyst impurities in a specially-designed microfluidic
device was also proposed [585]. The iron impurities of SWCNTs
were attracted towards areas of higher magnetic-flux density. The
purity of the as-received SWCNTs with Fe content of 18.14%
increased to 98e99%. However, the overall yield of this method was
very low. Another method combining conventional air oxidation
and hydrochloric acid treatment with magnetic gradient filtration
could remove ferromagnetic impurities from raw SWCNT materials
to levels where native SWCNT magnetic properties could indeed
predominate. Removal of ~99% of magnetic impurities resulted in
diamagnetic nanotubes as their ferromagnetism was reduced
nearly of two orders of magnitude from 1.04 to less than 0.013 emu/
g [427]. This procedure yielded samples of sufficient quality for
NMR analysis. TG analysis showed a reduction of overall mineral
content from 5-10 to 1.3 wt% (with the ferromagnetic metal content
in the range of only 50 ppm). However, the purification yield of
5 mg/h was indeed very low. The low yield yet good efficiency of
selective removal of only magnetic Fe, Co and Ni metals makes this
method practical for applications where purity from magnetic
metals is the top priority. In other cases, magnetic separation is
usually accompanied by conventional acid treatment. For instance,
a two-step purification of Tuball SWCNTs (OCSiAl) with initial iron
concentration of 7 wt% involving acid treatment with concentrated
HCl, HNO3, H2SO4 and HNO3/H2SO4 followed by magnetic separa-
tion yielded a material of 99% in purity, with a purification yield of
75 wt% [586]. The treatment with HCl produced pure SWCNTs
without damaged surfaces, while treatment with a HNO3/H2SO4
mixture caused detrimental oxidation and fragmentation of the
tubes.
Due to lack of surface tension and hence high diffusivity, su-
percritical carbon dioxide (Sc-CO2) is an effective solvent for
removing impurities from porous materials. Transition metals
embedded in solid materials can be extracted at moderate tem-
peratures using Sc-CO2 containing proper oxidizing and chelating
agents. The use of pure supercritical CO2 (without oxidizing/
chelating additives) for direct extraction is inefficient due to its
weak interaction with metallic phases. For this reason, complexa-
tion with appropriate ligands is necessary as it yields complexed
metal ions with good solubility in Sc-CO2. SWCNTs (HiPco) were
purified from Fe residues by using Sc-CO2 as a solvent [587]. The
purification process involved two steps: a pretreatment sonication
step with CO2-soluble nitric acid complex of tri-n-butyl phosphate
((TBP)(HNO3)1.8(H2O)0.6) for removal of amorphous carbon that
covers the iron particles followed by a supercritical fluid extraction
step in presence of disodium ethylenediaminetetraacetate dihy-
drate. As a result, over 98% (EDS) of the iron impurities were
removed from the as-grown SWCNTs. In another example, Sc-CO2
extraction of a SWCNT sample allowed removal of more than 80% of
iron and cobalt impurities (ICP-AES) [588].
In another uncommon approach encapsulated metal impurities
were removed from a MWCNT sample by means of the so-called
metal mobilization (fluidization) [589]. This method relies on the
use of metal-reactive carbon containing precursors (e.g. melamine)
and annealing them with CNTs at temperature of 900e1000  C. At
1000  C the thermal decomposition of melamine releases gaseous
carbon species which react with Ni to form metastable Ni carbides.
Since pure Ni has a higher melting point than the corresponding
carbide, the formation of carbide eutectics allows the fluidization
and leaching the Ni out of the CNT at a lower temperature. The
pyrolysis of MWCNTs in the presence of melamine induces the
leaching of encapsulated Ni either through the tubes’ open ends or
through the defect sites present along their walls. Subsequent acid
washing removes the metal impurities that leaked out from the
CNT interior. Due to metal particle fluidization, the leaching occurs
without damaging the original nanotube structure. Commercial
MWCNTs with a purity of 97 wt% were used as a starting material
[589]. The as-received MWCNTs contained ca. 10000 ppm of metal
impurities. Thermal annealing at 1000  C in the presence of mel-
amine followed by hydrochloric acid washing reduced the total
amount of impurities down to 926 ppm (0.09 wt%, ICP-MS).
Following four successive cycles of this two-step purification pro-
cedure the total amount of metal impurities was reduced to
100 ppm (0.01 wt%) [589].
The so-called reductive purification is another specific and un-
common type of CNT purification [590]. A comparative series of
CNT purifications including reductive purification were conducted
using Tuball SWCNT samples (OCSiAl). Each of the purification
procedures was selected for its potential scalability to bulk quan-
tities and evaluated for the extent of impurity removal, nanotube
damage, and the final yield. Seven purification strategies were
evaluated: (i) reductive purification (reduction with sodium
naphthalide (NaNp) in N,N-dimethylacetamide (DMAc)), (ii) reflux
in hydrochloric acid, (iii) reflux in nitric acid, (iv) treatment with
HCl/H2O2, (v) oxidation in air at 350  C, (vi) oxidization in steam at

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
900  C and (vii) electrochemical purification [590]. The sp2 carbon
framework was most effectively preserved in the case of reductive
purification using sodium naphthalide. Reductive purification relies
on the ability of carbon nanostructures to be electronically oxidized
or reduced to a positively- or negatively-charged carbon nano-
material (CCN) [134,591]. The CCNs show improved solubilities and
may exfoliate spontaneously to stable solutions of individual,
separated species. Six fundamental CCNs can be distinguished
based on the charge sign and the parent carbon nanostructure:
fulleride (Cn nþ n
60 ), fullerenium (C60 ), nanotubide (SWCNT ), nano-
tubium (SWCNT ), graphenide (Cn ) and graphenium (Cmþ
nþ m
n )
[134]. In a broader context, this type of carbon-based material
chemistry has been known since the 19th century in the form of
graphite intercalation compounds. Reductions of carbon nano-
structures can be carried out electrochemically, in liquid ammonia,
or with NaNp in DMAc. Reductive purification is performed via
charging of SWCNTs and their impurities in aprotic, polar solvents.
Upon charging, amorphous carbon particles, small catalyst particles
and short defective SWCNTs quickly diffuse into the solution, while
the long SWCNTs must reptate out (e.g. move out; convoluted fibers
have lower movability) of the swollen bulk powder, which takes
longer. As shown, reductive purification removed a significant
proportion of metal catalyst (29.5 wt% of initial inorganic residue
was reduced to 7.8 wt% (TG)), superior to all studied methods
except nitric acid purification [590]. HNO3 treatment was most
effective in removing metal impurities, but the sp2 carbon frame-
work was heavily damaged. Purification by air oxidation/HCl
washing was also less efficient in Fe removal than HNO3 treatment.
It was concluded that in cases where iron removal is a top priority,
HNO3 purification is the best purification route from the seven
methods subjected to scrutiny [590]; however, it also causes a
significant degree of SWCNT damage. Conversely, when the
removal of inorganic impurities is of lesser importance than the
retention of the SWCNT original sp2 framework, reductive purifi-
cation is a better choice since in this case the original carbon
framework was most effectively preserved. Similarly to reductive
purification, SWCNT bundles can be dispersed in polar amide sol-
vents (e.g. N,N-dimethylformamide (DMF) or N-methyl-2-
pyrrolidone (NMP)) to produce isolated, individual tubes with no
wall damage. For instance, to obtain pure SWCNTs, dry oxidation
was used as an initial step to remove amorphous carbon from CNT
soot followed by acid purification (HCl- or HNO3-reflux) to remove
the NieY catalyst. Finally, ultrasonic dispersion of the tubes into
either DMF or NMP was performed. Both HCl and HNO3 could
successfully remove the NieY below 1 wt% [592]. However, the
HNO3-reflux damaged the tubes’ walls and hence vacuum anneal-
ing at 1000  C was necessary to heal them.
Molten salts treatment followed by subsequent acid treatment
was also utilized to remove metal particles encapsulated within
carbon nanotubes [593]. Carbon encapsulating nickel particles was
fractured during the molten salt treatment and the nickel content
was reduced to 0.4 wt% (as measured by semi-quantitative SEM-
EDX analysis). Finally, various patents concerning purification of
CNTs give a good general description of procedures leading to
materials of purity 99.9% with respect to Fe impurities (ICP-MS)
[594]. Such descriptions are useful as they give specific, detailed
examples of certain procedures and the final achievable purity. For
instance, highly pure CNTs can by prepared by heat treatment of the
raw material in oxygen, then treating the CNTs in an acid solution
and further annealing in Cl2 followed by annealing in H2. Never-
theless, as highlighted even in the recent patents, to determine the
right conditions of purification a trial-and-error approach is always
necessary, since each batch of carbon materials (e.g. SWCNT) is
indeed different. Besides, as it can be noted, patents also still use
generic and unscientific expressions like for instance “removal of
807
nearly all inorganic impurities” [594].
6.2. Carbon nanomaterials as polydentate macro-ligands for
transition and heavy metal complexation
Removal of metal impurities and production of metal-free car-
bon-based materials can be disrupted by incidental reabsorption of
metallic ions on the purified material. Carbon (nano)materials and
their composites constitute attractive media for adsorption of metal
ions from liquids due to their developed specific surface area and
presence of functional groups. CNTs, CNFs or chemically-modified
graphene materials have been widely probed as sorbents of
metallic contaminants [595,596]. It is important to consider that
even without intentional functionalization, any carbon material of
developed surface area contains some oxygen and possibly also
nitrogen functional groups and hence exhibits enhanced affinity
towards metal ion capture. Graphene oxide is an especially inter-
esting case as it exhibits both a profusion of oxygen functional
groups and a large surface area [596]. About 1 CO2 molecule is
formed per every 55 carbon atoms during the oxidative synthesis of
GO from graphite [597]. Overoxidation of graphite substrate creates
vacancy defects in the final GO. Similarly, oxidative treatment of
carbon nanotubes or nanofibers results in extensive surface func-
tionalization and deformation of the graphitic framework. The
introduced defects can then act as active adsorption sites.
The adsorption mechanism of transition and heavy metal ions
on the surface of carbon (nano)materials involves physical and/or
electrostatic interactions, ion exchanges, surface complexation, and
precipitation (Fig. 46) [595]. All the processes may and often do
occur simultaneously. The contribution of physisorption and elec-
trostatic interaction to transition and heavy metal adsorption is
rather marginal and hence chemisorption is the dominant
adsorption mechanism. Ion exchange and surface complexation,
which both involve reactions with surface functional groups (e.g.
eCOOH, eNH2, eNO2, eSH, eSO3H, etc.), play a dominant role in
adsorption of heavy metals onto the carbon surface. For instance,
the anchoring of metal ions on GO is controlled by chemisorption
involving strong surface complexation of cations with the oxygen-
containing functional groups. As shown, surface complexation be-
tween metal ions and Oefunctional groups plays a dominated role
in the adsorption of Pb2þ on GO [598]. Consequently, GO and other
carbon structures with abundant heteroatom functionalities (O, N,
S, etc.) can indeed be seen as efficient ligands able to create com-
plexes with metal ions.
As a rule, the efficiency of binding metal ions to GO increases
with ionic charge and depends on the ability of the metal to form
coordinate-covalent bonds with GO oxygen functional groups. The
electronic configuration of the metal atom shell, the redox prop-
erties, ion radius and acidity of the involved ions play a crucial role
in their abilities to form complexes and hence determine the
sorption capacities of GO. Generally, metallic ions with hard acid
behavior exhibit higher sorption capacities on GO due to their
strong affinity toward oxygen functionalities as well as their ten-
dency toward hydrolysis. One should however consider that hy-
dration of metal ions by H2O molecules can cause a reduction in the
binding energies to the oxygen functional groups of GO. Conse-
quently, interactions between hydrated metal cations (aqua com-
plexes) and carbon-based ligands (GO) might be solely
electrostatic. Basically, only negatively-charged ligands of GO (e.g.
eCOOe) are able to replace water molecules from the first coordi-
nation spheres of metal cations. Interestingly, the dispersibility of
GO in water changes rapidly after complexation of heavy metals, as
GO-metal ion complexes undergo agglomeration and precipitate
from the solution [263].
The adsorption properties of GO (and any other carbon material)
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Fig. 46. Various adsorption mechanisms of transition and heavy metals onto carbon (nano)material surfaces. Reproduced with permission from Ref. [595]. Copyright 2019, Elsevier.
(A colour version of this figure can be viewed online.)

depend on its surface chemistry. On pristine graphene oxide
eCOOH groups dominate sorption ability however one should al-
ways consider that on GO containing additional heteroatoms (N, S,
P, etc.), the dopants may dominate the binding efficiency. For this
reason, GO materials obtained by different routes exhibit very
different affinities to metal cations. GO obtained either by the
Hummers or Hoffman methods showed significant differences in
their sorption capacity toward metal ions where the Hummers
graphene oxide was reported to exhibit much higher sorption ca-
pacity than Hoffman’s GO [599]. This is because permanganate
oxidation led to a high concentration of ketone and carboxylic acid
functionalities which enhance sorption capacities due to their
strong coordination abilities. The chlorate-based Hoffman method
yields GO where hydroxyl and epoxide groups are predominant
and such functionalities exhibit a lower coordination ability toward
metal ions. Both Hummers and Hoffman graphene oxides showed
high sorption capacity toward Fe2þ and Fe3þ in the range of ca.
50e90 mg/g. For alkali and alkali earth metals, higher sorption
capacity was associated with the higher ionic radii and higher co-
ordination abilities of larger cations. However, the absolute values
of adsorption capacities are significantly higher for 2þ ions than for
1þ ions due to their higher valency [599]. As shown, the majority of
carboxyl groups in GO are located at vacancy defects. The density of
these vacancies is of about one per 200 carbon atoms [600]. To
firmly bind ions like Mn2þ with coordinate-covalent bonds, many
carboxyl groups need to be within the vicinity of the TM cation.
Such a configuration is possible at a small vacancy defect where a
“carboxyl pool” can be created (Fig. 47a). Simultaneous binding to
five or six carboxy groups can also be realized in the sandwich-type
configuration (Fig. 47b) [600]. The strong binding of TM divalent
cations (i.e. Co, Ni, Mn and Fe) to GO was utilized in practice to
prepare TM/GO composites [601]. The amount of metal bound to
GO layers followed the order: Fe > Co > Mn > Ni, showing that GO
exhibited the highest sorption capacity for Fe ions. Such TM/GO
composites were proposed as electrode materials for electro-
chemical capacitors and as ORR electrocatalysts.
The interactions between the Agþ ions and the carboxylic
groups have been utilized for complexing silver ions and stabilizing
Ag particles on the surface of GO [602]. The GO sheets acted as an
electron donor for the growth of silver NPs (Fig. 48). In the first
stage of the deposition process Agþ ions were sequestered by
functional groups of GO (e.g. hydroxyl, epoxide and carboxylic
groups). Then Agþ was reduced by galvanic displacement and redox
reaction to form nuclei surrounding the interaction sites between

Fig. 47. Schematic representation of GO binding sites. (a) The chemical structure of the “carboxyl pool” formed at a small vacancy defect. (b) The 3D model for the sandwiched
geometry. The color representation is as follows: gray - carbon; red - oxygen; blue - hydrogen; pink - manganese. Reproduced from Ref. [600] with permission from the PCCP Owner
Societies. (A colour version of this figure can be viewed online.)

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
Fig. 48. Schematic of the growth process of Ag nanomaterials in situ on graphene oxides. Reproduced with permission from Ref. [602]. Copyright 2012 The Royal Society of
Chemistry. (A colour version of this figure can be viewed online.)
silver ions and GO, in which GO played dual role as substrates and
reducing agents. Utilizing similar approach, Au NPs were deposited
on rGO by simple inversion in an aqueous solution of AuCl 4 and
spontaneous reduction of Au3þ in the absence of any reducing
agents [603]. As elucidated by the authors, the reduction potential
of the rGO is around þ0.38 V vs SHE, which is below that of AuCl 4 [267,607,608]. Besides the ability to form complexes, N-doping in-
(þ1.002 V vs SHE). Consequently, Au3þ is reduced because of the
electrons donated from negative-charged rGO sheets.
Doping carbons with nitrogen significantly increases their
adsorption capacity for transition metals. For instance, N-doped
chars exhibited 4 times higher adsorption capacity for Cu2þ and
Cd2þ than their N-free counterparts [604]. Moreover, a strong and
positive correlation between the adsorption capacity and the con-
tent of graphitic nitrogen was observed. Surface nitrogen functional
groups act as coordination sites for the adsorption of TM ions from
aqueous solutions, resulting in higher adsorption capacities for
Cd2þ, Ni2þ and Cu2þ in comparison to corresponding N-free acti-
vated carbons [605]. Cu2þ was shown to be adsorbed to an espe-
cially greater extent than Cd2þ or Ni2þ. In contrast to the adsorption
of TM ions, nitrogen-rich carbons did not show increased adsorp-
tion of alkali earth metals when compared with undoped carbon.
Consequently one can presume that N-doped carbons show specific
adsorption selectivity to transition metal ions. N-free and N-doped
active carbons exhibit different adsorption mechanisms of TM: N-
functional groups coordinate TM ions whereas ion exchange at
carboxylic groups is responsible for metal adsorption (in carbons
with only oxygen functional groups) [605]. The amount of transi-
tion metal ions adsorbed also increases with the nitrogen content
of the N-doped carbons. The highly basic pyridinic surface groups
act as ligands through the formation of surface species such as
metal coordination compounds (Fig. 49).
As known, heterocyclic nitrogen compounds (i.e. phenanthro-
line, bathophenanthroline, terpyridine, etc.) are commonly used in
colorimetric determination of transition metals at very low levels of
ppb via formation of color complexes [210,606], Fig. 50. In fact,
there is a standard test method for iron in trace quantities using the
1,10-Phenanthroline method, which detects iron in the range of
1e100 mg. Similarly, N-doped carbon nanostructures could behave
as polydentate, macro-ligands. Consequently, single metal atoms
can be permanently anchored by the surface species of the carbon
support, for instance via pyridinic-type nitrogen sites.
809
In fact, this phenomenon is routinely utilized to obtain stable
metallic species on carbon supports containing N-chelating ligands.
Highly-dispersed N-functionalities prevent the single atom
metallic dopants from aggregation and allow formation of stable
carbon-nitrogen-metal catalysts even at elevated temperatures
creases basicity and hydrophilicity of the carbon surface, which
further facilitates binding/capture of metal ions from aqueous so-
lutions. For instance, a study of N-doped carbons proved that the
basicity of the support enables uniform precipitation of the Au from
the solution without any additional reducing agent [609]. The
binding energy of metal species to the N-doped carbon support is
higher in comparison to pure carbon, which improves the stability
of the metal species. In the case of N-doped carbons, surface
complexation by the nitrogen ligants is the predominant adsorp-
tion mode rather than ion-exchange processes. As such, N-doped
carbons can be considered as solid-state polydentate macroligands.
For this reason, obtaining truly metal-free N-doped carbon (nano)
materials might be far more difficult than it is commonly believed
and results concerning the chemistry of N-doped carbon (nano)
structures are contradictory. On one hand researchers report active
metal-free catalysts based on N-doped carbon materials yet
simultaneously N-doped carbons are studied as exceptionally effi-
cient and selective adsorbents of transition metals with the ability
Fig. 49. A schematic diagram of possible surface nitrogen functional groups in acti-
vated carbon for adsorption of transition metal ions. Reproduced with permission from
Ref. [605]. Copyright 2002 American Chemical Society.
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Fig. 50. Fe2þ phenanthroline complex formation. (A colour version of this figure can be
viewed online.)
to form permanent, firmly-bound metallic complexes.
6.3. Natural and synthetic graphite purification
Graphite is thermally stable in temperatures as high as 3400  C
and for this reason any organic material can be thermally trans-
formed to carbonaceous solids and eventually to graphite (though
they can be divided into graphitizable and non-graphitizable car-
bons). However, at temperatures above 3400  C, the vapor pres-
sures of carbon species begin to exceed 10 kPa and pronounced
vapor transport occurs [610]. From the structural point of view,
graphite exists in hexagonal and rhombohedral forms, which
correspond to different stacking of graphene layers [611,612]. The
hexagonal polymorph with Bernal ABAB stacking is also referred to
as 2H-graphite and the rhombohedral polymorph with ABCABC
stacking is referred to as 3R-graphite. Natural graphite usually
contains about 80% of the hexagonal structure (with an interlayer
spacing of 3.35 Å), ca. 15% of the rhombohedral structure (3.33 Å),
and ca. 5e6% of poorly-organized disordered graphite (turbostratic/
rotationally-faulted structure). Graphite with hexagonal ABAB
symmetry is the most stable form, while ABCABC-stacked graphite
is metastable and hence transforms to hexagonal stacking after
heating in temperatures above ca. 1300  C. Rhombohedral graphite
cannot be isolated in pure form. While from a theoretical point of
view graphite (just like a particural SWCNTs or graphene) is a well-
defined homogeneous material with a certain chemical and phys-
ical structure, in reality it exists in a variety of forms and structures,
which exhibit diverse physicochemical properties. For this reason,
one should rigorously specify a particular type and purity of the
studied graphite when it comes to experimental work.
Graphite materials can be divided into numerous subgroups, for
instance into natural and synthetic graphite, micro- and macro-
crystalline and into materials of different flake shape, size and
purity. Manufactured graphite (also referred to as synthetic or
artificial) differs significantly from its natural counterpart, and also
occurs in variety of forms (e.g. pyrolytic or nuclear graphite), where
the differences are associated with certain defects and level of
impurities. High-quality and high-purity graphite has been a crit-
ical highly-demanded material at least since the development of
nuclear technologies. It is also a material of pivotal importance in
the steelmaking industry. However, the demand for graphite has
recently increased rapidly, propelled by carbon-based energy
storage and conversion technologies. These new demands include
batteries, solar energy harvesting, fuel cells and semiconductors.
Consumption of natural graphite has increased from ~600,000 tons
in 2000 to ~2 million tons in 2016 [613,614]. The increasing demand
for high-purity natural and synthetic graphite products with up to
99.99% of carbon content has resulted in growing interest in the
development of new methods for graphite purification. For
advanced energy applications, the accepted level of impurities in
graphite lies in the ppm, or in some cases even in the ppb range
[615]. For instance, highly reactive transition metal impurities can
shorten the lifetime of batteries and capacitors as they cause
detrimental side reactions. However, processes like grinding, cut-
ting or milling to obtain a certain flake size cause additional un-
intended contamination.
The purity and crystallinity of natural graphite depends on its
geographical location. Natural graphite is usually divided into three
categories: crystalline flake graphite, vein graphite (the so-called
lump vein or Ceylon graphite) and amorphous graphite (i.e.
microcrystalline graphite). The ore of vein graphite exhibits high
crystallinity (basal plane separation of 0.335 nm) and the highest
purity, of ca. 90e99 wt% of carbon content, flake graphite has car-
bon content ranging from 80 to 98% and amorphous (microcrys-
talline) graphite has the lowest carbon content of 70e85 wt% [613].
The size of graphite flakes and the crystalline structure are espe-
cially important from the commercial standpoint. Gradual im-
provements in the purification of natural flake graphite have
enabled the production of ultrapure natural graphite (>99.95% of
carbon) [613,614].
Synthetic graphite materials exhibit higher purity than natural
graphite as most of the impurities are volatilized during the
graphitization process; however, they are more expensive and
usually less ordered. The ash content of artificial graphite varies
from 1.5% to less than 10 ppm with Fe, V, Ca and Si as predominant
impurities [610]. The final purity can be controlled by selection of
raw materials and conditions of preparation. Synthetic graphite can
be prepared either by high-temperature graphitization (often
referred to as Acheson graphite or electrographite), by CVD of hy-
drocarbons at above 2500 K (the so-called pyrolytic graphite), by
crystallization from metal melts oversaturated with carbon (i.e.
kish graphite) and/or by thermal decomposition of carbides.
Nowadays, most of synthetic, high purity graphite is produced by
using high quality and low ash petroleum/pitch coke as a raw filler
material and coal tar pitch as a binder [616]. Artificial graphite can
be produced with purities of up to 99.9995%. Synthetic graphites
with metal impurities below 5 ppm would be considered as the
cleanest available commercial graphites. A distinctive type of syn-
thetic graphite is the highly oriented pyrolytic graphite, which is
formed from hydrocarbons being cracked on a graphite substrate at
temperatures above 2000  C followed by additional annealing at ca.
3500  C often combined with the application of pressure. It is worth
mentioning, that experimental studies of graphite (carbon) prop-
erties are usually done using HOPG. However, one should consider
that HOPG only mimics the perfect arrangement found in single-
crystalline graphite as it is made of smaller discrete crystallites.
Purification methods of natural graphite are divided into two
types: hydrometallurgical (including froth flotation, acidebase
treatment and hydrofluoric acid purification) and pyrometallurgy
purification (including chlorination roasting and high-temperature
annealing). The hydrometallurgical method involves acidebase
treatment, where impurities react with NaOH under elevated
temperatures and are then leached by an acid solution. Hydroflu-
oric acid can be used instead of NaOH/acid treatment as it reacts
with almost all the impurities encountered in graphite. Pyromet-
allurgical methods include either annealing at temperatures
>2500  C or high-temperature halogenation. These methods can
achieve purities of 99.995% or above. However, they are expensive
and considered only for special applications. The initial purification
of graphite ores is based on froth flotation, which brings graphite
ore to a purity of 90%. Graphite is hydrophobic and was the first ore
mineral to be concentrated by flotation [613]. Fine graphite can be
upgraded to about 95% carbon content by flotation. After flotation,
natural graphites still contain various concentrations of a wide

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range of metallic or metalloid elements including K, Na, Ca, Mg, Al,
Co, Cr, Cu, Fe, Mo, Ni, Pb, Sb, Si, Sn and V. To achieve purity above
99%, chemical purification is necessary. Caustic baking at elevated
temperatures followed by acid washing, or hydrofluoric leaching
followed by sulfuric acid washing removes most impurities to yield
purity of up to 99.9 wt%. Leaching with HF produces graphite with
high purity as HF is efficient in leaching both the metallic impurities
and the silica content from natural graphite (e.g. clay minerals).
Hydrofluoric acid for graphite purification can be generated in situ
from sodium fluoride to make the process safer [617]. However, HF
purification should be avoided as it is extremely toxic, does not
remove pyrite and produces insoluble fluorides.
The alkali roastingeacid leaching of flotation products is widely
used as an industrial technique to refine graphite. Roasting is an
effective method to eliminate both silicates and sulfides from
graphite concentrates. Under temperature around 500  C impu-
rities composed of clay/silicates (Si, Al and Fe) react with NaOH and
are transformed to water- or acid-soluble components. By applying
microwave heating, pyrite may be selectively heated and decom-
posed. Leaching experiments with HCl, HNO3 and microwave ra-
diation led to increased graphite grades of up to 99.4% [613]. At
present most high-grade graphite products are produced by the
caustic roastingeleaching method. Although this process has many
advantages (as moderate processing temperatures (300e500  C)),
it consumes a huge amount of caustic soda and water. The treat-
ment of 1 ton of graphite flotation concentrate requires ca. 0.5 ton
of NaOH. While NaOH roasting is usually carried out at 500  C,
roasting with caustic soda and sulfuric acid leaching has been found
to be an effective method for graphite purification even at roasting
temperatures of 250  C [618]. The alkali roastingeacid leaching
method yields graphite with 99.99% carbon content and is able to
remove impurities even at ppm range [619]. However, since this
process consumes some portion of graphite via carbon oxidization
and is energy inefficient, cheaper alternatives are sought. For
instance, graphite with a carbon content of up to 98.36% was ob-
tained using simple aqueous NaOHeHCl leaching of flotation
concentrate of microcrystalline graphite (84.27% of carbon) [620].
Finally, if purity below 1000 ppm is insufficient for certain appli-
cations, thermal purification (pyrometallurgical purification) at
temperatures around 2800e3000  C with longer residence times
(up to a few days) is performed to reduce the impurity content
below 200 ppm. However, graphite materials still contain small
amounts of metallic impurities even after graphitization at around
2700e3000  C, in the form of carbides or as atoms substituted in
the graphite lattice. Higher purity can be attained utilizing vacuum
high-temperature heat treatment or thermochemical purification.
Using this approach and by adding gaseous halogens (the so-called
chlorination roasting) impurities may be reduced to below 10 or
even below 1 ppm. Cl2, Freon-12 (CCl2F2), chlorine salts or other
halogen-containing compounds can be utilized for chlorination
roasting. The reason for using Freon-12 at a temperature of ca.
2000  C is that fluorine efficiently removes boron, otherwise boron
forms very stable carbides [616].
Synthetic graphite is used as a neutron moderator and reflector
due to its moderating properties and low neutron capture cross-
section. The demand for high-quality graphite as a moderator in
nuclear reactors propelled research concerning the production of
synthetic and the purification of natural graphite in the late 1950s
[621]. The total neutron absorption cross-section (NACS) of com-
mercial graphite depends on its purity. Elemental carbon has a very
low theoretical NACS (ca. 3.5 mb), and the purpose of thorough
purification of graphite for nuclear technologies is to decrease the
concentration of neutron-absorbing impurities to a level that gives
a NACS value below 4.5e4.8 mb [622,623]. Impurities of high NACS
(especially boron and transitional metals) increase the effective
811
NACS of graphite and degrade its serviceability. For instance, TMs
impurities decrease the corrosion resistance of carbon materials
causing open porosity, which decreases the strength and thermal
conductivity of graphite. A direct proportionality was observed
between the rate of corrosion and the total impurity content in
nuclear graphite [622]. Metals such as Ag, Cd, Ga, Hg, In, Pb, Sb, Sn
and Zn cause loss of ductility of nuclear flexible graphite making it
brittle (the so-called embrittlement process) [165]. The acceptable
impurity concentrations in reactor graphite are of the order of
ppms for elements having a high NACS (B, Cd, Li, Ge, Ti, V, Fe, Gd, Co,
etc). Graphite produced for use in reactors contains on average
20e30 ppm of ash and ca. 200e250 ppm of boron [624]. Nuclear
graphite is produced from petroleum coke and a mineral pitch
binder. The term nuclear graphite is often incorrectly used for any
type of graphite in a nuclear reactor, yet part of it serves only for
structural purposes where the purity standards are much lower.
The extremely high purity of nuclear graphite is assured either by
using raw materials of minimal ash content or by additional post-
purification. Thermal refining of graphite consists of heating the
mixture for several days or even weeks at above 2000  C [616].
Graphitization is always preceded by an even longer carbonization
process. Interestingly, different batches of nuclear graphite pro-
duced by the same factory may have different impurity distribu-
tions [183]. Reactor-grade graphite can also be obtained by a
combination of thermo-diffusion purification with chemical puri-
fication using fluorine, chlorine, freons/argon mixtures or halide
salts. Graphitization at 2400e2500  C with chlorine purification
sharply decreases the ash content. However, the sources of
contamination of nuclear graphite are not only the raw materials,
but also the metal-containing technological equipment used for
further manufacturing (cutting, grinding, sieving, etc.). Conse-
quently, secondary impurities can be introduced to the already
purified graphite. For instance, Fe mass fraction can increase by a
factor of 10 during additional processing of already purified
graphite [622].
Decontamination of irradiated graphite from radionuclides is
another, important problem to consider. The reason for the radio-
active contamination of reactor graphite is the activation of im-
purities as a result of long-lasting neutron irradiation. The total
amount of irradiated graphite in the world reaches 250000 tons
hence at least this much irradiated graphite must be considered as
radioactive waste for the next few centuries [625,626]. Most ra-
dioisotopes can be removed by using the same purification
methods applied during the manufacture of nuclear graphite.
Medium-range (decades) and long-range (hundreds/thousands of
years) predictions of radioactivity of spent graphite require data on
the content of Li, N, B, Cl, Fe, Co, Ni, Zn, Cs, Eu, Th, U, and other
elements in it. 60Co is one of the main emitters of high-energy g-
radiation from spent graphite during the first 40 years after a
reactor is shut down. To secure safety during disposal of the irra-
diated graphite bricks, it is necessary to collect information about
the radioactive contaminants present within graphite. Aside from
nuclear energy, other technologies such as those utilized in the
aluminum industry require graphite of high purity. The production
of one metric ton of aluminum by the Hall-He
roult process requires
about 400e500 kg of carbon used in sacrificial electrodes. There are
strict specifications for concentrations of Ca, Fe, V, Ni and Si for the
anodes’ purity [177,627]. Low ash content anodes are required in
the Al industry as impurities tend to concentrate in the Al produced
during carbon consumption.
Graphite is a common feedstock for synthesis of chemically-
modified graphene materials. The properties of graphene-based
materials obtained via graphite exfoliation are determined by the
sources of graphite stock [628,629]. Natural graphite is the most
common precursor for bulk-quantity production of GO and rGO.
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However, since natural graphites exhibit diversified properties
depending on their geological origin and purification treatment,
the derived graphene materials also exhibit extremely variant
characteristics [630]. Commercial samples of natural graphite
usually contain up to 2 wt% of metallic impurities (e.g. Fe, Ni, Co,
Mo, Mn, V, and Cr) while synthetic graphite exhibits 10e100 times
lower concentrations of impurities. Fe and Ni are the most abun-
dant TMs in both types of graphites [246,630]. Metallic impurities
present in both natural and synthetic graphites still remain in
samples of GO and rGO obtained by oxidation-reduction of graphite
[145,246,340,630]. One of the most efficient method for removal of
metallic impurities from reduced graphene oxides obtained from
graphite is thermal treatment in a Cl2 atmosphere at 1000  C [246].
This method is indeed much more efficient than refluxing in a
mixture of concentrated HCl/HNO3 acids or of H2O2/HCl.
Due to their electrical and thermal conductivity, corrosion
resistance, low density, ability to develop large surface areas and
undergo reversible intercalation reactions, graphitic carbon mate-
rials found applications in a range of energy storage/conversion
devices including batteries, capacitors and fuel cells, to name a few.
However, metallic impurities in graphitic carbon can significantly
deteriorate the performance and life cycle of such devices. In fact,
trace metallic impurities (that is, impurities below 0.01%
(100 ppm)) often determine the final performance in the applica-
tion of carbon materials in this field of technology [615]. For
instance, metal impurities from carbon can cause electrolyte
decomposition in batteries and the so-called shuttle self-discharge
of electrochemical capacitors (ECs). It was reported that due to Fe-
based impurities within carbonaceous materials the Fe-shuttle
mechanism is one of the dominant self-discharge mechanisms of
ECs [631e633].
Even though the use of graphite as an anode enabled commer-
cialization of Li-ion batteries 30 years ago, graphite still remains the
most important anode material for this type of batteries. Unlike in
the area of cathode materials, graphite has totally dominated the
market of anode materials for LIBs [634,635]. LIBs are now being
utilized in larger-scale applications like electric vehicles (EVs)
including cargo trucks and grid-scale energy storage. Consequently,
the growth of LIB production driven by EV popularization will
massively increase graphite demand over the next decade as
contemporary all-electric vehicles currently use only Li-ion batte-
ries. Interestingly, the name lithium-ion battery is somewhat
misleading as (depending on the cathode material used) a lithium-
ion battery requires up to 15e20 times more graphite than lithium.
By weight, graphite is the second largest component in LIBs. One
million electric vehicles would require ca. 100000 tons of natural
graphite for their batteries. An average hybrid electric vehicle re-
quires ca. 10 kg of graphite, while an average plug-in electric vehicle
requires as much as 70e90 kg [634]. A battery electric vehicle such
as the Tesla Roadster uses ca. 110 kg of purified graphite per vehicle.
In order to make LIBs, only flake graphite, which can be upgraded to
99.90e99.95% purity, can be used and some specific impurities,
such as Fe, should be below 50 ppm (0.005%). Highly reactive
metallic impurities in graphite result in reactions with the elec-
trolyte causing its decomposition and anode ageing. Graphite an-
odes for LIBs can be derived from both natural and synthetic
sources. Lithium-ion batteries primarily use synthetic graphite
from petroleum coke which is pure but much more expensive. As a
result, there is a significant increase in the use of cheaper natural
graphite for battery applications. Flake graphite is the dominant
natural source of graphite for production of battery-grade graphite.
However, it must be not only purified but also mechanical spher-
oidized in order to be used in LIBs. Compared to flake graphite,
spherical graphite with well-rounded spherules enables efficient
packing and increases the overall volumetric energy capacity of the
anode. However, production of spheroidal graphite is an expensive
process as it wastes up to 70% of the flake graphite feed [636]. Only
graphite that can be economically spheroidized and purified is a
suitable feedstock to produce spherical graphite. Almost all the
natural spherical graphite is currently produced in China and pu-
rified using acid leaching. New battery mega-factories around the
world have been announced, resulting in an increased demand for
superior quality natural graphite. This in turn encourages the
search for more efficient, environmentally benign and cheap pu-
rification methods. For instance, comparative studies of the Li-ion
cell electrochemical performance of natural graphite purified by
chemical and thermal processes were performed [637]. High tem-
perature heat treatment (>2300  C) significantly improved the life
cycle of natural graphite in Li-ion cells but thermal purification of
natural graphite to obtain a highly-purified sample is less
economically viable. A cheaper approach to produce graphite for
LIBs is a treatment with concentrated acids, for instance hydro-
chloric and concentrated sulfuric acid treatment under evaluated
temperature and pressure [638]. Chlorination was also employed to
purify natural graphite for LIBs and allowed production of spherical
graphite with up to 99.99% carbon content and large flake graphite
with up to 99.83% [639]. Natural graphite cathodes are also utilized
in aluminum-ion batteries [640]. Recently, kish graphite flakes have
been utilized as an electrode material in an aluminum
chlorideegraphite battery [641]. During its formation kish graphite
encases metal oxides (slag) such as iron oxides, zinc oxide, man-
ganese oxides, and magnesia. Consequently, despite its high-
quality structure, kish graphite has been considered a waste
(called dust). Purification by hydrochloric acid yielded kish graphite
with 95e99% carbon content [641]. In another approach kish
graphite was purified by mechanochemical ball-milling in the
presence of iodine. The resultant iodinated kish graphite had a low
impurity content (1.83 at%, EDX) [642]. However, the Fe content of
24500 ppm was still high because Fe intercalates into graphitic
layers during steelmaking and cannot be thoroughly removed by
ball-milling and acid leaching.
In summary, while the term “graphite” stands for the well-
defined theoretical crystal structure of the most stable form of
carbon in reality graphite represents an extremely diverse group of
materials. They differ significantly by origin, structure, purity and
morphology. The processing of natural graphite materials and
synthesis conditions of artificial graphites determine their final
properties. However, unlike SWCNTs or graphene, graphite has
found numerous highly-advanced applications and hence the de-
mand for high-quality and high-purity graphite will grow rapidly
over the coming decades. The content of metallic impurities de-
termines the usability of graphite for a number of applications. For
this reason, only specific types of graphite materials are suitable for
demanding applications such as nuclear reactors, energy storage
devices or as a substrate for chemically-modified graphenes. The
search for a cheap and environmentally benign purification process
for various forms of graphite, especially natural flake graphite, is an
important scientific and technological challenge. Graphite is the
largest input raw material into LIBs while the demand for Li is
significantly lower. Graphite has yet to receive as much attention as
lithium and cobalt, as for the time being there are no feasible
substitutes for its use in LIB anodes. In fact, its regeneration from
scrapped LIBs has become an attractive alternative to satisfy the
growing demand for graphite for energy storage systems [643].
Similarly to graphite, activated carbons once considered obsolete/
primitive materials are now viewed as advanced carbons for elec-
trochemical capacitors. Determining the minimum quantity of
metallic impurities within this type of carbon that does not cause
self-discharge is an urgent problem to study [644]. Overall, carbo-
naceous materials will remain indispensable in energy-related

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W. Kicin
applications and where CNTs and graphene failed, crude graphite,
carbon black and activated carbons prove to hold great application
potential.
6.4. GO purification
Graphite oxide, which upon exfoliation yields graphene oxide,
possesses an idealized empirical formula of C8O2(OH)2. Neverthe-
less, one must consider that in reality GO stands for an extremely
diverse family of chemical entities [14,18]. The term graphene oxide
does not define a particular chemical structure and there is no such
thing as “the” graphene oxide, just as there is no such thing as “the”
SWCNT. The most commonly observed C:O ratio for different GO
samples is around 2 and hence C8O2(OH)2 stands for its general
formula. Since it is easy and cheap to make in bulk quantities,
graphene oxide has been routinely used as a starting substrate for a
vast family of graphene-based materials (often referred to as:
reduced graphene oxide, chemically-modified graphene or
chemically-converted graphene (CCG)). In fact, most research pa-
pers concerning graphene in reality describe some kind of carbon-
based material obtained via oxidation of graphite and reduction of
the resultant graphene oxide. Such rGO materials are very different
from the graphene materials obtained by CVD on Cu foil or by SiC
heating. However, the ideal, perfectly flat graphene is of less in-
terest in chemical applications as it is a highly inert material, hence
rGO became a more common object of examination [9]. GO puri-
fication has tremendous impact on its properties. Interestingly, the
structure and properties of graphene oxide depend as much on the
purification procedure as on the type of graphite and oxidation
protocol used for its production [597,645]. However, purification of
GO is a complicated technological challenge. GO has a high acidity
(aqueous solutions have a pH between 3 and 4) and 100 g of GO
contains up to 800 mmol of active acidic sites which means 1 acidic
site for every 6e8 carbon atoms [597]. These sites take part in
cation exchange reactions. Large specific surface areas, abundant
functional groups, high water dispersibility/solubility and a ten-
dency to gelation make graphite oxide and graphene oxide perfect
traps for metallic ions to be (permanently) captured. GO creates
highly viscous slurries in aqueous solutions, which are difficult to
work with.
The modified Hummers’ method, which involves oxidizing
graphite with KMnO4 in H2SO4, is the most common and best-
optimized approach to GO production from graphite, but the ma-
terial obtained is extensively contaminated by metallic impurities
such as Mnþ2, Naþ and Kþ and the impurities from the graphite (e.g.
Fe) and the utilized reagents. Metal impurities affect a variety of GO
and rGO properties. For instance, potassium salts increase GO
flammability. As a result, as-synthesized GO requires thorough
purification, which is the biggest obstacle to the large-scale in-
dustrial production of GBMs. Numerous studies pursue the optimal
conditions for GO purification such as purification agent, contact
time, stirring intensity and temperature [646,647]. Removal of
metal ions from the reaction solution is realized through filtration,
centrifugation, dialysis, and to lesser extent via precipitation and
decantation in large-scale production. Conventional dead-end-
filtration is difficult, owing to the extensive gelation and enor-
mous swelling of GO in water, whereas dialysis is time consuming
and requires huge amounts of water. The energy consumption and
yield of conventional dialysis do not make it a feasible industrial
purification technique. Both dead-end filtration and cross-flow
filtration may be used in GO purification, where cross-flow filtra-
tion has proven to be more efficient [648]. Utilization of cross-flow
filtration allowed efficient removal of Mn-based impurities from
GO to a level of 0.02 wt% (as measured by AAS) [648]. Generally,
HNO3 is preferred over HCl in the acidic purification of GO, because
813
nitrates can be readily removed, whereas HCl may produce prob-
lematic chloride impurities. In another example, a combination of
cross flow filtration with stirring in concentrated HCl (or H2O2 at
acidic pH) permitted reduction of the Mn content in GO to 0.05 wt%
(AAS) [649]. Continuous counter-current hollow fiber-based
membrane dialysis operating in totally recycle mode was also
proposed as a feasible scale-up method to purify GO suspensions
[650,651].
6.5. Demineralization and demetallation of fossil fuels: coal and
crude oils
Biomass and fossil fuels (i.e. coals or crude oils) are carbon-rich
raw materials and some of the cheapest feedstocks for the pro-
duction of advanced carbon-based materials. While cheap and
widely available, such raw materials constitute highly heteroge-
neous composites and contain substantial amounts of heteroatoms
(e.g. N, S, P, Cl, etc.) and metals (besides ubiquitous alkali and
alkaline earth metals, also Fe, Ni, V, Co, Ti, Mn, Cu, Cr, Mo and W to
mention a few). Accordingly, these heteroatoms and metallic im-
purities are transferred into the final carbonaceous materials pre-
pared from biomass (biochars) and fossil fuels. If a natural raw
material is to be utilized in the synthesis of advanced carbon-based
materials, the amount of mineral and non-carbon elements should
first be precisely assessed. Metallic impurities exist in biomaterials
and fossil fuels either as organic complexes or inorganic minerals.
One of the common examples of organically-bound metals are
metalloporphyrins originated from living organism sources. Por-
phyrins represent tetrapyrrolic macrocycles and occur in all living
organisms in their metalated form, where they are responsible for a
variety of biological functions (such as photosynthesis (chloro-
phylls), oxygen transportation (hemoglobin) and respiration (cy-
tochromes)). In addition, cobalt present in fossil fuels originates
from vitamin B12. Nearly all metals can form coordination com-
plexes with the porphyrin nucleus. Porphyrin possesses an 18 p-
electron substructure that gives it aromatic properties and hence
high thermal stability. For these reasons, metalloporphyrins are
ubiquitous in bio- and fossil fuels. Natural carbon precursors exhibit
diverse properties and compositions, depending on their origin and
type. For instance, coals differ significantly by their structure, and
nitrogen, sulfur, phosphorus and ash content depending on their
rank. Nevertheless, coals of different grades possess a unique mo-
lecular structure and represent a cheap alternative to synthetic
carbonaceous materials, and hence have been used to produce
graphene, carbon nanotubes and nanofibers as well as carbon
quantum dots [652e655]. In fact, graphene quantum dots were
extracted from various types of coal, and it was stated that the
unique coal structure has an advantage over pure sp2-hybridized
carbon allotropes for obtaining such materials (Fig. 51) [654].
Metal contaminants in coals remain a serious limitation in their
utilization as a feedstock for functional advanced carbonaceous
materials. High rank coals like anthracite are probed to produce
high-end carbon products, including high-purity synthetic graphite
[656,657]. Conversion of anthracites to graphite materials offers a
competitive alternative to petroleum coke, which is currently used
as the filler material in the manufacture of synthetic graphite. The
purity of the petroleum coke depends on the quality of the crude oil
feedstock and determine the purity and quality of the final syn-
thetic graphite. Coal is an abundant raw material that could be
utilized as a cheaper substitute for oil and natural gas to produce a
wide range of fuels and chemicals [658]. Clean coal free of ashes is
referred to as a solid fuel and can be used in direct carbon fuel cells,
which offer 60% power generation efficiency based on its higher
heating value basis [659]. Unfortunately, the mineral matter pre-
sent in coal prohibits its use as an oil and gas substitute. Clay, quartz
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Fig. 51. Synthesis and characterization of bituminous coal-derived graphene quantum dots (b-GQDs). (a) Image and simplified illustrative nanostructure of coal. (b) SEM image of
ground bituminous coal. Scale bar, 50 mm. (c) Schematic illustration of the synthesis of b-GQDs. Oxygenated sites are shown in red. (d) TEM image of b-GQDs showing a regular size
and shape distribution. Scale bar, 20 nm. (e) HRTEM image of representative b-GQDs from d; the inset is the 2D FFT image that shows the crystalline hexagonal structure of these
quantum dots. Scale bar, 2 nm. (f) AFM image of b-GQDs showing height of 1.5e3 nm. Scale bar, 100 nm. Reprinted with permission from Ref. [654]. Copyright © 2013, Springer
Nature.

and pyrites account for ca. 90% of the inorganic mineral matter.
Similarly to natural graphite processing, there are two approaches
for coal cleaning: initial physical beneficiation and deep chemical
demineralization. Chemical demineralization of coal can be divided
into two approaches: (i) leaching minerals out of coal by inorganic
acids and alkalis e the product obtained is named an ultra-clean
coal (UCC) or (ii) solvent extraction of coal matter by organic sol-
vents e the product is referred to as ash-free coal (AFC) also known
as hyper-coal (HPC) [660,661]. These two technologies work in
opposite manners e UCC is produced by inorganic mineral matter
extraction from the coal bulk, while AFC/HPC is produced by
extraction of the carbon-rich matter leaving behind the inorganic
residues. Extraction by organic solvents provides solid fuels of
higher purity than acid/alkali washing. The history of chemical coal
purification can be traced back to the 1940s when alkali solutions
followed by acid washing were applied as a purification procedure
to manufacture carbon electrodes. Nevertheless, soon after this,
demineralized coal was replaced by petroleum coke and the
interest in commercialization of the chemical purification of coal
has stalled for decades.
Acid or alkali washing followed by further treatment with
diluted acids are the simplest methods to produce UCC with the ash
content in the range of 0.15e1.0 wt% [660]. According to the liter-
ature, the most effective treatment of coal is HF followed by HNO3
leaching, achieving an ash content as low as 0.15 wt%. Alkali/acid
leaching involves the use of a NaOH solution followed by diluted
acid (HCl or H2SO4) treatment. HF is practically the only available
acid able to dissolve quartz and clay minerals but it is not suitable
for pyrite removal. Moreover, insoluble compounds can also be
formed when the concentration of HF exceeds its stoichiometric
amount required [662]. Nitric acid is used after HF washing to
remove the HF-insoluble pyrite and fluoride compounds, but HNO3
reacts with the pyrite only above a particular concentration due to
its preferential reaction with the organic coal structure [663]. In the
case of alkali purification, the compounds formed upon leaching
are weakly soluble in alkali solutions, hence a further treatment

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with diluted acid solution is required. However, the concentration
of the acid must be carefully controlled to prevent the formation of
silica gels. Furthermore, in the case of alkali leaching at higher alkali
concentration, the dissolution of silica and alumina decreases due
to formation of insoluble sodium-aluminosilicate [664]. Thus, the
concentration of reagents and the sequence of leaching is of special
importance in the chemical purification of coals using HF/HNO3 or
NaOH/acid wash.
The solvent extraction technique to produce AFC/HPC utilizes a
highly polar organic solvent to extract organic moieties out of the
coal matrix and then precipitate the obtained solid fuel. This pro-
cess is usually performed at 300e400  C and 1 MPa. Polar organic
solvents such as N-methyl-2-pyrrolidinone or N,N-dime-
thylformamide exhibit good coal dissolving capabilities and thus
allow high extraction yields. NMP and DMF constitute a special
group of highly polar and non-hydrogen-bonding Lewis bases. Coal
swells due to solvent-induced relaxation upon mixing with a polar
organic solvent and heating above the softening temperature.
Subsequently, the soluble carbon-rich portion of coal is dissolved
into the solvent leaving behind the high-ash-content byproduct.
The use of more polar organic solvent and higher temperature
conditions increases the extraction yield. The extraction yield for
NMP varies from 70 to 90%, but a large amount of NMP is lost due to
a strong linkage with coal molecules. Coal obtained via organic
solvent extraction exhibits much lower ash content than UCC. AFC/
HPC is characterized by ash content as low as 200 ppm [660,661].
However, this process (unlike the acid/alkali leaching) completely
alters the original structure of coal. Interestingly, even though pu-
rification of coal by NMP extraction has been known for decades
[665], this phenomenon was “re-discovered” in 2008 as a new
method for high-yield production of graphene by NMP-driven
exfoliation of graphite [666]. Similarly to coal and graphite,
SWCNTs can be debundled and eventually dissolved into separated
tubes using polar amide solvents such as NMP or DMF [592]. N,N-
dimethylacetamide, g-butyrolactone and 1,3-dimethyl-2-
imidazolidinone can also be used to disperse SWCNTs, exfoliate
graphite into graphene or extract carbon-rich phases from coals
[592,666].
When one compares coal purification methods, two questions
arise: why does organic solvent extraction produce coals with
much higher purity than acid/alkali leaching and what kind of
metallic impurities are still present in the extract obtained from
coal? Metals are present in coal in two forms: mineral grains and
organically-bound species. While acid/alkali leaching removes the
inorganic species the organically-bound transition metals, partic-
ularly Fe, are resistant to mineral lixiviants but exhibits a high af-
finity to organic solvent extraction [661]. Metallic impurities in the
form of organic solvent-soluble complexes are also ubiquitous in
crude oils. Fe constitutes as much as 50e80 wt% of the organically-
bound transition metals in coal extracts, whereas V and Ni are the
most abundant transition metals in natural petroleum (with up to
2000 ppm of V and up to 250 ppm of Ni). As the weight of oil in-
creases, its amount of heteroatoms (N and S) and associated with
them metals also increases. The depletion of light crude oils forces
the petrochemical industry to process heavier crudes with higher
metal content (heavy oil makes up about 80% of world oil reserves)
[667]. Metallic impurities induce undesirable side reactions during
crude oil processing and are transferred to products obtained from
petroleum (such as coke and graphite).
The quantity and chemical forms of the organically-bound
transition metals in fossil fuels are still poorly understood. For
instance, it is presumed that organic iron is present in coal matrices
mainly as high-spin octahedral Fe3þ chelated with oxygen- and
nitrogen functionalities and forming porphyrin or ferritin-like
structures/nanoparticles which are insoluble in mineral acids
815
[661]. Metallopetroporphyrins are the only unequivocally identi-
fied organic metal species in crude oils. Up to 80% of V and Ni exists
in crude oils as metal porphyrin complexes. Transition metals
chelated in thermally-stable porphyrinic ligands are compatible
with petroleum fractions, therefore metal removal from petroleum
feedstock is truly challenging. The polar and aromatic properties of
the organic metal complexes cause their concentration in the
asphaltene fraction, which is the heavier portion of the residuum
[668]. The demetallization of heavy petroleum feedstock can be
achieved via destructive chemical thermal/catalytic conversions
(e.g. hydrogenation) or nondestructive physical mass transfer
processes (e.g. distillation, solvent extraction and/or adsorption)
[669,670]. The main objective of chemical demetallization is to
selectively remove the metal from the organic moieties with min-
imal alteration of the remaining petroleum. This can be achieved by
using mineral acids. As porphyrins are reversibly demetallated by
acids, a variety of liquid-phase acids have been used for metal
removal at an industrial scale. Porphyrins can be classified by their
resistance to demetallation by different acids (acetic, hydrochloric
and sulfuric acid). Metal atoms are more easily removed from their
porphyrin complexes if they are in their more reduced state [671].
A high degree of metalloporphyrins aromaticity assures their
thermal and chemical stability. Yet, catalytic hydrogenation of such
structures leads to their permanent demetallation. Removal of
heteroatoms and metallic impurities from liquid petroleum feed-
stock is realized by a catalytic hydrogenation process called
hydrotreating, which can be divided into hydrodemetallation,
hydrodenitrogenation and hydrodesulfurization (depending on the
type of element removed). The extent of hydrogenation necessary
for demetallation (the number of hydrogen atoms added to the
porphyrinic ring) varies depending upon reaction conditions. The
strains of the ring induced by hydrogenation can cause metal
release even before ring breakage. Upon ring cleavage, the metals
are released from the compound according to the following
scheme: MP # MPH2 / metal deposit þ hydrocarbon, where
M and P represent the starting metal and porphyrin respectively
[669,672]. Metal deposition occurs from the metalloporphyrin in-
termediate (MPH2). Fig. 52 shows a scheme of the model hydro-
genation reaction of a metal-porphyrin complex.
Demetallation of metalloporphyrins can also occur without
destruction of the tetrapyrrole macrocycle ring by selective
removal of metal through mild bromination with NaBr. This is an
alternative heavy oils demetallation method to the common acid
leaching which causes undesirable side reactions. Ni can be selec-
tively removed utilizing the mild bromination approach [673]
(Fig. 53). Unfortunately, this method cannot be used for vanadium
removal.
In summary, thermally and chemically stable organometal
complexes (such as porphyrins with TMN4 motifs) are ubiquitous
in biomaterials and fossil fuels. Unlike inorganic impurities, they
withstand mineral purification and flit easily into the final carbo-
naceous materials produced from feedstocks of natural origin. En-
zymes with TMN4 structures are abundant in all living matter and
during pyrolysis they can be accumulated and transferred into
redox active TMNxC catalysts. Consequently such cabons (e.g.
biochar) can behave as carbon-based artificial enzymes [674]. As all
living organisms contain a diversity of heteroatom-chelated TMs
[675], research on fossil fuel demetallization constitutes a valuable
source of practical knowledge concerning the purification of
carbonaceous material derived from biomss, and also makes us
wonder whether bio-derived mass can constitute a source of a truly
metal-free carbon.
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Fig. 52. Hydrodemetalation pathways for model Ni petroporphyrin compounds. Reprinted with permission from Ref. [672]. Copyright © 2001, Taylor & Francis.

6.6. Processing of CVD-grown graphene: common sources of
contamination
High quality, large-area single-, or few-layered graphene films
are fabricated on a large scale by chemical vapor deposition using
Cu, Ni or CueNi alloys as catalysts on which graphene is deposited
via cracking of light hydrocarbons. However, while the quality of
CVD-grown graphene is high, it still needs to undergo a transfer
from the metal foil onto a variety of substrates for certain advanced
applications [676]. There are many transfer techniques available
but chemical etching is one of the most common. During this
process, the metal catalyst foil is gradually etched away using re-
agents such as iron-based salts, acids, ammonium persulfate (e.g.
FeCl3, HNO3, (NH4)2S2O8) or commercial copper etchants, leaving
behind free graphene film. However, contamination of the gra-
phene film with metallic impurities occurs due to incomplete metal
dissolution and also originates from the applied etching solutions.
Consequently, the quality of graphene is strongly downgraded
during this process. There are many reports pointing out strong
interactions between graphene defects and metallic impurities
originating from the etchants used to remove Cu substrate. For
instance, Fig. 54 depicts transferred graphene samples contami-
nated with copper etchant (Type CE-100, Transene) which contains
iron ions [677]. Iron/iron oxide core-shell nanoparticles originating
from the etchant were firmly anchored to the graphene’s edges and
folds, indicating strong interactions between the defects and the
Fe-containing nanoparticles.
Furthermore, formation of graphene wrinkles during cooling of
the Cu/graphene system can result in Cu atoms being permanently
trapped in graphene folds even before the transfer process. While
more thorough and aggressive etching yields graphene of higher
purity, there is a trade-off between the purity of the graphene layer
and its structural integrity. Further improvements in transfer and
cleaning technologies are required to provide graphene materials of
high purity and quality for advanced applications. One of the most
promising applications of graphene or graphene nanoribbons (as
previously envisaged for SWCNTs) is as a future replacement for
silicon in electronics and spintronics to build faster and smaller
chips. However, microelectronics requires extremely pure gra-
phene standing on insulating substrates. As known, detection and

Fig. 53. Scheme of the selective removal of Ni from the porphirinic ring by mild bromination. Reprinted with permission from Ref. [673]. Copyright © 2015, Elsevier. (A colour
version of this figure can be viewed online.)

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Fig. 54. (A, B) HR-TEM images of graphene synthesized by CVD using Cu as catalyst. (C) contaminant nanoparticles indicated by arrows (from the Cu etchant) decorating graphene
edges/folds (please note that the graphene sample was not treated with a post-cleaning step involving HCl solution after etching the Cu foil). (D) Graphene nanostrips and
nanoribbons (along the arrows). Reproduced with permission from Ref. [677]. Copyright 2010 American Chemical Society.

control of metal contaminants are of the utmost importance in
manufacturing Si-integrated circuits [678,679]. Even extremely low
concentrations of trace metals (1010e1011 atoms/cm2), pose a
serious threat. Residual metallic impurities of graphene such as Cu,
Fe or Ni associated with the transfer from metal catalysts can
significantly alter the electronic properties of semiconductor de-
vices (e.g. lifetime and dielectric strength degradation) [678]. For
instance, iron contaminations cause p-doping in graphene and
constitute an uncontrollable factor that changes the conductivity of
graphene [680]. Contaminations with metallic residues also cause a
large reduction in the thermal conductivity of graphene, e.g. a 76%
reduction was reported for graphene transferred by ferric nitrate
etchant as compared to that transferred by (NH4)2S2O8 [681]. As
such, transition-metal free ammonium persulfate is a better
etchant in the transfer process of graphene than iron-containing
FeCl3 or Fe(NO3)3 as it provides a cleaner graphene free of FexOy
residues. A variety of etchants have been studied to find the optimal
conditions for wet transfer of graphene films [682]. When multi-
layer graphene grown on Ni foil was treated by FeCl3 etching,
13 ppm of Fe and 0.2 ppm of Ni were detected by ICP-MS in the final
purified sample [683]. These impurities alter the electrochemical
behavior of the transferred graphene when applied as an electrode
material (a phenomenon previously observed for contaminated
CNTs). Consequently, electrochemical delamination and chemical
etching using metal-free mixtures have been explored to avoid
incidental metal contamination [684]. Metal-free etching agents
such as a HCl/H2O2 mixture permit production of graphene with
less metallic impurities. Redox-accessible metallic impurities can
be removed from graphene materials via electrochemical purifi-
cation. Electrochemical etching was successfully applied to remove
more than 90% of the copper traces in transferred graphene, which
resulted in improvement in both the electrochemical and
electronic-transport properties of the final purified graphene
sample [685]. 20 cycles of electrochemical etching of graphene in
HCl/H2O2 solution were sufficient to completely remove any para-
sitic electrochemical signals arising from Cu traces otherwise
observed in the electrocatalytic reduction and oxidation of L-
glutathione and cumene hydroperoxide.
Electrochemical bubbling is an especially convenient technique
for etching-free graphene transfer. The electrochemically-assisted
delamination of CVD-grown graphene is faster than chemical
etching, and more importantly, it assures minimal structural
damage and basically no residual contaminations. In this approach,
graphene grown on metals is used as the cathode and is detached
from the metals by the H2 bubbles generated by H2O electrolysis.
Etching-free electrochemical bubbling transfer was applied to
graphene grown on platinum for example. Pt as an inert metal
remained intact after thousands of transfers and permitted
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production of graphene free of metal residues (although whether
the graphene was really free of Pt remains unclear) [686].
Electrochemically-delaminated graphene films showed almost no
electrocatalytic effects arising from either Fe or Ni impurities, while
graphene prepared with an FeCl3 etchant displayed significant
electrocatalytic activity due to the Fe residues. Consequently, gra-
phene films delaminated using electrochemical bubbling are the
most suitable as electrode materials since they are probably free of
transition metal impurities.
Time-of-flight secondary ion mass spectrometry and total
reflection XRF were used to assess residual contamination (with
sensitivity better than 109 atoms/cm2) in graphene grown on Cu
foils and transferred to Si-wafers by wet etching or electrochemical
delamination [678]. Traces of copper and iron (~1013e1014 atoms/
cm2) were always found in the transferred graphene regardless of
the transfer method and subsequent cleaning. Increasing the
chemical etching time from 8 to 72 h reduced the amount of re-
sidual metal by ca. 50%, but at the cost of graphene integrity. As
noticed, a part of the residual Cu atoms is trapped within the gra-
phene layer/pockets and remains totally inaccessible to cleaning
treatments. During the CVD growth of graphene on copper, the
graphene surface is also contaminated by amorphous carbon. The
production of graphene transistors demands reliable electrical
contact. Unfortunately, common transition metals utilized as con-
tacts adsorb preferentially on the contaminated regions after
deposition, which causes poor contact between the metal and
graphene. CVD-derived graphene devoid of amorphous carbon
(>99.0%) was proposed to circumvent this problem [687]. Much
research work is also focused on the reduction of the organic res-
idue on graphene layers. Surprisingly, the presence of metallic
impurities on the surface of graphene hinders the removal of
organic impurities residing on the opposite site of the surface [688].
As a result, removal of metallic impurities permits the production
of higher purity graphene, free of organic contaminants. To obtain a
clean surface, the graphene sample is usually thermally treated to
burn off the organic polymer residue after transfer and device
fabrication. The thermal treatment is usually performed in air, CO2
or in a reductive H2 atmosphere at a temperature ranging from 150
to 350  C [689]. In fact, mild CO2 oxidation of amorphous carbon
commonly utilized for selective SWCNT purification has recently
been applied to CVD-grown graphene purification. A treatment
temperature of 400e550  C was indicated as optimal for guaran-
teeing a high etching rate of amorphous carbon without etching of
the graphene phase [690].
Besides heavy transition metal impurities, CVD-grown graphene
is also contaminated by Si, or alloys of Mg, Al, and Ti elements,
which originate from the quartz tube of the CVD furnace and from
impurities incorporated in the Cu foil [691]. In fact, quartz tubes are
not appropriate vessels for the CVD growth of graphene on Cu
substrates since white particulate impurities are usually observed
on the final graphene layer. Cu vapors diffuse into the quartz at
elevated temperatures (a phenomenon accompanied by its devit-
rification) and SiO vapors are released from the tube walls and form
the white particles [692]. Consequently, the ageing of quartz tubes
and sample holders introduces contaminations and deteriorates
reproducibility in graphene batches. The quartz tube can be
modified by inserting an internal coaxial alumina screen tube,
while tantalum can be used as the sample holder [692]. Such
modification of a CVD set-up yields contamination-free graphene
samples on Cu foils over extended periods of exploitation. However,
if quartz tubes are the only available option, silicate contamination
of graphene can be still avoided by sandwiching the sample be-
tween protective aluminum nitride substrates [693].
Since the Cu substrate constitutes the support, the quality of the
Cu foil influences the final quality of the obtained graphene and the
reproducibility of the growth process. Contaminations (e.g. Fe, Ca,
Si, Al, Pt, Ru and Ce) have been observed on the surface of high-
purity Cu foils [694]. Such contaminations are transferred to the
graphene. In addition, impurities with high carbon solubility (like
Ni or Al) constitute graphene nucleation sites yielding non-uniform
graphene films. As a result, the purity of the utilized Cu substrate is
of pivotal importance. Chemical treatments to dissolve the surface
contamination particles residing on Cu foil using HCl, KOH, HF,
HNO3, (NH4)2S2O8, commercial etchants and a combination of HCl/
KOH have been proposed [694,695]. By targeted removal of the Cu
foil surface impurities, the quality of graphene obtained can be
significantly improved. Importantly, different batches (with the
same catalog number) of commercial copper foil were studied to
assess the effect of copper pre-cleaning [696]. Reproducible
growths were obtained only when initial pre-cleaning was per-
formed. However, removal of impurities from the surface of Cu foil
is still not sufficient since impurities diffuse from the bulk to the
surface during the high-temperature growth. Consequently, a
method to remove impurities not only from the Cu surface but also
from the bulk was proposed where a solid cap was utilized as a sink
during annealing (Fig. 55) [697].
Fig. 56 shows the most common pretreatment approaches for
polycrystalline Cu catalyst foil and their abilities to reduce the
monolayer graphene nucleation density (GND) [698]. It has been
realized that carbon impurities within the Cu catalyst constitute a
serious obstacle in the production of high-quality monolayer gra-
phene [698]. Oxidizing the backside of the Cu foil was proven as an
efficient method to remove such impurities. Oxygen acts as scav-
enging agent for deleterious carbon impurities. This pretreatment
outranks other common pretreatment methods in terms of
reduction in the GND. The backside oxidation triggered reduction
in GND by six orders of magnitude as it leads to a redistribution of
the carbon impurity present in the Cu foil. In contrast, surface-
etching of the catalyst to remove contaminants allows reduction
of the GND only by two orders of magnitude for given conditions. A
similar level of GND reduction can be achieved by covering the
carbon impurities with a cleaner film of Cu on top of the Cu foil.
Electropolishing also allows the removal of surface carbon impurity
and the reduction in surface roughness.
6.7. Synthetic approaches to produce bulk quantities of GBMs
Ultrasonication or ball-milling are commonly utilized tech-
niques in the processes of preparation of chemically-modified/
converted graphenes from graphite. Ultrasonication is used to
exfoliate graphite oxide to graphene oxide. However, it can enhance
the redox availability of metallic impurities originating from
graphite. For instance, the concentration of Fe in the solution of
reduced graphene oxide showed a twentyfold increase when the
solution was subjected to a 180 min ultrasonication treatment
(from the initial 0.1 ppb of Fe before ultrasonication treatment)
[699]. Ball-milling of graphite is an easy method to obtain bulk
quantities of graphene-related materials. However, graphene ma-
terials produced by ball-milling are heavily contaminated with
metallic impurities originating from the grinding bowls and balls.
Nuclear-grade graphite (99.9995%) was utilized as a starting ma-
terial to assess the degree of such contamination [700]. Graphene
materials produced using stainless steel apparatus contained
drastically more metallic impurities (81657 ppm of Fe, 19907 ppm
of Cr, 1198 ppm of Ni, and 2328 ppm of Mo) than those produced
using a zirconium dioxide apparatus. Despite the application of the
“metal-free” ceramic zirconium dioxide ball-milling apparatus, a
small fraction of metallic impurities was still present in the ob-
tained material (95 ppm of Fe, 13 ppm of Mo, 8 ppm of Ni and Cr).
These metallic impurities constitute active catalysts in

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Fig. 55. Scheme of solid-diffusion-facilitated cleaning of copper foil to improve the quality of CVD graphene: (a) schematic of evaporation and solid diffusion pathways; (b) depth
profile of Al in copper foils in non-capped and capped annealing configurations; (c) enhancement in Al surface concentration proportion compared to non-capped and capped
annealed copper; (d) particle density versus the surface portion of Al in copper foils. Reproduced with permission from Ref. [697]. Copyright © 2019, Springer Nature.

Fig. 56. Overview of Cu pretreatments and their effect on graphene nucleation density (GND) and Cu surface roughness (Ra). Pretreatments are classified into categories IIII. (I)
Pretreatments that remove/cover the contamination layer on the surface of the catalyst, i.e. surface etching, performed by floating the Cu foil on a FeCl3 solution for different etching
times (green triangles) and sputtering 250 nm Cu on top of the Cu foil (“PVD”, green star). (II) Pretreatments that reduce the Cu surface roughness, i.e. electropolishing, indicated by
blue squares with increasing polishing times. The chemical mechanically-polished (CMP) sample is shown as a blue pentagon. (III) Pretreatments utilizing oxygen, i.e. backside
oxidization samples (BO) annealed in Ar are shown as red circles for various backside oxidation times. (b) Schematic indicating the cause of the reduction in nucleation density for
surface pretreatments IIII. Reproduced from Ref. [698] under a Creative Commons Attribution (CC-BY) License. (A colour version of this figure can be viewed online.)
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electrochemical processes.
7. Transition metal catalyst-free synthesis for metal-free
carbon (nano)materials
The most common, large-scale methods to prepare graphene,
carbon nanotubes and other carbon nanostructures involve either
graphite as a starting material (exfoliation, laser ablation, arc
discharge, etc.) or light carbon-containing molecules for CVD.
While there is no doubt that large-scale production of high-quality
carbon nanostructures requires TM catalysts, many alternative
methods of metal catalyst-free synthesis have been proposed on
the laboratory scale. These metal catalyst-free procedures rely on
the idea that any nanoscale curvatures, present for instance in
nanopowders or porous materials or as pits (cracks) in smooth
surfaces, can serve as sites (as seeds) for carbon nanostructure
growth instead of transition metal particles/surfaces. Some hy-
potheses suggest that the key role of catalysts is merely to provide a
template for fullerene-like cap formation in the case of SWCNT
growth. This class of methods would rely on high-temperature
CVD-like processes where metal catalysts are replaced by non-
metallic ones. The non-metallic material serves as a site where
light hydrocarbons are cracked and growth of the carbon material is
initiated. Besides high-temperature CVD-like processes, another
more ambitious approach to metal-free synthesis of CNMs is an
organic synthesis of carbon materials starting from simple organic
reagents. This is an ambient temperature and liquid-based organic
chemistry synthesis, but this approach is much more challenging
than CVD methods.
SiC in the form of films or NPs in one of the most common non-
metallic catalysts in the preparation of carbon nanostructures.
Decomposition of SiC at high temperatures under a vacuum (or
noble gases) is routinely used for graphene production and con-
stitutes a general method for the production of pure carbon ma-
terials (for instance graphite films) [701]. During high-temperature
annealing of SiC, Si evaporates leaving behind a Si-depleted surface,
which evolves into tetrahedral carbon and subsequently rearranges
into thermodynamically stable sp2 carbon. Electronic-grade wafers
can be utilized to obtain various graphenic structures of high purity.
Among numerous examples, a film of MWCNTs was produced by
the decomposition of SiC NPs using laser heating [702]. However, in
contrast to thermal decomposition of carbides, CVD-based syn-
theses are more attractive options for the industrial production of
carbon (nano)materials. Interestingly, both techniques can be
combined to obtain metal-free CNMs. For instance, SiC nano-
particles were used as a catalyst to selectively produce pure semi-
conducting SWCNTs. SiC NPs were used as templates to produce
carbon nanocaps, which then served as seeds to grow SWCNTs
[703]. Si atoms evaporated from SiC NPs upon heating and carbon
atoms formed nanocaps on the SiC surface. Next, the more chem-
ically active carbon caps of metallic chirality were preferentially
etched away under a H2 atmosphere. Finally, pure s-SWCNTs
without any residue metal impurities were obtained via deposition
of ethanol on the caps with semiconducting chirality. These metal-
free s-SWCNTs were then successfully used to fabricate thin film
transistors [703].
One of the classical “catalyst-free” CVD routes to CNTs and
porous carbons employs porous Al2O3 as a template [704]. In this
approach, porous Al2O3 fulfills the role of a catalyst and template,
which provides an interface for graphitic carbon formation. Porous
alumina oxides are often utilized as 2D templates in the prepara-
tion of arranged MWCNTs by the CVD method. Yet a large number
of ceramics/semiconductors in addition to alumina or carbo-
rundum have been employed to obtain carbon materials of nano-
fibrous morphology. Pure nanopowders of non-TM oxides (e.g.
SiO2, MgO, Ga2O3 or Al2O3) exhibit a catalytic graphitization ability
to produce graphenic structures under conditions typically used for
TM-assisted CVD synthesis of CNTs, CNFs and graphene [705]. The
catalytic activity of ceramics is attributed to the ubiquitous surface
defect sites on the nanosized oxides. Oxide nanopowders were
proposed for the mass production of permeable graphitic nanoc-
ages which may be applied in electric double-layer capacitors [705].
From the wide range of non-TM oxides, SiO2 is of special interest as
a catalyst for SWCNT/graphene production due to its ability for
direct application in silicon-based electronic technology. The
metal-free growth of SWCNTs on Si/SiO2 wafers is compatible with
temporary Si-based microelectronics [706]. The discovery that SiO2
NPs act as a catalyst for the CVD growth of SWCNTs at temperatures
of 800e900  C was indeed a breakthrough in metal-free production
of pure SWCNTs. It permitted synthesis of SWCNTs whose proper-
ties are not dominated by residual transition metal catalysts. Using
SiO2 film deposited onto a Si/SiO2 wafer, pure SWCNTs were
reproducibly obtained on the substrate by metal catalyst-free
deposition of CH4 at 900  C [707]. In addition, SWCNTs will grow
around the scratches during the CVD process after simple
scratching of the SiO2 surface [708]. Scratching produces SiO2 NPs
and particles of less than 2 nm in size act as active catalysts for
SWCNT growth. In fact, it has been claimed that any “small” par-
ticles (meaning powders with a suitable particle size) can catalyze
SWCNTs growth regardless of their chemical composition. How-
ever, the purity of the SiO2 NPs produced during scratching of silica
surface was assessed only by XPS - which might not be the right
technique to assure the absence of Fe, Co or Ni [708]. In addition, it
was still unclear whether the SiO2 nanoparticles themselves act as
the catalytically-active species or whether SiO2 undergoes carbo-
thermal reduction and SiC is formed in situ, serving as the effective
catalyst. Eventually it was shown that SiO2 nanoparticles can
indeed undergo carbothermal reduction to SiC during the CVD
synthesis of graphitic carbon nanostructures at 900  C [709].
Doubts on whether transition metal impurities are also involved in
the CVD synthesis of SWCNTs were clarified. SWCNTs were grown
on SiO2 substrates at 850  C by depositing ethanol and a precise
analysis of the metal content at different stages of the process was
performed (by total reflection XRF) to rule out the possibility of TM
involvement in nanotube growth [710]. While the content of Co and
Ni in the substrate was too low to be involved anyhow, the presence
of some Fe was detected. However, its catalytic contribution over
SiO2 in the formation of SWCNTs was excluded due to its low
concentration [710]. SiOx nanoparticles were also utilized to
selectively synthesize metal-free s- and m-SWCNTs by depositing
ethanol at 900  C [711]. Interestingly, control over nanoparticle size
and oxygen content of the SiOx catalyst played a crucial role in the
selective growth of SWCNTs of particular chirality. These nanotubes
were then utilized to fabricate all-SWCNT thin-film transistors to
demonstrate the potential application of these metal-free SWCNTs
in electronic devices [711].
One of the problems concerning the synthesis of carbon mate-
rials with TM-free catalysts is the somewhat low quality of the
materials’ graphitic structure and their poorly defined morphology.
For instance, thermal deposition of ethanol on a SiO2 catalyst often
leads to the formation of highly defective carbon nanofibers con-
sisting of stacked graphitic caps with a large number of Y junctions
and branches (Fig. 57) [709]. Another disadvantage of the SiO2
catalyst is low synthesis yield and hence difficulties in the large-
scale production of metal-free carbon structures. However, there
are some successful attempts to elaborate a continuous CVD syn-
thesis of CNTs at gram scale via metal-free catalysis [712]. This is of
special importance as the mass production of CNTs without any
metal contaminants would accelerate studies of the inherent
properties of carbon nanomaterials and their applications in

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Fig. 57. TEM images of the carbon nanostructures synthesized in CVD experiments from SiC particles: (a) overview image, (b) carbon nanostructure capped tip, (c) carbon
nanostructure open end, (d) branch on a nanofiber, (e) junction, (f) branch with SiC particle residing at the junction. Inset: FFT of the cubic SiC particle (200). (g) SiC particle at the
root of a carbon nanofiber, (h) higher magnification of the cubic SiC particle in panel g. Inset: FFT of cubic SiC particle (100). Ethanol was used in the CVD process (900  C, 30 min).
Reproduced with permission from Ref. [709]. Copyright 2009 American Chemical Society. (A colour version of this figure can be viewed online.)

electroanalysis, electrocatalysis and electronic devices. In one of
numerous examples, the synthesis of CNTs on silica NPs with the
addition of water provided MWCNTs of high quality as water
selectively removed amorphous carbon from the product [712]. In
fact, water-assisted CVD synthesis can provide high quality SWCNTs
with purity of 99.98% and Fe content of 0.013 wt% (XRF) even using
a Fe catalyst [475].
CVD utilizing copper as a catalyst is the most efficient method
for the synthesis of large-area and high-quality graphene films.
Unfortunately, graphene grown on a metal surface must be trans-
ferred to semiconducting or dielectric substrates for application.
The cumbersome transfer process became a serious hindrance to
the application of CVD-grown graphene in devices compatible with
the current Complementary Metal Oxide Semiconductor (CMOS)-
based technologies. Metallic impurities cause performance deteri-
oration of the electronic devices produced. Consequently, synthesis
of high-quality graphene films through CVD directly on non-
metallic substrates (semiconductors and dielectrics) could solve
this problem. A few reviews recently appeared dealing with tran-
sition metal-catalyst free CVD synthesis of graphene on techno-
logically critical dielectric (e.g. SiO2, h-BN, Si3N4, Al2O3, AlN, MgO)
and semiconducting (e.g. Ge, Si, SiC, GaN) substrates [713,714].
Similarly to the metal-catalyst free synthesis of CNTs, the TM-free
direct CVD growth of graphene on SiO2 has been reported by a
number of researchers. Si or Ge are also attractive substrates for
metal-free graphene growth. Few-layer graphene can be grown
directly on a Si surface without any metal catalyst following the van
der Waals growth model where Si acts only as a support/surface
where graphene can develop [715,716]. This is similar to the role of
Si-based catalysts in the metal-free production of CNTs. However, Si
is not the best metal-free support for graphene growth as it exhibits
relatively high carbon solubility at high temperatures, yielding
graphene films of low quality. In contrast to Si, germanium is a far
better substrate as it possesses higher catalytic activity, extremely
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low carbon solubility and high diffusivity, even at its melting point
[713]. Large-area, high-quality, and uniform graphene films were
successfully produced using a Ge substrate. The equilibrium phase
diagram of the GeeC system is very similar to the CueC system,
where carbon and the second ingredient are mutually immiscible
in solid and liquid states. Since carbon solubility in Ge is negligible,
surface-mediated and self-limiting graphene growth was observed
on Ge, which is similar to the Cu-catalyzed growth of graphene. In
addition, easy mechanical delamination of the graphene is possible
due to the weak binding energy between the graphene and the Ge
substrate [717]. Al2O3 is also an efficient catalyst for TM-free growth
of graphene. As shown, utilization of r-plane sapphire is beneficial
for growing uniform graphene even at a low CVD temperature due
to the excellent catalytic effect of the surface [718]. In the case of c-
plane and a-plane sapphire, graphene grew only in the pits in
which the Al-rich surface appeared and showed its catalytic effect
for graphene growth. However, it must be highlighted that gener-
ally, graphene growth on insulators (oxides, nitrides, etc.) is chal-
lenging as their catalytic activity is weak (in comparison to TMs).
The quality of graphene grown on insulators is usually inferior to
that of graphene obtained on metal catalysts.
Besides ceramics, pure carbon materials without any addition of
metal catalysts may also serve as supports in the production of
carbon nanostructures. High-surface-area or defective carbon ma-
terials (e.g. carbon black, activated carbons or graphite nano-
powder) are capable of carbon-catalyzed decomposition of light
hydrocarbon molecules (CH4, C2H6, etc.) in the CVD regime [719]. It
has been proposed that the catalytic properties of carbonaceous
materials are determined by their surface structure where defects
and dangling protrusions constitute active sites [720]. MWCNTs
were produced on a porous carbon surface at 800  C by decom-
posing ethylene and using carbon black (with specific surface area
of 1450 m2g-1) as a substrate [721]. To eliminate the influence of
residual metals, the utilized carbon black materials were purified to
reduce trace amounts of metallic impurities (Fe, Ni and Co) to levels
undetectable by ICP-MS. The fullerene-like surface defects and
pores of the carbon black were indicated as a key factor in the
catalysis of CNT growth. It is also possible to grow carbon nanotubes
directly on defect-rich graphite [722]. MWCNTs grow directly on
defective graphite surfaces through ethylene deposition at 850  C.
Growth was performed on flake graphite powder (purity >99.99%)
and on HOPG (grade ZYA) which exhibited only ppm levels of metal
elements (ICP-MS). An amorphous carbon film was also used as a
catalyst layer to deposit metal-free, bamboo-like MWCNTs from
methane but the final purity of the obtained CNTs was verified only
by EDS [723]. Nanodiamond particles (4e5 nm in size) can also act
as metal-free and entirely solid-state catalysts for SWCNT growth at
850  C using ethanol as a carbon source [724]. However, as dia-
mond particles do not have the ability to decompose carbon-
bearing molecules, the NPs were referred to not as a catalyst but
as “growth seeds”. In fact, fragments of carbon nanostructures have
been extensively utilized as seeds to grow CNTs [703]. Metal-free
SWCNTs can be prepared using carbon caps synthesized via ther-
mal opening of C60 [725]. The carbon caps serve as initiate sites to
SWCNT growth using a thermal ethanol CVD technique. Similarly,
an open-end SWCNT can be used as a seed to duplicate (clone) new
nanotubes without involving any metal catalyst [726]. Long
SWCNTs were cut into short segments via electron beam lithog-
raphy and the open-end SWCNT segments obtained were applied
as seeds to duplicate SWCNTs by CVD via an open-end growth
mechanism. The unique advantage of utilizing carbon nano-
structures as seeds is not only the ability to produce metal-free
CNTs, but also to get nanotubes of certain chirality [17,703]. For
instance, pre-selected single-chirality SWCNTs were used as seeds
for subsequent metal catalyst-free growth resembling the vapor
phase epitaxy (VPE) routinely used for semiconductor films [727].
Single-chirality SWCNTs were first obtained using a DNA-based
chromatographic separation technique. Secondly, separated
SWCNT seeds were used as templates for metal catalyst-free VPE
growth using CH4 or C2H5OH as the carbon sources. The catalyst-
free VPE-cloning-based approach might in principle solve the
problem of mixed nanotube chirality. However, the yield of VPE-
grown CNTs is low.
Water-soluble alkali metal salts (for instance NaNO3, K2CO3,
NaCl, etc.) are also able to decompose simple organic molecules
during chemical vapor deposition and act as catalysts for the
growth of fibrous CNMs [728e732]. Similarly, as in the cases of
ceramics and carbon supports/seeds, the nanoparticles of salts
serve as seeds on which the nucleation for CNT occurs. The great
advantage of this method is that the final carbon material can be
purified by simple water washing. In addition, synthesis of carbon
nanostructures over alkali salts is usually performed at low tem-
peratures of 450e500  C. For instance, N-doped carbon nanofibers
were prepared utilizing Na2CO3 powder as the catalyst, acetylene as
the carbon source and NH3 as the nitrogen source [731]. The salt
catalyst was removed by washing with water and the metal-free, N-
doped carbon of high purity was easily separated. However, carbon
nanostructures produced via salt-assisted catalysis exhibit poorly
defined morphology representing a complex mixture of fibers with
diverse lengths and diameters including linear and helical carbon
nanofibers and bamboo-like CNTs. The obtained structures are
generally of low quality (branched, kinked and poorly graphitized).
Carbon nanostructures (nanotubes, graphene and their compos-
ites) are considered as prospective microwave absorbing materials,
but residual metal catalysts interfere with their intrinsic optical
properties. To understand their intrinsic microwave absorption
properties, metal-free CNTs were obtained over water-soluble
K2CO3 particles [732]. The leftover catalyst imposes negative ef-
fects on the intrinsic microwave absorption properties of CNTs,
while an enhanced microwave absorption performance was
observed for the metal-free CNT sample obtained using K2CO3.
Apart from the abovementioned representative examples, there
are other interesting approaches to prepare metal-free carbon
nanostructures. For instance, transition metal-depleted graphene
materials were obtained via reduction of CO2 (dry ice with purity of
99.9993%) by elemental lithium (purity of 99.9%) [733]. The
graphene-based materials produced contained 0.67% of Li, 0.001%
of Cr, 0.0088% of Fe, and 0.0058% of Pb (wt%, ICP-MS and ICP-AES)
and were employed as electrochemical impurity-free materials.
Synthesis of carbon materials from CO2 or CO is in fact a very
common practice (e.g. HiPco and CoMoCAT processes) and in some
sense these methods resemble the synthesis of carbon blacks e
which can be obtained as high-purity carbons free of TM
contaminations.
Bottom-up organic synthesis offers a unique ability to synthe-
size carbon nanostructures (CNTs or nanosized graphene-based
molecules) with atomic precision [16,734,735]. Consequently,
nanocarbon entities of perfectly-defined chemical structure can be
prepared. This is of special importance since the CVD-based
method always yields a mixture of carbon nanostructures with
diverse properties. In principle, a certain type of nanotube can be
constructed using chemical reactions, starting from a suitable hy-
drocarbon template. For instance, reactions between C2H2 and
polycyclic aromatic hydrocarbons in organic solvents have been
proposed for metal-catalyst-free synthesis of SWCNTs [736].
Organic chemistry synthesis can be also combined with a VPE-
based elongation process for the metal-catalyst-free growth of
SWCNTs of specific chirality. 100% pure end-caps of a (5,5) nano-
tube (that is C50H10 molecules) were prepared using an organic
chemistry approach and then used as seeds for chirality-controlled

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growth of SWCNTs via metal-free VPE elongation [737]. However,
organic synthesis of carbon nanostructures is still in its infancy and
it will take decades for this brand new division of organic chemistry
to become well developed. For now, the yields are low and the
procedures are very expensive [16].
In summary, non-metallic or TM-free catalysis to produce CNMs
via CVD is based on the principle that any nanosized object/feature
with some defects (nanopores, exposed open edges, scratches, etc.)
can act as seeds to initiate the growth of graphenic structures [738].
As a result, ceramic nanopowders, porous carbon materials or
fragments of carbon nanostructures constitute active catalysts/
seeds for the metal-free catalysis for the growth of carbon struc-
tures. However, despite impressive advances in the development of
non-metallic catalysts, the yield and quality (crystallinity and
morphology) of the carbon nanostructures produced are still infe-
rior to those of materials obtained with the assistance of TM cata-
lysts. In addition, for many of the metal-free catalyzed CNMs
studied, appropriate purity tests were not performed, so there is
insufficient evidence to support the hypothesis that the materials
obtained did not contain a substantial amount of transition metals.
The search for mass production methods of CNMs over non-
metallic catalysts is still poorly developed. These methods are
however highly desirable for applications where metal impurities
impose serious problems (i.e. medicine, sensing and nano-
electronics). Organic chemistry synthesis permits the production of
carbon nanobjects with atomic precision. In fact, this approach
might produce carbon-based materials with purity and uniformity
approaching 100%, but implementation of this brand new division
of chemical synthesis for industrial production is still decades away.
8. Turning metallic impurities into an advantage
As substantiated above, some specific carbon structures are
inherently destined to exist as transition metal-contaminated
structures. This is (or, might be) the case for any carbon structure
obtained by methods involving metals as reagents, catalysts, tem-
plates, supports, etc. during synthesis. While the presence of
metallic impurities (as single atoms, few-atom clusters, NPs or
more complex compounds) exhibit diverse detrimental effects,
there are potential advantages to their presence. One of the most
prominent examples is the employment of TM impurities as a
catalyst supported on carbon scaffolds. Metallic impurities in car-
bon fibers facilitate their oxidation and hence improve shear
properties of their composites. However, less obvious examples can
also be pointed out. A peculiar example is the employment of CNT-
encapsulated Fe NPs in the unzipping of tubes to obtain GNRs [739].
Thermal treatment of nanotubes containing Fe NPs for 26 h at
1100  C under an Ar atmosphere yielded nanoribbons 15e40 nm
wide and 100e500 nm long. At 1100  C, the encapsulated Fe NPs
react with the carbon causing its dissociation and breakage of the
tube. Yet intentional utilization of metallic residues to serve a
certain purpose still requires detailed knowledge concerning their
type, location and most importantly concentration.
8.1. Metallic impurities as a proxy for detection and tracking of
carbon (nano)structures
Analytical techniques to quantify and qualify carbon nano-
materials rely on the unique features that differentiate them from
other materials/substances. For instance, in contrast to organic
molecules, carbon nanotubes and nanofibers have huge and variant
molecular weight, exhibit a wide distribution of lengths and di-
ameters and are insoluble in most solvents. Consequently, tradi-
tional analytical methods designed for the analysis of organic
compounds are not suitable for the identification of carbon
823
nanomaterials in natural or laboratory environments [150]. As
shown in previous chapters, the diversity of carbon nanomaterials
presents a challenge in the development of analytical methods for
their qualification and quantification. Detection of engineered
carbonaceous materials could simply rely on carbon analysis.
However, this approach is unreliable due to ubiquitous presence of
carbon in the environment. For instance, the current method for
detection of airborne CNTs in factories applies thermo-optical
analysis for elemental carbon determination. Unfortunately, this
approach does not distinguish between CNT and non-CNT sources
of elemental carbon. The same issue occurs with Raman spectros-
copy or UVeVIS spectrophotometry. In addition, structures like
CNTs found in the natural environment or in workplaces occur as
micron-scale clumps or agglomerates and not as individual fibers.
Metal catalyst impurities inherent in structures such as SWCNTs
can be conveniently utilized as a specific proxy to identify and
qualify CNTs in natural and man-made environments. Metal im-
purities may allow the differentiation of synthetic carbon materials
from natural background sources of elemental carbon. Specific
metals can serve as taggants - a unique signature characteristic only
applicable to a certain material that can be used to track down and
follow synthetic CNMs in an environment. For example, if analysis
of an environmental sample would reveal elevated values of un-
common elements (e.g. yttrium or molybdenum) or specific ratios
of metals (e.g. Co to Mo), this could be correlated with the presence
of synthetic CNTs. A number of studies employed metal catalyst
impurities as proxies for the detection of CNTs/CNFs not only in the
natural environment, but also more importantly to monitor the
exposure of workers in workplaces. However, this method could be
successful only if the catalysts used to synthesize carbon nano-
structures are of an element with low concentrations in naturally
occurring matrices (e.g. Y or Mo). In addition, considering the di-
versity of metal catalysts used in the synthesis of carbon materials,
a universal marker for such materials does not exist. The Fe catalyst
routinely used for CNTs synthesis is not a reliable proxy due to its
common occurrence in the natural environment and factories. As
shown, iron is not an appropriate marker for the exposure of em-
ployees to inhalable MWCNTs/CNFs because of its high background
concentrations [740]. To eliminate random interferences, selection
of the right proxy requires an initial analysis of the carbon material
to be identified and the analysis of elements occurring in the
background environment. Besides the presence of unique metals or
atypical metal/metal ratios, the unique metal/carbon ratio of syn-
thetic carbon materials could also be used to trace them. For
example, when Ni was used as a catalyst in SWCNT synthesis, the
Ni/C ratio in the product varied between 0.20 and 0.37 [486]. These
proportions are orders of magnitude higher than those of other
common carbon aerosols, such as coals. Rasmussen et al. presented
a series of reports concerning the detection of carbon structures via
metallic tracers to assess exposure of staff involved in production of
CNTs and nanofibers [741e743]. Exposure of workers to CNTs can
occur at various stages of the manufacturing process and during
storage and transport. The specific Y/Ni ratio was proven to be a
useful marker to distinguish aerosolized SWCNTs from background
aerosols in a research laboratory environment [741]. This approach
proved to be viable as concentrations of Y and Ni were thousands of
times lower in ambient air particles. However, it is important to
note that the SWCNT material used in that study contained a high
amount of metallic impurities of up to 30e35 wt% with 2.6% of Y
and 13% of Ni (ICP-MS) [741]. In other similar studies, Co was used
as a marker since the elemental ratios of Co/Fe permitted distinc-
tion of the CNT from non-CNT sources of contamination [742,743].
Moreover, stable isotopes (such as Pb) could be deliberately
incorporated into carbon materials during production as taggants
to allow assessment of health risks to employees or of the fate of
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W. Kicin
such materials in the environment. A Pb isotope that was unin-
tentionally introduced into CNTs during their production was
indeed utilized for identifying aerosolized CNTs in workplaces
[742]. In fact, carbon nanomaterials from different factories could
be easily identified and monitored if they had distinctive isotope
signatures. The Fe/Ni ratio was also used to estimate employee
exposures to SWCNTs [744]. However, detection was once again
facilitated by a high content of Fe and Ni (30 wt% combined mass) in
the unrefined SWCNT material.
Presently, the most common application of advanced carbon
nanomaterials concerns composites based on carbon fibrous
structures or carbon nanopowders embedded in polymer matrices.
Likewise, metal impurities have been used as proxies for the
quantification of CNTs in polymer composites and to assess the
exposure to CNT in CNT/polymer composite production [745e747].
However, such studies usually rely on high contents of metallic
impurities in the carbon material of interest. While metal catalyst
qualification and quantification is a convenient way to assess
exposure to raw carbon nanomaterials, this approach may be not
adequate when it comes to their purified counterparts which
contain only traces of metals. Consequently, using metallic impu-
rities to detect purified carbon structures is more challenging or
potentially impossible, unless specific markers (for instance rare
yet stable isotopes) are intentionally introduced during the
manufacturing process [748]. Another difficulty is the well-known
variability of catalyst content and ratio from batch to batch in the
production of synthetic carbons.
While qualification and quantification of carbon nanomaterials
in laboratories and factories is already challenging, their detection
in the natural environment is far more complicated. Environmental
concentrations of carbon nanotubes are in a low range of ng/L and
hence only exceptionally sensitive analytical techniques are fit for
detecting such amounts. A single-particle inductively-coupled
plasma mass spectrometry (spICP-MS) has been proposed as such a
sensitive tool for detection of single- and MWCNTs by monitoring
metal impurities [749e751]. In one specific case, the monoisotopic
Co and Y elements were selected as the most reliable for differen-
tiation of SWCNTs from the background [749]. Use of the residual
catalyst as a proxy in spICP-MS was proven effective for mass
quantification of CNTs in environmental exposure assessments. The
ability of spICP-MS to quantify CNTs in biological tissues is its most
important advantage over traditional ICP-MS analysis [750]. Due to
low background yttrium concentrations in wastewater, Y was used
to track MWCNT removal during wastewater treatment [751]. The
detection limit of the specific MWCNTs was 0.82 mg/L using Y as a
surrogate, compared with >100 mg/L for other techniques applied
for MWCNT quantification in wastewater biomass. However, spICP-
MS also has some serious limitations. Not all CNTs contain detect-
able levels of metallic particles and the distribution of particle
mass/size among CNTs is highly heterogeneous, resulting in
undercounting of CNTs.
Since CNTs are usually quantified in organisms and natural ex-
tracts using near-infrared fluorescence spectroscopy (NIRF), the
catalyst proxy approach is proposed as an efficient complementary
method for detecting CNTs that are not intrinsically fluorescent in
the environment. For instance, Schierz et al. combined NIRF and
ICP-MS and used the Co/Mo ratio to determine SWCNT occurrence
in sediments after a simulated spill of SWCNTs in wetland ecosys-
tems [215]. CoMoCAT SWCNTs (containing ca. 0.9 wt% of Co and
2.1 wt% of Mo) were used in that study as received without any
further purification. An interesting method for the selective
detection of CNTs in aerosol samples utilizing native metal impu-
rities was proposed by Neubauer and Kasper [752]. They proposed
utilization of catalyst impurities for a dual purpose: CNT detection
and catalysis of chemical reactions. Nickel impurities (of high
content, up to 38 wt%) were used as a catalyst for the oxidation of
CO to CO2 at 470  C. Nickel was exposed at that temperature by
burning off the carbon, yielding a linear relationship between CO
conversion and Ni mass. Monitoring of the change in concentration
of the reactants (CO/CO2) permitted estimation of MWCNT con-
centration. Metallic impurities can also be exploited to identify
graphite samples. INAA studies of eight samples of graphite (nu-
clear and commercial grade materials) demonstrated that the trace
element profile of each graphite sample from different sources is
unique and can be used as a fingerprint to differentiate between
graphite materials [753]. This could be of use in specific cases of
forensic investigation where graphite-containing devices (for
instance explosive devices) are utilized.
In summary, using metal impurities as a proxy to track and
quantify engineered carbon (nano)materials is an attractive yet
challenging approach. Metallic impurities are reliable fingerprints
only if they are homogenously distributed throughout the carbon
material, do not easily leach out from the carbon matrix and have
low background occurrence in the environment of interest. In re-
ality, the amount and state of metallic impurities in carbon matrices
change over time and the interference of metals from the envi-
ronment is difficult to overcome. So far, this method was proven to
be viable only for samples with large amounts of less-common
metallic impurities.
8.2. Advantages of metallic impurities in (electro)catalysis and
energy storage
Since transition metals are intentionally deposited on carbo-
naceous supports to fabricate (electro)catalysts, the deliberate use
of residual metallic phases in engineered carbon materials is a
reasonable, low-cost approach for the production of advanced
functional carbon/metal composites. Such materials have been
utilized not only in heterogeneous catalysis but also in applications
concerning electrochemical capacitors, sensors and adsorbents.
Pumera, who has published vast amounts of data questioning the
“metal-free” (electro)catalytic properties of nanocarbons, has also
highlighted that metallic impurities do not always have to be
considered as a disadvantage. As a proof of concept, he showed that
residual metal catalysts (Fe, Ni, Cu, Co and Mo) present in thermally
reduced GO can be employed in electroanalysis [754]. A prominent
example of using metal impurities as catalysts is the ORR electro-
catalyst prepared via exfoliation of the outer walls of fWCNTs
containing 3.7 wt% of Fe [755]. The outer walls were partially
unzipped, creating sheets of graphene. The presence of Fe impu-
rities in the obtained structure (1.1 wt% (0.24 at%)) permitted the
formation of FeeNx/C catalysts once the unzipped CNTs with the
exposed residual iron were annealed in NH3 at 900  C. Fe impurities
(0.57 wt%) present in the graphite flakes utilized as a precursor of
graphene yielded enhanced electrocatalytic activity in the obtained
MnOx/N-doped graphene composite towards both the oxygen
reduction and the oxygen evolution reactions [756]. More exam-
ples of reports on the role of intentional use of carbon materials
with TM impurities for the catalysis of ORR and OER can be found in
the literature [589]. As-synthesized commercial CNTs (from Bayer
Materials Science and Applied Sciences Inc.) were also shown to be
a highly active catalyst for NH3 decomposition [757]. The content of
residual ashes in the Co- and Fe-containing CNTs were 4.1 and
2.8 wt%, respectively. The CNTs were used as catalysts without
additional chemical pretreatment. An efficient conversion of NH3
was achieved at 650  C and iron nitride (FeNx) was identified as the
active phase for its decomposition [757]. Metallic impurities have
also been used as a catalyst for the oxidation of organic molecules.
A MWCNT sample containing 2.1 wt% of intrinsic iron was exploited
for the electro-oxidation of benzene to quinones, where the iron

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin 825

impurity acted as an electro-Fenton catalyst [758].
Carbon nanostructures with native metallic impurities can also
be exploited to produce amperometric sensors. Pristine (i.e. as-
received, without further purification) MWCNTs containing
0.211 wt% of Fe and 0.115 wt% of Co were selected to develop highly
sensitive amperometric sensors for drugs and antioxidants [759].
Fe and Co impurities played a key role in the sensitivity enhance-
ment of the electrochemical sensors. Kumar et al. published
extensive experimental data concerning the use of TM impurities in
CNTs for electrocatalytic and electroanalytic applications
[760e764]. For example, the derivatization of an intrinsic iron
impurity (2.1 wt%) in MWCNTs resulted in a hybrid electrode which
was applied as an electrochemical detector for the analysis of DNA
purine bases [760]. A SWCNT sample (40e60 wt%) containing Ni
(8.7%), Fe (4.5%) and Zn (7%, ICP-MS) was utilized for amperometric
detection of Bisphenol A. Interestingly, the acid-purified SWCNTs
did not show any characteristic redox peaks during the electro-
oxidation of Bisphenol A, which indicates that the presence of a
residual metal in SWCNTs plays a vital role in electro-oxidation of
this molecule [761]. However, a variety of carbon blacks can serve
similar purposes in addition to CNTs. Conductive carbon black
characterized by a high surface area (1000 m2ge1, particle size
<15 nm, ash content <0.60%) and trace metal impurities (Fe
(108 ppm) and Ni (8.1 ppm), ICP-AES) was applied for electro-
catalytic oxidation and detection. Ni and Fe played significant roles
in reducing the overpotential and enhancing the oxidation/sensing
of L-cysteine [762]. Finally, the electrochemical properties of
metallic impurities in CNMs were also utilized to enhance carbon
nanotube capacity for supercapacitor electrodes. Implementation
of CNTs for electrochemical double layer capacitors still remains
unrealized due to their inherent low energy density. To increase the
capacity of MWCNTs containing residual iron particles (of up to
6.0e9.0 wt%, EDX), the tubes were either fractured by voltammetric
cycling (Fig. 58) or unzipped by KMnO4/H2SO4 treatment to expose
the iron phase [765,766]. This provided additional Faradaic charge
storage caused by the Fe2þ/Fe3þ transition, which yielded a 350%
increase in the peak capacitance of MCWNT electrodes (from 70
Fge1 for the purified MWCNT electrodes to 316 Fge1 for the Fe-
containing nanotubes).
In another example, the combination of the developed surface
area of CNTs and the redox activity of the exposed catalyst particles
permitted a significant increase in capacitance of the CNT/iron
oxide composite [767]. Controlled amounts of Fe catalyst from a
CNT sponge were exposed by annealing in air at 450  C. The
resulting CNTeFe2O3 sponge was utilized as a porous catalyst
substrate for further growth of new CNTs. The obtained CNTeFe2O3
sponge composite was then tested as a freestanding supercapacitor
electrode which showed a 9-fold capacitance increase in compar-
ison to the original CNT sponges. Interestingly, this report showed
that exposed metallic catalysts within CNTs can be used to grow
new nanotubes on the existing ones (Fig. 59) [767]. Other examples
where Fe impurities in carbonaceous materials (e.g. in pencil lead
graphite) yielded enhanced capacitance of electrodes for super-
capacitors via Faradaic reactions were also reported [768].
8.3. Carbon materials with residual metallic impurities for
diagnostic and medical treatment
Since metal particles encapsulated inside carbon nanostructures
are often considered stable and difficult to remove, such compos-
ites garnered significant attention in medical research. Owing to
their optical activity, high surface area (high surface area to volume
ratio) and hence propensity to adsorption and chemical and
physical functionalization, carbonaceous nanomaterials are still
considered a promising platform for biomolecular imaging, bio-
sensing, and drug and gene delivery [769e771]. For instance,
different carbon nanostructures have been employed to develop
composite magnetic resonance imaging (MRI) contrast agents
[769]. MRI is probably the most important noninvasive imaging
technique in medicine. Chemical contrast agents are used to
improve its sensitivity. Superparamagnetic Fe3O4 NPs represent
one of the most common contrast agents. Fe3O4 particles can act

Fig. 58. Schematic representation of the electrochemical activation process of MWCNT electrodes, inferred from TEM images (shown in insets) and electrochemical analysis. The
initial structure of MCWNT electrodes containing Fe/Fe3C catalyst particles (a) is physically stressed (b) when the electrochemical potential is increased beyond 0.9 V, leading to
etching (c) and rapid oxidation (d) upon electrolyte infiltration. The electrochemistry associated with these processes are illustrated by the cyclic voltammetry scan (e), which shows
the current during electrolysis (pink) and an anodic current spike associated with Fe ion dissolution during the etching (blue). The cyclic voltammetry profile after treatment (f)
shows the contribution of the Fe2þ/Fe3þ redox couples (green) to the electrochemical behavior of the MWCNT electrodes. Reproduced with permission from Ref. [765]. Copyright
2014 American Chemical Society. (A colour version of this figure can be viewed online.)
826
W. Kicin
Fig. 59. Schematic illustration of the synthetic method towards exposed residual catalysts in CNTs and the applications of CNTeFe2O3 composite sponges for porous catalyst
substrates and supercapacitor electrodes. Adapted with permission from Ref. [767]. Copyright 2016 The Royal Society of Chemistry. (A colour version of this figure can be viewed
online.)
either as a ferromagnetic or superparamagnetic material depend-
ing on the particle size. They attenuate the NMR signals of water
molecules in surrounding tissues and yield hypointense regions in
the MR image. Fe3O4 NPs induce dephasing of the proton spin by
energy exchange between the atomic nuclei, resulting in a decrease
in spin-spin relaxation time T2 (T2 is the proton relaxation time)
and thus allow creation of the image contrast [772]. Both single-
and MWCNTs represent some of the most common CNMs studied
as promising candidates for MRI contrast agents. However, the ef-
ficacy of these types of agents depends on the amount of iron re-
sidual catalyst retained by CNTs after their synthesis and
processing. Furthermore, specific types of MR diagnosis require
CNTs with variant Fe-contents. For instance, pulmonary bio-
distribution studies of SWCNTs with Fe content of 10.14 wt% (CNI®
Buckytubes, HiPco) and their super-purified counterparts with only
0.8% of iron (ICP-MS) showed that only the tubes with higher Fe
content could be detected in vivo and had the properties of a good
contrast agent [772]. Iron impurities in carbon nanomaterials also
enable their detection, monitoring and fate within living organisms
by MRI. Hyperpolarized 3He was proven effective for the pulmo-
nary biodistribution of high Fe-content SWCNTs, while standard
proton MR was useful for systemic investigation upon injection of a
nanotube solution. However, some reports suggested that even
traces of Fe impurities can yield a significant contrasting effect.
Functionalized commercial SWCNTs containing only traces of iron
oxide (0.07 wt% Fe) proved to be efficient MRI contrast agents for
in vitro and in vivo imaging in mice organs [773]. Unlike the iron-
free nanotubes, the functionalized SWCNTeCOOH exhibited cor-
relation between the presence of iron oxide and the transversal
water proton relaxivity. The observed T2 effect was attributed to the
presence of trace Fe. Moreover, cytotoxicity studies showed no
detrimental effect related to the presence of CNTs [773]. Torti et al.
elucidated that the r2 relaxivity of as-grown MWCNTs (CVD) in-
creases linearly with the mass content of the iron catalyst in the
studied range of 1.26e2.92 wt% [774]. The enhancement of the
magnetic resonance contrast properties of MWCNTs was directly
linked to their Fe content. The produced MWCNTs were washed by
ultrasonication in H2SO4/HNO3 (3/1) before experiments to elimi-
nate any exposed iron particles. On the other hand, some in vitro
experiments showed that MWCNTs with a high Fe content (10 wt%)
tended to agglomerate and the best MRI contrast and biocompat-
ibility was achieved at lower iron contents of ca. 2% [775]. The
sample with 2 wt% of Fe yielded better contrasting results than the

ski, S. Dyjak / Carbon 168 (2020) 748e845
studied CNT/Fe nanocomposites dispersed in both water and cul-
ture media, and exhibited higher stability (with respect to
agglomeration) in such environments. Moreover, MWCNTs with
lower Fe content exhibited a lower cytotoxic effect [775].
As one could expect, there is serious inconsistency in the liter-
ature when it comes to the optimal amount of iron oxide phase
within CNTs to obtain good contrasting performance in MRI. For
instance, SWCNTs (HiPco, Carbon Nanotechnologies, Inc.) contain-
ing 17.2 wt% of iron catalyst were purified using liquid Br2 to lower
the Fe content to 6.1%. The purified SWCNTs were then cut into
ultra-short tubes by fluorination using a He/F2 mixture (2F2 þ C /
CF4) at 50  C [776]. The cutting process reduced the metal content
to 0.63 wt% (ICP-AES). The superparamagnetic ultra-short SWCNT
material exhibited high efficacy contrast properties originating (as
the authors claimed) not only from the iron catalyst particles, but
also from the SWCNT material itself. Importantly, it was demon-
strated that a higher concentration of metal catalyst does not
necessarily produce better contrast properties. Besides, better
relaxivities of SWCNTs with lower metal content were of special
importance, since this could lower the possible toxicity of such
materials when used as in vivo MRI agents. Knowing that the
catalyst-containing carbon nanostructures exhibit contrasting
properties, MRI can be used to detect and evaluate the bio-
distribution and biological impact of CNTs in animal and human
organs [772]. This approach may be complementary to quantify
carbon nanotube concentrations in organs using the Raman spec-
troscopy technique. In fact, the strong resonance-enhanced Raman
scattering of SWCNTs has often been utilized for their in vitro and
in vivo imaging. For instance, in vivo MRI imaging of carbon nano-
tubes was utilized to evaluate accidental exposure to CNTs via
respiration. This approach allowed study of CNT distribution in
organisms upon inhalation [772]. MWCNTs were proven to be
powerful in-vitro/in-vivo contrast agents for the labeling and
tracking of cells, including those of human origin (human pancre-
atic islets) [777]. In this application, MWCNTs show similar effects
when compared to the commonly-used superparamagnetic iron
oxide nanoparticle ferumoxide (Endorem) in MRI cell labeling. This
is especially interesting since the amount of Fe in the utilized
MWCNTs was approximately 2.5 wt%, in comparison to 76% in
Endorem. As mentioned above, CNTs can also serve as multimodal
imaging agents. Functionalized HiPco SWCNTs containing Fe
(6.26 wt%) and Co (0.3 wt%, ICP-AES) were used as multimodal
probes for simultaneous stem cell labeling and tracking [778]. Their

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W. Kicin
strong intrinsic vis-to-NIR optical absorption and the presence of
magnetic particles made them universal photoacoustic tomogra-
phy and MR imaging contrast agents. In another study, HiPco
SWCNTs with an iron oxide nanoparticle content of 35 wt% were
used to image macrophage cells by MRI and NIR mapping [779].
The magnetic properties of iron oxide NPs and the near-infrared
fluorescence of SWCNTs yielded an efficient multimodal bio-
imaging agent. As cells do not autofluoresce in the NIR, intrinsic
SWCNT fluorescence has been routinely utilized to map the
pathway of cellular nanotube uptake [780]. Semiconducting
SWCNTs possess band-gap photoluminescence with emission in
the NIR to IR range, which is a useful optical property for imaging in
biological systems. However, one should consider that the lumi-
nescence properties of CNTs are strongly influenced by the pres-
ence of metallic impurities and in reality, the luminescence of many
CNT samples might indeed be extrinsic (caused by metallic impu-
rities) [212].
Carbon nanostructures containing residual metal catalysts can
be used not only for diagnosis, but also for therapy. Fe-containing
MWCNTs were applied for simultaneous MRI and in vivo thermal
ablation of tumors (laser-induced thermotherapy for cancer treat-
ment) [774]. Thermal ablation therapy employs the ability of CNTs
to absorb NIR radiation and generate heat. The heat-generating
abilities of Fe-containing MWCNTs (with Fe content in the range
of ca. 1.3e2.9 wt%) upon exposure to near infrared laser irradiation
was determined in vitro and in vivo. Significant tumor regression
was observed in mice treated with the MWCNTs upon NIR laser
irradiation. This property of MWCNTs with Fe residues allowed
both treatment of the tumor and simultaneous collection of suc-
cessive MR images without the need for further injection of
contrast agents. Gene delivery into cells has also been realized
utilizing CNTs containing Ni particles enclosed in their tips [781].
That approach was based on the mechanical penetration of nano-
tubes into cell membranes by a magnetic field driving force. This
so-called nanotube spearing allowed implantation of plasmid DNA
immobilized onto the nanotubes into the targeted cells. At that
time the authors assumed that Ni particles were fully encapsulated
and hence could not cause any adverse effects. However, now we
know that this assumption is overoptimistic and Ni phase can be
released from the nanotubes in the cellular environment and
induce toxicity.
In summary, CNMs containing residual iron particles have been
successful applied as effective MRI contrast agents and proven to be
competitive in relation to their commercial counterparts. However,
the type of carbon nanostructure, their additional functionalization
and the iron content significantly affects the carbon/metal com-
posite effectiveness as an MRI contrast. Furthermore, specific im-
aging modes require carbon nanostructures with variant Fe-
content. As observed by Vittorio et al., the utility of CNTs contain-
ing residual catalyst as MRI contrast agents must be determined
individually for each specific sample [782]. Techniques relying on
the optical properties of CNTs must also take into consideration the
variance of emission, which is dependent upon the presence of
specific metallic impurities. Eventually, the application of carbon/
TM structures in therapy is not as promising as it may seem because
even tightly encapsulated metal NPs may be mobilized by body
fluids causing various toxic effects [783].
9. Conclusion
While graphene and SWCNTs have yet not revolutionized
technology in any visible way, apparently obsolete carbonaceous
materials such as graphite, carbon black and activated carbons are
now at the frontier of portable electronics and the electric vehicle
revolution [784]. New carbon nanomaterials are also outshined by
827
ordinary activated carbon in the field of medicine. As recently
stated by Mikhailovsky, the biggest use of carbonaceous materials
in medicine is in the treatment of acute poisoning by activated
carbon (also used in medical devices such as extracorporeal blood
purification) [785]. From coals and natural graphite to engineered
carbon nanostructures, the variety of sp2/sp2þεehybridized carbon-
based materials yielded a large number of reports on their prop-
erties and applications. Carbon nanostructures are particularly
interesting as they lie on the vague border between molecular and
bulk material chemistry. High heterogeneity, affinity to hetero-
atoms, large specific surface area and ease of intercalation make
graphenic carbon materials especially susceptible to contamina-
tion. Unlike the main-group elements, transition metals are a
unique type of impurity and a source of artifacts, which may
dominate the properties of carbonaceous materials. It is all down to
interaction between the semi-vacant d-orbitals of TMs and the p-
orbitals of carbon atoms. The adverse effects of TM impurities
within carbon materials include, but are not limited to:
 secondary catalytic effects and interference with the native
catalytic properties of carbon structures
 interference or domination over the native magnetic properties
of carbon
 increase in the reactivity of carbon structures and induction of
secondary/side redox reactions (e.g. in the process of composite
preparation)
 acceleration of carbon material corrosion (e.g. embitterment of
graphite)
 decrease in oxidation resistance, induction of pyrophoric prop-
erties and explosibility
 induction of carbon material toxicity
 interference with adsorption properties including H2 storage
capacities
 limitation of graphitic materials’ usability in nuclear technolo-
gies (and, to lesser extent, in the industrial production of
aluminum)
 modification of thermal and electric/electronic conductivity and
band-gap (especially problematic for SWCNTs and graphene)
 decrease in mechanical strength of carbon structures and their
composites
 decrease in the lifetime of electrode materials in supercapacitors
and batteries
 modification of the native optical properties of carbon (e.g.
luminescence properties of CNTs).
A classic example of artifacts caused by TM impurities is the Mn
contamination in rGO which contributes to the electrocatalytic
activity of GO-derived materials. In hindsight, the artifacts caused
by Mn impurities were easy to predict since parallel effects were
observed earlier for carbon nanotubes [786]. The history of nano-
carbons repeats itself in this aspect.
Direct observation of substitutional Au atoms in the structure of
CNTs [91] helped us realize that most TM atoms can easily diffuse
deep into graphitic structures and form stable bonds with the sp2
carbon lattice. Consequently, TM catalyst-assisted syntheses always
contaminate graphitic structures and it is impossible to completely
remove such TM impurities by any known liquid-based purification
method. Even if carbon nanostructures are obtained in metal-free
processes, defects present within their structure act as traps for
transition metal atoms. Once bonded, TM atoms form thermally
and chemically stable sites and alter all the fundamental properties
of carbon (nano)objects/materials. The strong covalent CeC bonds
within the hexagonal carbon lattice and its ability to self-heal via
saturating dangling bonds by creating non-hexagonal rings make
substitutional doping of sp2-hybridized carbon difficult. However,
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W. Kicin
once a TM atom is trapped as a substitutional defect site (TM@va-
cancy complex), it remains firmly bonded and resistant to removal
by common purification techniques. N-doped carbon materials are
especially prone to metal contamination as they constitute a kind of
solid-state ligands forming stable complexes with TMs. Since N-
doped carbon (nano)materials constitute efficient adsorbents of
transition metals and exceptional catalyst supports for stabilizing
single metal atoms, caution must be taken when they are studied as
metal-free multifunctional catalysts. A similar effect is expected for
carbons doped with other p-group heteroatoms (B, S, P, etc.)
because heteroatoms increase the reactivity of the sp2 basal panel
and cause a profusion of defects. For this reason, obtaining truly
metal-free yet p-heteroatom-doped carbon (nano)materials might
be far more difficult than commonly perceived. Two recent
important reports showed that truly metal-free carbon-based
materials are electrocatalytically inactive (or poorly active) [245],
while N-doped carbons become active electrocatalysts upon se-
lective in situ adsorption of Fe impurities from electrolyte solutions
and formation of highly dispersed FeeN sites [280]. Single atom
metal sites are difficult to detect, yet they can be created inadver-
tently if N-doped carbons are subjected to annealing [129].
Consequently, one might not be aware of their presence. We now
know that if CNTs contain residual TM impurities, single atom sites
can be created, which then likely dominate the catalytic properties
of a carbocatalyst [787]. In fact, as far back as 17 years ago, it was
demonstrated that CeO2-supported Au and Pt catalysts retain their
catalytic activity even after extensive removal of metal NPs from
the support, proving that the isolated, single Au and Pt cations were
the active sites, while metallic particles did not contribute to the
activity [788]. On the other hand, some more recent reports do
present strong evidence supporting the notion of truly metal-free
carbon-based electrocatalysts [316]. There is also mounting evi-
dence that oxygen-functional groups in pure, metal-free carbon
materials are responsible for their redox properties [789].
Chemical purification of carbon-based fossil fuels and natural
graphite, which has been intensively investigated for at least 70
years, presents a valuable source of knowledge for the demetalli-
zation of engineered carbon (nano)materials. For instance, the
well-known extraction of coals by polar aprotic solvents to obtain
ash-free solid fuels, was “rediscovered” as a way to extract gra-
phene from graphite. Likewise, there is no need to rediscover effi-
cient methods of demetalation of CNTs or graphene. Further
exploration of the available techniques for purification of tradi-
tional carbon-based solids (e.g. purification of graphite to a nuclear
grade) should be pursued instead. Since the majority of commercial
products sold as graphene or CNTs are nowhere near their theo-
retical structure, it is necessary to thoroughly analyze the purity of
carbon-based (nano)materials before any studies are undertaken.
To prove that a carbon sample is truly free of metallic impurities is
not as easy as it may seem as quantification/qualification of metallic
impurities within carbonaceous matrices is a truly complex matter.
Widely available techniques like ICP-MS/AES are often recom-
mended but sample preparation strongly determines the final
result. Validation of the results obtained also remains challenging
due to the lack of appropriate references. A specific technique must
be deliberately selected depending on what information concern-
ing the metal impurity is really required; critical limitations of the
technique(s) selected to study purity must be considered. More-
over, the language used in scientific reports must be more precise;
expressions like “completely metal-free” or “very low content”
should be avoided. If TMs were involved at any stage in the pro-
duction of the carbon material, the precise content of metal im-
purities should always be reported, or it should be specified that
the content is below a certain detection limit. There are fields of
practical applications where carbons with transition metals below
ppm levels would be necessary. However, while deleterious TM
impurities may impede some advanced applications, it does not
mean that they are always of critical importance. Commercializa-
tion of carbon-supported gold particles for the industrial produc-
tion of vinyl chloride, which turned out to be a single-atom Au(I/III)
redox catalyst, is a great example of a spectacular success of an SACs
based on an ordinary carbon support [790]. In addition, the com-
mercial success of carbon fibers was not precluded by native
metallic impurities as the global demand for carbon fibre is esti-
mated to oscillate around 100000 tonnes in 2020 [791]. TM resi-
dues do not prevent some sophisticated applications of engineered
carbons, yet one must be aware of their presence and hence
possible interferences. As recently demonstrated, TM impurities in
a commercially available graphene/polylactic acid filament do
affect performance of devices constructed using this material [792].
From the whole range of carbon demetalation methods, gas-
phase halogenation, hydrogenation and high-temperature heat
treatment under a dynamic vacuum seem to be the most efficient.
Reductive hydrogenation removes non-metal heteroatoms, in-
creases carbon surface homogeneity and unifies the variety of
metallic impurities into more coherent groups of phases (by
reduction of oxidized metallic impurities) that are more easily
removed by acid leaching. H2 annealing permits production of not
only metal- but also heteroatom-free carbon materials. Halogena-
tion does not affect the carbon phase and allows selective removal
of metallic phase only. In fact, thermochemical extraction has been
used for decades for industrial processing of graphite and, more
recently, for commercial production of porous carbons. As a result,
the infrastructure for carbon annealing under halogens already
exists and the procedures are well-optimized. Purification by
chlorination next to or complemented by high-temperature heat
treatment is one of the most feasible ways to obtain carbon ma-
terials with low metal content on an industrial scale. Fluorination
can be used for extremely persistent impurities although fluorine
does react with carbon phase as well. Multi-stage gas-phase puri-
fication generally seems to be the most suitable method for large-
scale upgrading to produce pure CNMs with minimum mass loss
and structure deformation. In oxidative purification (either liquid-
or gas-phase based), high-temperature annealing is often utilized
to restore the original structure of the purified carbons. Neverthe-
less, one must consider that only a fraction of the initial carbon
structure can be recreated via annealing. As reduction of GO cannot
provide graphene (and for this reason we refer to such material as
rGO), annealing of other carbon structures upon oxidative purifi-
cation cannot restore their original structure. Once disrupted, their
structure remains defective. Large-scale production methods of
carbon nanomaterials where different batches would have identical
properties should allow more reproducible results. Lack of stan-
dardized production and purification methods is the major draw-
back for applications of carbon nanomaterials in medicine,
electroanalysis, sensing or electronics since reproducibility is a
crucial factor for such applications. New carbon nanomaterials
perform well when used in macroscopic quantities (e.g. slurries)
because the inhomogeneities of individual nano-objects are aver-
aged out, but in such applications they are no different from
traditional carbon black, graphite powders, activated carbons, or
carbon fibers. Bottom-up strategies will eventually allow the pro-
duction of well-defined carbon nanostructures with atomic preci-
sion, but for now they remain confined to highly-advanced
laboratory research [793].
Finally, studies concerning the versatile family of carbonaceous
materials bring some more general conclusions, which might be of
help for future developments in this field. For instance, a general
definition of the purity of carbon-based materials needs to be
established. Researchers should also try to coordinate the

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
terminology used for the structural/morphological characterization
of carbonaceous materials; ad hoc naming of new carbon nano-
structures must be avoided as it brings much unnecessary confu-
sion. Herein we tackled only one particular issue which leads to
conflicting results concerning properties of advanced carbon ma-
terials and eventually hinders their commercialization. We hope
that this critical perspective will inspire other researchers to
pinpoint and characterize similar obstacles as this may help to push
the fascinating field of carbon-based materials forward.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This work was supported by National Science Centre, Poland,
UMO-2016/23/B/ST5/00127.
References
[1] V. Smil, Still the Iron Age: Iron and Steel in the Modern World, Butterworth-
Heinemann, 2016, https://doi.org/10.1016/C2014-0-04576-5.
[2] H.K.D.H. Bhadeshia, Cementite, Int Mater Rev 65 (1) (2020) 1e27, https://
doi.org/10.1080/09506608.2018.1560984.
[3] A.I. Babich, D.G. Senk, Coal use in iron and steel metallurgy, in: D. Osborne
(Ed.), The Coal Handbook: towards Cleaner Production, vol. 2, Woodhead
Publishing, 2013, pp. 267e311, https://doi.org/10.1533/
9781782421177.3.267.
[4] Y. Shen, Carbothermal synthesis of metal-functionalized nanostructures for
energy and environmental applications, J. Mater. Chem. 3 (25) (2015)
13114e13188, https://doi.org/10.1039/c5ta01228g.
[5] K.R. Olson, Activated charcoal for acute poisoning: one toxicologist’s journey,
J. Med. Toxicol. 6 (2) (2010) 190e198, https://doi.org/10.1007/s13181-010-
0046-1.
[6] V. Georgakilas, J.A. Perman, J. Tucek, R. Zboril, Broad family of carbon
nanoallotropes: classification, chemistry, and applications of fullerenes,
carbon dots, nanotubes, graphene, nanodiamonds, and combined super-
structures, Chem. Rev. 115 (11) (2015) 4744e4822, https://doi.org/10.1021/
cr500304f.
[7] E. Braun, Y. Lee, S.M. Moosavi, S. Barthel, R. Mercado, I.A. Baburin, et al.,
Generating carbon schwarzites via zeolite-templating, Proc. Natl. Acad. Sci.
U.S.A. 115 (35) (2018) E8116eE8124, https://doi.org/10.1073/
pnas.1805062115.
[8] F. Kreupl, Carbon-nanotube computer scaled up, Nature 572 (2019)
588e589, https://doi.org/10.1038/d41586-019-02519-2.
[9] A. Eftekhari, H. Garcia, The necessity of structural irregularities for the
chemical applications of graphene, Mater. Today Chem. 4 (2017) 1e16,
https://doi.org/10.1016/j.mtchem.2017.02.003.

[10] A. Oya, H. Marsh, Phenomena of catalytic graphitization, J. Mater. Sci. 17 (2)
(1982) 309e322, https://doi.org/10.1007/BF00591464.
[11] J.-M. Aguiar-Hualde, Y. Magnin, H. Amara, C. Bichara, Probing the role of
carbon solubility in transition metal catalyzing single-walled carbon nano-
tubes growth, Carbon 120 (2017) 226e232, https://doi.org/10.1016/
j.carbon.2017.05.035.
[12] T.W. Ebbesen, T. Takada, Topological and sp3 defect structures in nanotubes,
Carbon 33 (7) (1995) 973e978, https://doi.org/10.1016/0008-6223(95)
00025-9.
[13] A.P. Kauling, A.T. Seefeldt, D.P. Pisoni, R.C. Pradeep, R. Bentini, R.V.B. Oliveira,
et al., The worldwide graphene flake production, Adv. Mater. 30 (44) (2018)
1803784, https://doi.org/10.1002/adma.201803784.
[14] C.A. Amadei, P. Arribas, C.D. Vecitis, Graphene oxide standardization and
classification: methods to support the leap from lab to industry, Carbon 133
(2018) 398e409, https://doi.org/10.1016/j.carbon.2018.02.091.
[15] A.S.R. Bati, L. Yu, M. Batmunkh, J.G. Shapter, Synthesis, purification, proper-
ties and characterization of sorted single-walled carbon nanotubes, Nano-
scale 10 (47) (2018) 22087e22139, https://doi.org/10.1039/c8nr07379a.
[16] Y. Segawa, H. Ito, K. Itami, Structurally uniform and atomically precise carbon
nanostructures, Nat. Rev. Mater. 1 (2016) 15002, https://doi.org/10.1038/
natrevmats.2015.2.
[17] B. Liu, F. Wu, H. Gui, M. Zheng, C. Zhou, Chirality-controlled synthesis and
applications of single-wall carbon nanotubes, ACS Nano 11 (1) (2017) 31e53,
https://doi.org/10.1021/acsnano.6b06900.
[18] T.M. McCoy, G. Turpin, B.M. Teo, R.F. Tabor, Graphene oxide: a surfactant or
particle? Curr. Opin. Colloid Interface Sci. 39 (2019) 98e109, https://doi.org/
10.1016/j.cocis.2019.01.010.
829
[19] K. Lacina, O. Kubesa, V. Hora
ckova
, Z. Moravec, J. Kuta, P. Vanýsek, et al.,
Graphene oxide from improved Hummers’ method: is this material suitable
for reproducible electrochemical (bio)sensing? ECS J. Solid State Sci. Technol.
7 (10) (2018) M166eM171, https://doi.org/10.1149/2.0171810jss.
[20] R. Jalili, D. Esrafilzadeh, S.H. Aboutalebi, Y.M. Sabri, A.E. Kandjani,
S.K. Bhargava, et al., Silicon as a ubiquitous contaminant in graphene de-
rivatives with significant impact on device performance, Nat. Commun. 9
(2018) 5070, https://doi.org/10.1038/s41467-018-07396-3.
[21] S.M. Tan, M. Pumera, Two-dimensional materials on the rocks: positive and
negative role of dopants and impurities in electrochemistry, ACS Nano 13 (3)
(2019) 2681e2728, https://doi.org/10.1021/acsnano.8b07795.
[22] X. Liu, L. Dai, Carbon-based metal-free catalysts, Nat. Rev. Mater. 1 (2016)
16064, https://doi.org/10.1038/natrevmats.2016.64.
[23] C. Rivera-Ca
rcamo, P. Serp, Single atom catalysts on carbon-based materials,
ChemCatChem 10 (22) (2018) 5058e5091, https://doi.org/10.1002/
cctc.201801174.
[24] N.D. Orekhov, V.V. Stegailov, Graphite melting: atomistic kinetics bridges
theory and experiment, Carbon 87 (2015) 358e364, https://doi.org/10.1016/
j.carbon.2015.02.049.
[25] R.B. Heimann, S.E. Evsvukov, Y. Koga, Carbon allotropes: a suggested clas-
sification scheme based on valence orbital hybridization, Carbon 35 (10e11)
(1997) 1654e1658, https://doi.org/10.1016/S0008-6223(97)82794-7.
[26] A.O. Erkimbaev, V.Y. Zitserman, G.A. Kobzev, Systematization of data on the
physical and chemical properties and application of carbon nanostructures,
High Temp. 48 (6) (2010) 830e836, https://doi.org/10.1134/
S0018151X1006009X.
[27] E.A. Belenkov, V.A. Greshnyakov, Classification schemes for carbon phases
and nanostructures, N. Carbon Mater. 28 (4) (2013) 273e282, https://doi.org/
10.1016/S1872-5805(13)60081-5.
[28] S.H. Pun, Q. Miao, Toward negatively curved carbons, Acc. Chem. Res. 51 (7)
(2018) 1630e1642, https://doi.org/10.1021/acs.accounts.8b00140.
[29] J. Kang, Z. Wei, J. Li, Graphyne and its family: recent theoretical advances,
ACS Appl. Mater. Interfaces 11 (3) (2019) 2692e2706, https://doi.org/
10.1021/acsami.8b03338.
[30] R. Hoffmann, A.A. Kabanov, A.A. Golov, D.M. Proserpio, Homo citans and
carbon allotropes: for an ethics of citation, Angew. Chem. Int. Ed. 55 (37)
(2016) 10962e10976, https://doi.org/10.1002/anie.201600655.
[31] A. Bianco, H.-M. Cheng, T. Enoki, Y. Gogotsi, R.H. Hurt, N. Koratkar, et al., All
in the graphene family e a recommended nomenclature for two-
dimensional carbon materials, Carbon 65 (2013) 1e6, https://doi.org/
10.1016/j.carbon.2013.08.038.
[32] I. Suarez-Martinez, N. Grobert, C.P. Ewels, Nomenclature of sp2 carbon
nanoforms, Carbon 50 (3) (2012) 741e747, https://doi.org/10.1016/
j.carbon.2011.11.002.
[33] P. Wick, A.E. Louw-Gaume, M. Kucki, H.F. Krug, K. Kostarelos, B. Fadeel, et al.,
Classification framework for graphene-based materials, Angew. Chem. Int.
Ed. 53 (30) (2014) 7714e7718, https://doi.org/10.1002/anie.201403335.
[34] E. Fitzer, K.H. Kochling, H.P. Boehm, H. Marsh, Recommended terminology
for the description of carbon as a solid (IUPAC recommendations 1995), Pure
Appl. Chem. 67 (3) (1995) 473e506, https://doi.org/10.1351/
pac199567030473.
[35] M. Giedyk, K. Goliszewska, D. Gryko, Vitamin B12 catalysed reactions, Chem.
Soc. Rev. 44 (11) (2015) 3391e3404, https://doi.org/10.1039/c5cs00165j.
[36] M.R. Axet, O. Dechy-Cabaret, J. Durand, M. Gouygou, P. Serp, Coordination
chemistry on carbon surfaces, Coord. Chem. Rev. 308 (Part 2) (2016)
236e345, https://doi.org/10.1016/j.ccr.2015.06.005.
[37] E. Bekyarova, S. Sarkar, F. Wang, M.E. Itkis, I. Kalinina, X. Tian, et al., Effect of
covalent chemistry on the electronic structure and properties of carbon
nanotubes and graphene, Acc. Chem. Res. 46 (1) (2013) 65e76, https://
doi.org/10.1021/ar300177q.
[38] F. Wang, M.E. Itkis, E.B. Bekyarova, X. Tian, S. Sarkar, A. Pekker, et al., Effect of
first row transition metals on the conductivity of semiconducting single-
walled carbon nanotube networks, Appl. Phys. Lett. 100 (2012) 223111,
https://doi.org/10.1063/1.4723717.
[39] S. Sarkar, S. Niyogi, E. Bekyarova, R.C. Haddon, Organometallic chemistry of
extended periodic p-electron systems: hexahapto-chromium complexes of
graphene and single-walled carbon nanotubes, Chem. Sci. 2 (7) (2011)
1326e1333, https://doi.org/10.1039/c0sc00634c.
[40] I. Kalinina, E. Bekyarova, S. Sarkar, F. Wang, M.E. Itkis, X. Tian, et al., Hex-
ahapto-metal complexes of single-walled carbon nanotubes, Macromol.
Chem. Phys. 213 (10e11) (2012) 1001e1019, https://doi.org/10.1002/
macp.201100661.
[41] M. Chen, A. Pekker, W. Li, M.E. Itkis, R.C. Haddon, E. Bekyarova, Organome-
tallic chemistry of graphene: photochemical complexation of graphene with
group 6 transition metals, Carbon 129 (2018) 450e455, https://doi.org/
10.1016/j.carbon.2017.12.025.
[42] H. Wang, Y. Xie, R.B. King, H.F. Schaefer, Bis(cycloheptatrienyl) derivatives of
the first-row transition metals: variable hapticity of the cycloheptatrienyl
ring, Eur. J. Inorg. Chem. 2008 (23) (2008) 3698e3708, https://doi.org/
10.1002/ejic.200800299.
[43] D.E. Jiang, B.G. Sumpter, S. Dai, Structure and bonding between an aryl group
and metal surfaces, J. Am. Chem. Soc. 128 (18) (2006) 6030e6031, https://
doi.org/10.1021/ja061439f.
[44] F. Banhart, Interactions between metals and carbon nanotubes: at the
interface between old and new materials, Nanoscale 1 (2) (2009) 201e213,
830
ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
https://doi.org/10.1039/b9nr00127a.
[45] F. Banhart, N. Grobert, M. Terrones, J.C. Charlier, P.M. Ajayan, Metal atoms in
carbon nanotubes and related nanoparticles, Int. J. Mod. Phys. B 15 (31)
(2012) 4037e4069, https://doi.org/10.1142/S0217979201007944.
[46] C.-M. Sung, M.-F. Tai, Reactivities of transition metals with carbon: impli-
cations to the mechanism of diamond synthesis under high pressure, Int. J.
Refract. Met. Hard Mater. 15 (4) (1997) 237e256, https://doi.org/10.1016/
S0263-4368(97)00003-6.
[47] S. Esconjauregui, C.M. Whelan, K. Maex, The reasons why metals catalyze the
nucleation and growth of carbon nanotubes and other carbon nano-
morphologies, Carbon 47 (3) (2009) 659e669, https://doi.org/10.1016/
j.carbon.2008.10.047.
[48] Smithells Metals Reference Book, eighth ed., Butterworth-Heinemann, 2004
https://doi.org/10.1016/B978-075067509-3/50014-2, 11-1-11-534.
[49] V. Jourdain, C. Bichara, Current understanding of the growth of carbon
nanotubes in catalytic chemical vapour deposition, Carbon 58 (2013) 2e39,
https://doi.org/10.1016/j.carbon.2013.02.046.
[50] F.J. Derbyshire, A.E.B. Presland, D.L. Trimm, Graphite formation by the dis-
solutiondprecipitation of carbon in cobalt, nickel and iron, Carbon 13 (2)
(1975) 111e113, https://doi.org/10.1016/0008-6223(75)90267-5.
[51] C. Mattevi, H. Kim, M. Chhowalla, A review of chemical vapour deposition of
graphene on copper, J. Mater. Chem. 21 (10) (2011) 3324e3334, https://
doi.org/10.1039/c0jm02126a.
[52] M. He, H. Amara, H. Jiang, J. Hassinen, C. Bichara, R.H. Ras, et al., Key roles of
carbon solubility in single-walled carbon nanotube nucleation and growth,
Nanoscale 7 (47) (2015) 20284e20289, https://doi.org/10.1039/c5nr06045a.
[53] X. Li, W. Cai, L. Colombo, R.S. Ruoff, Evolution of graphene growth on Ni and
Cu by carbon isotope labeling, Nano Lett. 9 (12) (2009) 4268e4272, https://
doi.org/10.1021/nl902515k.
[54] L. Lin, B. Deng, J. Sun, H. Peng, Z. Liu, Bridging the gap between reality and
ideal in chemical vapor deposition growth of graphene, Chem. Rev. 118 (18)
(2018) 9281e9343, https://doi.org/10.1021/acs.chemrev.8b00325.
[55] G.A. Lo
pez, E.J. Mittemeijer, The solubility of C in solid Cu, Scripta Mater. 51
(1) (2004) 1e5, https://doi.org/10.1016/j.scriptamat.2004.03.028.
[56] T. Wu, X. Zhang, Q. Yuan, J. Xue, G. Lu, Z. Liu, et al., Fast growth of inch-sized
single-crystalline graphene from a controlled single nucleus on Cu-Ni alloys,
Nat. Mater. 15 (2016) 43e47, https://doi.org/10.1038/nmat4477.
[57] D.J. Young, J. Zhang, Metal dusting: catastrophic corrosion by carbon,
J. Occup. Med. 64 (12) (2012) 1461e1469, https://doi.org/10.1007/s11837-
012-0476-0.
[58] M. Ding, Y. Yang, B. Wu, Y. Li, T. Wang, L. Ma, Study on reduction and
carburization behaviors of iron phases for iron-based FischereTropsch syn-
thesis catalyst, Appl. Energy 160 (2015) 982e989, https://doi.org/10.1016/
j.apenergy.2014.12.042.
[59] L.C. Campos, V.R. Manfrinato, J.D. Sanchez-Yamagishi, J. Kong, P. Jarillo-
Herrero, Anisotropic etching and nanoribbon formation in single-layer gra-
phene, Nano Lett. 9 (7) (2009) 2600e2604, https://doi.org/10.1021/
nl900811r.
[60] A.L. Elias, A.R. Botello-Mendez, D. Meneses-Rodriguez, V. Jehova Gonzalez,
D. Ramirez-Gonzalez, L. Ci, et al., Longitudinal cutting of pure and doped
carbon nanotubes to form graphitic nanoribbons using metal clusters as
nanoscalpels, Nano Lett. 10 (2) (2010) 366e372, https://doi.org/10.1021/
nl901631z.
[61] S. Bhattacharjee, U.V. Waghmare, S.C. Lee, An improved d-band model of the
catalytic activity of magnetic transition metal surfaces, Sci. Rep. 6 (2016)
35916, https://doi.org/10.1038/srep35916.
[62] A. Maiti, A. Ricca, Metalenanotube interactions e binding energies and
wetting properties, Chem. Phys. Lett. 395 (1e3) (2004) 7e11, https://doi.org/
10.1016/j.cplett.2004.07.024.
[63] Y. Zhang, N.W. Franklin, R.J. Chen, H. Dai, Metal coating on suspended carbon
nanotubes and its implication to metaletube interaction, Chem. Phys. Lett.
331 (1) (2000) 35e41, https://doi.org/10.1016/S0009-2614(00)01162-3.
[64] B.P. Klein, S.E. Harman, L. Ruppenthal, G.M. Ruehl, S.J. Hall, S.J. Carey, et al.,
Enhanced bonding of pentagoneheptagon defects in graphene to metal
surfaces: insights from the adsorption of azulene and naphthalene to
Pt(111), Chem. Mater. 32 (3) (2020) 1041e1053, https://doi.org/10.1021/
acs.chemmater.9b03744.
[65] Y. Fan, B.R. Goldsmith, P.G. Collins, Identifying and counting point defects in
carbon nanotubes, Nat. Mater. 4 (2005) 906e911, https://doi.org/10.1038/
nmat1516.
[66] C.E. Banks, T.J. Davies, G.G. Wildgoose, R.G. Compton, Electrocatalysis at
graphite and carbon nanotube modified electrodes: edge-plane sites and
tube ends are the reactive sites, Chem. Commun. (7) (2005) 829e841,
https://doi.org/10.1039/b413177k.
[67] X. Liu, M. Hupalo, C.-Z. Wang, W.-C. Lu, P.A. Thiel, K.-M. Ho, et al., Growth
morphology and thermal stability of metal islands on graphene, Phys. Rev. B
86 (2012), https://doi.org/10.1103/PhysRevB.86.081414, 081414(R).
[68] X. Liu, C.-Z. Wang, M. Hupalo, H.-Q. Lin, K.-M. Ho, M. Tringides, Metals on
graphene: interactions, growth morphology, and thermal stability, Crystals 3
(1) (2013) 79e111, https://doi.org/10.3390/cryst3010079.
[69] R.C. Haddon, p-Electrons in three dimensions, Acc. Chem. Res. 21 (6) (1988)
243e249, https://doi.org/10.1021/ar00150a005.
[70] A. Hirsch, Functionalization of single-walled carbon nanotubes, Angew.
Chem. Int. Ed. 41 (11) (2002) 1853e1859, https://doi.org/10.1002/1521-
3773(20020603)41:11<1853::AID-ANIE1853>3.0.CO;2-N.
[71] H. Valencia, A. Gil, G. Frapper, Trends in the adsorption of 3d transition metal
atoms onto graphene and nanotube surfaces: a DFT study and molecular
orbital analysis, J. Phys. Chem. C 114 (33) (2010) 14141e14153, https://
doi.org/10.1021/jp103445v.
[72] M. Manade
, F. Vin
~ es, F. Illas, Transition metal adatoms on graphene: a sys-
tematic density functional study, Carbon 95 (2015) 525e534, https://doi.org/
10.1016/j.carbon.2015.08.072.
[73] X. Liu, C.Z. Wang, Y.X. Yao, W.C. Lu, M. Hupalo, M.C. Tringides, et al., Bonding
and charge transfer by metal adatom adsorption on graphene, Phys. Rev. B
83 (2011) 235411, https://doi.org/10.1103/PhysRevB.83.235411.
[74] J.A. Rodriguez-Manzo, O. Cretu, F. Banhart, Trapping of metal atoms in va-
cancies of carbon nanotubes and graphene, ACS Nano 4 (6) (2010)
3422e3428, https://doi.org/10.1021/nn100356q.
[75] F. Banhart, J. Kotakoski, A.V. Krasheninnikov, Structural defects in graphene,
ACS Nano 5 (1) (2011) 26e41, https://doi.org/10.1021/nn102598m.
[76] N. Jing, Q. Xue, C. Ling, M. Shan, T. Zhang, X. Zhou, et al., Effect of defects on
Young’s modulus of graphene sheets: a molecular dynamics simulation, RSC
Adv. 2 (24) (2012) 9124e9129, https://doi.org/10.1039/c2ra21228e.
[77] H. Wang, Q. Wang, Y. Cheng, K. Li, Y. Yao, Q. Zhang, et al., Doping monolayer
graphene with single atom substitutions, Nano Lett. 12 (1) (2012) 141e144,
https://doi.org/10.1021/nl2031629.
[78] I. Suarez-Martinez, A. Felten, J.J. Pireaux, C. Bittencourt, C.P. Ewels, Transition
metal deposition on graphene and carbon nanotubes, J. Nanosci. Nano-
technol. 9 (10) (2009) 6171e6175, https://doi.org/10.1166/jnn.2009.1557.
[79] H. Valencia, A. Gil, G. Frapper, Trends in the hydrogen activation and storage
by adsorbed 3d transition metal atoms onto graphene and nanotube sur-
faces: a DFT study and molecular orbital analysis, J. Phys. Chem. C 119 (10)
(2015) 5506e5522, https://doi.org/10.1021/jp512920f.
[80] A.V. Krasheninnikov, P.O. Lehtinen, A.S. Foster, P. Pyykko, R.M. Nieminen,
Embedding transition-metal atoms in graphene: structure, bonding, and
magnetism, Phys. Rev. Lett. 102 (2009) 126807, https://doi.org/10.1103/
physrevlett.102.126807.
[81] A. Bhattacharya, S. Bhattacharya, C. Majumder, G.P. Das, Transition-metal
decoration enhanced room-temperature hydrogen storage in a defect-
modulated graphene sheet, J. Phys. Chem. C 114 (22) (2010)
10297e10301, https://doi.org/10.1021/jp100230c.
[82] E.J.G. Santos, A. Ayuela, D. Sa
nchez-Portal, First-principles study of substi-
tutional metal impurities in graphene: structural, electronic and magnetic
properties, New J. Phys. 12 (2010), https://doi.org/10.1088/1367-2630/12/5/
053012, 053012.
[83] A.V. Markevich, M. Baldoni, J.H. Warner, A.I. Kirkland, E. Besley, Dynamic
behavior of single Fe atoms embedded in graphene, J. Phys. Chem. C 120 (38)
(2016) 21998e22003, https://doi.org/10.1021/acs.jpcc.6b06554.
[84] M. Sun, Q. Ren, Y. Zhao, J.-P. Chou, J. Yu, W. Tang, Electronic and magnetic
properties of 4d series transition metal substituted graphene: a first-
principles study, Carbon 120 (2017) 265e273, https://doi.org/10.1016/
j.carbon.2017.04.060.
[85] I.A. Pasti, A. Jovanovic, A.S. Dobrota, S.V. Mentus, B. Johansson,
N.V. Skorodumova, Atomic adsorption on graphene with a single vacancy:
systematic DFT study through the periodic table of elements, Phys. Chem.
Chem. Phys. 20 (2) (2018) 858e865, https://doi.org/10.1039/c7cp07542a.
[86] F. Banhart, J. Charlier, P.M. Ajayan, Dynamic behavior of nickel atoms in
graphitic networks, Phys. Rev. Lett. 84 (4) (2000) 686e689, https://doi.org/
10.1103/PhysRevLett.84.686.
[87] M. Ushiro, K. Uno, T. Fujikawa, Y. Sato, K. Tohji, F. Watari, et al., X-ray ab-
sorption fine structure (XAFS) analyses of Ni species trapped in graphene
sheet of carbon nanofibers, Phys. Rev. B 73 (2006) 144103, https://doi.org/
10.1103/PhysRevB.73.144103.
[88] H.J. Qiu, Y. Ito, W. Cong, Y. Tan, P. Liu, A. Hirata, et al., Nanoporous graphene
with single-atom nickel dopants: an efficient and stable catalyst for elec-
trochemical hydrogen production, Angew. Chem. Int. Ed. 54 (47) (2015)
14031e14035, https://doi.org/10.1002/anie.201507381.
[89] L. Zhang, Y. Jia, G. Gao, X. Yan, N. Chen, J. Chen, et al., Graphene defects trap
atomic Ni species for hydrogen and oxygen evolution reactions, Inside Chem.
4 (2) (2018) 285e297, https://doi.org/10.1016/j.chempr.2017.12.005.
[90] D.I. Kochubey, V.V. Chesnokov, S.E. Malykhin, Evidence for atomically
dispersed Pd in catalysts supported on carbon nanofibers, Carbon 50 (8)
(2012) 2782e2787, https://doi.org/10.1016/j.carbon.2012.02.040.
[91] Y. Gan, L. Sun, F. Banhart, One- and two-dimensional diffusion of metal
atoms in graphene, Small 4 (5) (2008) 587e591, https://doi.org/10.1002/
smll.200700929.
[92] T. Zoberbier, T.W. Chamberlain, J. Biskupek, M. Suyetin, A.G. Majouga,
E. Besley, et al., Investigation of the interactions and bonding between car-
bon and group VIII metals at the atomic scale, Small 12 (12) (2016)
1649e1657, https://doi.org/10.1002/smll.201502210.
[93] Z. He, K. He, A.W. Robertson, A.I. Kirkland, D. Kim, J. Ihm, et al., Atomic
structure and dynamics of metal dopant pairs in graphene, Nano Lett. 14 (7)
(2014) 3766e3772, https://doi.org/10.1021/nl500682j.
[94] A.W. Robertson, B. Montanari, K. He, J. Kim, C.S. Allen, Y.A. Wu, et al., Dy-
namics of single Fe atoms in graphene vacancies, Nano Lett. 13 (4) (2013)
1468e1475, https://doi.org/10.1021/nl304495v.
[95] M.F. Chisholm, G. Duscher, W. Windl, Oxidation resistance of reactive atoms
in graphene, Nano Lett. 12 (9) (2012) 4651e4655, https://doi.org/10.1021/
nl301952e.
[96] F. Banhart, P. Redlich, P.M. Ajayan, The migration of metal atoms through

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
carbon onions, Chem. Phys. Lett. 292 (4e6) (1998) 554e560, https://doi.org/
10.1016/S0009-2614(98)00705-2.
[97] D. Ugarte, How to fill or empty a graphitic onion, Chem. Phys. Lett. 209 (1e2)
(1993) 99e103, https://doi.org/10.1016/0009-2614(93)87208-K.
[98] J. Jiao, S. Seraphin, X. Wang, J.C. Withers, Preparation and properties of
ferromagnetic carbon-coated Fe, Co, and Ni nanoparticles, J. Appl. Phys. 80
(1) (1996) 103e108, https://doi.org/10.1063/1.362765.
[99] B.B. Bokhonov, Permeability of carbon shells during sulfidation of encapsu-
lated silver nanoparticles, Carbon 67 (2014) 572e577, https://doi.org/
10.1016/j.carbon.2013.10.030.
[100] M. Fronczak, O. Łabe˛ d
z, W. Kaszuwara, M. Bystrzejewski, Corrosion resis-
tance studies of carbon-encapsulated iron nanoparticles, J. Mater. Sci. 53 (5)
(2017) 3805e3816, https://doi.org/10.1007/s10853-017-1793-z.
[101] P. Wilhite, A.A. Vyas, J. Tan, J. Tan, T. Yamada, P. Wang, et al., Metal-
enanocarbon contacts, Semicond. Sci. Technol. 29 (5) (2014), https://doi.org/
10.1088/0268-1242/29/5/054006, 054006.
[102] Q. Ran, M. Gao, X. Guan, Y. Wang, Z. Yu, First-principles investigation on
bonding formation and electronic structure of metal-graphene contacts,
Appl. Phys. Lett. 94 (2009) 103511, https://doi.org/10.1063/1.3095438.
[103] Y. Matsuda, W.-Q. Deng, W.A. Goddard, Contact resistance properties be-
tween nanotubes and various metals from quantum mechanics, J. Phys.
Chem. C 111 (29) (2007) 11113e11116, https://doi.org/10.1021/jp072794a.
[104] Y. Matsuda, W.-Q. Deng, W.A. Goddard, Contact resistance for “end-con-
tacted” metalgraphene and metalnanotube interfaces from quantum
mechanics, J. Phys. Chem. C 114 (41) (2010) 17845e17850, https://doi.org/
10.1021/jp806437y.
[105] S.C. Lim, J.H. Jang, D.J. Bae, G.H. Han, S. Lee, I.-S. Yeo, et al., Contact resistance
between metal and carbon nanotube interconnects: effect of work function
and wettability, Appl. Phys. Lett. 95 (2009) 264103, https://doi.org/10.1063/
1.3255016.
[106] J. Roth, H. Graupner, S.P. Withrow, D. Zehner, R.A. Zuhr, Chemical interaction
of Si, Ti, and Mo with graphite surfaces, J. Appl. Phys. 79 (10) (1996)
7695e7702, https://doi.org/10.1063/1.362673.
[107] R. Martel, V. Derycke, C. Lavoie, J. Appenzeller, K.K. Chan, J. Tersoff, et al.,
Ambipolar electrical transport in semiconducting single-wall carbon nano-
tubes, Phys. Rev. Lett. 87 (2001) 256805, https://doi.org/10.1103/
PhysRevLett.87.256805.
[108] Y. Zhang, T. Ichihashi, E. Landree, F. Nihey, S. Iijima, Heterostructures of
single-walled carbon nanotubes and carbide nanorods, Science 285 (5434)
(1999) 1719e1722, https://doi.org/10.1126/science.285.5434.1719.
[109] M.S. Wang, D. Golberg, Y. Bando, Superstrong low-resistant carbon
nanotube-carbide-metal nanocontacts, Adv. Mater. 22 (47) (2010)
5350e5355, https://doi.org/10.1002/adma.201003010.
[110] J.A. Rodriguez-Manzo, M.-S. Wang, F. Banhart, Y. Bando, D. Golberg, Multi-
branched junctions of carbon nanotubes via cobalt particles, Adv. Mater. 21
(44) (2009) 4477e4482, https://doi.org/10.1002/adma.200901321.
[111] Y. Zhang, H. Dai, Formation of metal nanowires on suspended single-walled
carbon nanotubes, Appl. Phys. Lett. 77 (19) (2000) 3015e3017, https://
doi.org/10.1063/1.1324731.
[112] G.M. Ilari, F.S. Hage, Y. Zhang, M.D. Rossell, Q.M. Ramasse, M. Niederberger,
et al., Carbon-metal interfaces analyzed by aberration-corrected TEM: how
copper and nickel nanoparticles interact with MWCNTs, Micron 72 (2015)
52e58, https://doi.org/10.1016/j.micron.2015.03.004.
[113] G.M. Ilari, V. Chawla, S. Matam, Y. Zhang, J. Michler, R. Erni, Electron energy
loss spectroscopy analysis of the interaction of Cr and V with MWCNTs,
Micron 84 (2016) 37e42, https://doi.org/10.1016/j.micron.2016.02.009.
[114] J.A. Rodriguez-Manzo, F. Banhart, M. Terrones, H. Terrones, N. Grobert,
P.M. Ajayan, et al., Heterojunctions between metals and carbon nanotubes as
ultimate nanocontacts, Proc. Natl. Acad. Sci. U.S.A. 106 (12) (2009)
4591e4595, https://doi.org/10.1073/pnas.0900960106.
[115] J. Lahiri, M. Batzill, Graphene destruction by metal-carbide formation: an
approach for patterning of metal-supported graphene, Appl. Phys. Lett. 97
(2010), https://doi.org/10.1063/1.3464173, 023102.
[116] W.S. Leong, C.T. Nai, J.T. Thong, What does annealing do to metal-graphene
contacts? Nano Lett. 14 (7) (2014) 3840e3847, https://doi.org/10.1021/
nl500999r.
[117] C. Gong, S. McDonnell, X. Qin, A. Azcatl, H. Dong, Y.J. Chabal, et al., Realistic
metal-graphene contact structures, ACS Nano 8 (1) (2014) 642e649, https://
doi.org/10.1021/nn405249n.
[118] C. Yi, S. Bagchi, C.M. Dmuchowski, F. Gou, X. Chen, C. Park, et al., Direct
nanomechanical characterization of carbon nanotubes - titanium interfaces,
Carbon 132 (2018) 548e555, https://doi.org/10.1016/j.carbon.2018.02.069.
[119] C. Bittencourt, X. Ke, G. Van Tendeloo, S. Thiess, W. Drube, J. Ghijsen, et al.,
Study of the interaction between copper and carbon nanotubes, Chem. Phys.
Lett. 535 (2012) 80e83, https://doi.org/10.1016/j.cplett.2012.03.045.
[120] C. Gong, A.W. Robertson, K. He, C. Ford, A.A. Watt, J.H. Warner, Interactions of
Pb and Te atoms with graphene, Dalton Trans. 43 (20) (2014) 7442e7448,
https://doi.org/10.1039/c4dt00143e.
[121] R. Zan, U. Bangert, Q. Ramasse, K.S. Novoselov, Interaction of metals with
suspended graphene observed by transmission electron microscopy, J. Phys.
Chem. Lett. 3 (7) (2012) 953e958, https://doi.org/10.1021/jz201653g.
[122] K. Asaka, Y. Saito, Spontaneous graphenization of amorphous carbon on
clean surfaces of nanometer-sized nickel particles at room temperature,
Carbon 103 (2016) 352e355, https://doi.org/10.1016/j.carbon.2016.03.031.
[123] M. Yang, L. Wang, M. Li, T. Hou, Y. Li, Structural stability and O2 dissociation
831
on nitrogen-doped graphene with transition metal atoms embedded: a first-
principles study, AIP Adv. 5 (2015), https://doi.org/10.1063/1.4922841,
067136.
[124] C.W.B. Bezerra, L. Zhang, K. Lee, H. Liu, A.L.B. Marques, E.P. Marques, et al.,
A review of FeeN/C and CoeN/C catalysts for the oxygen reduction reaction,
Electrochim. Acta 53 (15) (2008) 4937e4951, https://doi.org/10.1016/
j.electacta.2008.02.012.
[125] Z. Zhang, Y. Chen, L. Zhou, C. Chen, Z. Han, B. Zhang, et al., The simplest
construction of single-site catalysts by the synergism of micropore trapping
and nitrogen anchoring, Nat. Commun. 10 (2019) 1657, https://doi.org/
10.1038/s41467-019-09596-x.
[126] J. Liu, M. Jiao, L. Lu, H.M. Barkholtz, Y. Li, Y. Wang, et al., High performance
platinum single atom electrocatalyst for oxygen reduction reaction, Nat.
Commun. 8 (2017) 15938, https://doi.org/10.1038/ncomms15938.
[127] H. Yang, L. Shang, Q. Zhang, R. Shi, G.I.N. Waterhouse, L. Gu, et al., A universal
ligand mediated method for large scale synthesis of transition metal single
atom catalysts, Nat. Commun. 10 (2019) 4585, https://doi.org/10.1038/
s41467-019-12510-0.
[128] Y. Qu, Z. Li, W. Chen, Y. Lin, T. Yuan, Z. Yang, et al., Direct transformation of
bulk copper into copper single sites via emitting and trapping of atoms, Nat.
Catal. 1 (2018) 781e786, https://doi.org/10.1038/s41929-018-0146-x.
[129] S. Wei, A. Li, J.C. Liu, Z. Li, W. Chen, Y. Gong, et al., Direct observation of noble
metal nanoparticles transforming to thermally stable single atoms, Nat.
Nanotechnol. 13 (2018) 856e861, https://doi.org/10.1038/s41565-018-
0197-9.
[130] J. Yang, Z. Qiu, C. Zhao, W. Wei, W. Chen, Z. Li, et al., In situ thermal atom-
ization to convert supported nickel nanoparticles into surface-bound nickel
single-atom catalysts, Angew. Chem. 130 (43) (2018) 14291e14296, https://
doi.org/10.1002/ange.201808049.
[131] J. Li, L. Jiao, E. Wegener, L.L. Richard, E. Liu, A. Zitolo, et al., Evolution pathway
from iron compounds to Fe1(II)-N4 sites through gas-phase iron during py-
rolysis, J. Am. Chem. Soc. 142 (3) (2020) 1417e1423, https://doi.org/10.1021/
jacs.9b11197.
[132] J.C. Liu, H. Xiao, J. Li, Constructing high-loading single-atom/cluster catalysts
via an electrochemical potential window strategy, J. Am. Chem. Soc. 142 (7)
(2020) 3375e3383, https://doi.org/10.1021/jacs.9b06808.
[133] J. Li, H. Zhang, W. Samarakoon, W. Shan, D.A. Cullen, S. Karakalos, et al.,
Thermally driven structure and performance evolution of atomically
dispersed FeN4 sites for oxygen reduction, Angew. Chem. Int. Ed. 58 (52)
(2019) 18971e18980, https://doi.org/10.1002/anie.201909312.
[134] A.J. Clancy, M.K. Bayazit, S.A. Hodge, N.T. Skipper, C.A. Howard, M.S.P. Shaffer,
Charged carbon nanomaterials: redox chemistries of fullerenes, carbon
nanotubes, and graphenes, Chem. Rev. 118 (16) (2018) 7363e7408, https://
doi.org/10.1021/acs.chemrev.8b00128.
[135] M.S. Dresselhaus, G. Dresselhaus, Intercalation compounds of graphite, Adv.
Phys. 51 (1) (2002) 1e186, https://doi.org/10.1080/00018730110113644.
[136] D.D.L. Chung, Review graphite, J. Mater. Sci. 37 (8) (2002) 1475e1489,
https://doi.org/10.1023/A:1014915307738.
[137] Y. Li, Y. Lu, P. Adelhelm, M.M. Titirici, Y.S. Hu, Intercalation chemistry of
graphite: alkali metal ions and beyond, Chem. Soc. Rev. 48 (17) (2019)
4655e4687, https://doi.org/10.1039/c9cs00162j.
[138] J. Xu, Y. Dou, Z. Wei, J. Ma, Y. Deng, Y. Li, et al., Recent progress in graphite
intercalation compounds for rechargeable metal (Li, Na, K, Al)-ion batteries,
Adv. Sci. 4 (10) (2017) 1700146, https://doi.org/10.1002/advs.201700146.
[139] C.M. Fang, M.H. Sluiter, M.A. van Huis, C.K. Ande, H.W. Zandbergen, Origin of
predominance of cementite among iron carbides in steel at elevated tem-
perature, Phys. Rev. Lett. 105 (2010), https://doi.org/10.1103/Phys-
RevLett.105.055503, 055503.
[140] O. Cretu, A.V. Krasheninnikov, J.A. Rodriguez-Manzo, L. Sun, R.M. Nieminen,
F. Banhart, Migration and localization of metal atoms on strained graphene,
Phys. Rev. Lett. 105 (2010) 196102, https://doi.org/10.1103/
PhysRevLett.105.196102.
[141] A.V. Krasheninnikov, R.M. Nieminen, Attractive interaction between
transition-metal atom impurities and vacancies in graphene: a first-
principles study, Theor. Chem. Acc. 129 (3e5) (2011) 625e630, https://
doi.org/10.1007/s00214-011-0910-3.
[142] M.E. Itkis, D.E. Perea, R. Jung, S. Niyogi, R.C. Haddon, Comparison of analytical
techniques for purity evaluation of single-walled carbon nanotubes, J. Am.
Chem. Soc. 127 (10) (2005) 3439e3448, https://doi.org/10.1021/ja043061w.
[143] T. Kolodiazhnyi, M. Pumera, Towards an ultrasensitive method for the
determination of metal impurities in carbon nanotubes, Small 4 (9) (2008)
1476e1484, https://doi.org/10.1002/smll.200800125.
[144] B.P. Bittova, M. Kalbac, S. Kubickova, A. Mantlikova, S. Mangold,
J. Vejpravova, Structure and magnetic response of a residual metal catalyst in
highly purified single walled carbon nanotubes, Phys. Chem. Chem. Phys. 15
(16) (2013) 5992e6000, https://doi.org/10.1039/c3cp00087g.
[145] A. Ambrosi, S.Y. Chee, B. Khezri, R.D. Webster, Z. Sofer, M. Pumera, Metallic
impurities in graphenes prepared from graphite can dramatically influence
their properties, Angew. Chem. Int. Ed. 51 (2) (2012) 500e503, https://
doi.org/10.1002/anie.201106917.
[146] A.A. Ammann, Inductively coupled plasma mass spectrometry (ICP MS): a
versatile tool, J. Mass Spectrom. 42 (4) (2007) 419e427, https://doi.org/
10.1002/jms.1206.
[147] J.H. Lehman, M. Terrones, E. Mansfield, K.E. Hurst, V. Meunier, Evaluating the
characteristics of multiwall carbon nanotubes, Carbon 49 (8) (2011)
832
ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
2581e2602, https://doi.org/10.1016/j.carbon.2011.03.028.
[148] K.L. Eric, R.L. Watters, Certificate of Analysis Standard Reference Material
2483 Single-Wall Carbon Nanotubes (Raw Soot), National Institute of Stan-
dards & Technology, Department of Commerce, USA, 2011.
[149] Z. Mester, Certificate of Analysis, SWCNT-1 Single-Wall Carbon Nanotubes
Certified Reference Material, National Research Council, Ottawa, Canada,
2013.
[150] E.J. Petersen, D.X. Flores-Cervantes, T.D. Bucheli, L.C. Elliott, J.A. Fagan,
A. Gogos, et al., Quantification of carbon nanotubes in environmental
matrices: current capabilities, case studies, and future prospects, Environ.
Sci. Technol. 50 (9) (2016) 4587e4605, https://doi.org/10.1021/
acs.est.5b05647.
[151] F.R. Simoes, N.M. Batra, B.H. Warsama, C.G. Canlas, S. Patole, T.F. Yapici, et al.,
Elemental quantification and residues characterization of wet digested
certified and commercial carbon materials, Anal. Chem. 88 (23) (2016)
11783e11790, https://doi.org/10.1021/acs.analchem.6b03407.
[152] S.P. Patole, F. Simoes, T.F. Yapici, B.H. Warsama, D.H. Anjum, P.M. Costa, An
evaluation of microwave-assisted fusion and microwave-assisted acid
digestion methods for determining elemental impurities in carbon nano-
structures using inductively coupled plasma optical emission spectrometry,
Talanta 148 (2016) 94e100, https://doi.org/10.1016/j.talanta.2015.10.053.
[153] J. Kameník, F.R.F. Simo ~es, P.M.F.J. Costa, J. Ku
cera, V. Havra
nek, INAA and ion-
beam analysis of elemental admixtures in carbon-based nanomaterials for
battery electrodes, J. Radioanal. Nucl. Chem. 318 (3) (2018) 2463e2472,
https://doi.org/10.1007/s10967-018-6200-y.
[154] J. Vejpravova, B. Pacakova, M. Kalbac, Magnetic impurities in single-walled
carbon nanotubes and graphene: a review, Analyst 141 (9) (2016)
2639e2656, https://doi.org/10.1039/c6an00248j.
[155] C. Ge, F. Lao, W. Li, Y. Li, C. Chen, Y. Qiu, et al., Quantitative analysis of metal
impurities in carbon nanotubes: efficacy of different pretreatment protocols
for ICPMS spectroscopy, Anal. Chem. 80 (24) (2008) 9426e9434, https://
doi.org/10.1021/ac801469b.
[156] R. Zeisler, R.L. Paul, R. Oflaz Spatz, L.L. Yu, J.L. Mann, W.R. Kelly, et al.,
Elemental analysis of a single-wall carbon nanotube candidate reference
material, Anal. Bioanal. Chem. 399 (1) (2011) 509e517, https://doi.org/
10.1007/s00216-010-4275-6.
[157] K.X. Yang, M.E. Kitto, J.P. Orsini, K. Swami, S.E. Beach, Evaluation of sample
pretreatment methods for multiwalled and single-walled carbon nanotubes
for the determination of metal impurities by ICPMS, ICPOES, and instrument
neutron activation analysis, J. Anal. At. Spectrom. 25 (8) (2010) 1290e1297,
https://doi.org/10.1039/c0ja00012d.
[158] J.E. Decker, A.R. Hight Walker, K. Bosnick, C.A. Clifford, L. Dai, J. Fagan, et al.,
Sample preparation protocols for realization of reproducible characterization
of single-wall carbon nanotubes, Metrologia 46 (2009) 682e692, https://
doi.org/10.1088/0026-1394/46/6/011.
[159] F.R.F. Simoes, M. Batra Nitin, A.-H. Emwas, P.M.F.J. Costa, Validation of
alkaline oxidation as a pre-treatment method for elemental quantification in
single-walled carbon nanotubes, Anal Methods 11 (14) (2019) 1884e1890,
https://doi.org/10.1039/c8ay02213e.
[160] S.R. Krzyzaniak, G.D. Iop, A.P. Holkem, E.M.M. Flores, P.A. Mello, Determi-
nation of inorganic contaminants in carbon nanotubes by plasma-based
techniques: overcoming the limitations of sample preparation, Talanta 192
(2019) 255e262, https://doi.org/10.1016/j.talanta.2018.09.050.
[161] A. Zhang, H. Wang, P. Zha, M. Wang, H. Wang, B. Fan, et al., Microwave-
induced combustion of graphene for further determination of elemental
impurities using ICP-OES and TXRF, J. Anal. At. Spectrom. 33 (11) (2018)
1910e1916, https://doi.org/10.1039/c8ja00229k.
[162] S.R. Mortari, C.R. Cocco, F.R. Bartz, V.L. Dresssler, E.M. Flores, Fast digestion
procedure for determination of catalyst residues in La- and Ni-based carbon
nanotubes, Anal. Chem. 82 (10) (2010) 4298e4303, https://doi.org/10.1021/
ac100429v.
[163] F.G. Antes, F.A. Duarte, M.F. Mesko, M.A. Nunes, V.A. Pereira, E.I. Muller, et al.,
Determination of toxic elements in coal by ICP-MS after digestion using
microwave-induced combustion, Talanta 83 (2) (2010) 364e369, https://
doi.org/10.1016/j.talanta.2010.09.030.
[164] S.M. Cruz, L. Schmidt, F.M. Dalla Nora, M.F. Pedrotti, C.A. Bizzi, J.S. Barin, et al.,
Microwave-induced combustion method for the determination of trace and
ultratrace element impurities in graphite samples by ICP-OES and ICP-MS,
Microchem. J. 123 (2015) 28e32, https://doi.org/10.1016/
j.microc.2015.05.008.
[165] M.S.P. Enders, J.P. de Souza, P. Balestrin, PdA. Mello, F.A. Duarte, E.I. Muller,
Microwave-induced combustion of high purity nuclear flexible graphite for
the determination of potentially embrittling elements using atomic spec-
trometric techniques, Microchem. J. 124 (2016) 321e325, https://doi.org/
10.1016/j.microc.2015.09.015.
[166] P. Grinberg, R.E. Sturgeon, LdO. Diehl, C.A. Bizzi, E.M.M. Flores, Comparison of
sample digestion techniques for the determination of trace and residual
catalyst metal content in single-wall carbon nanotubes by inductively
coupled plasma mass spectrometry, Spectrochim. Acta B 105 (2015) 89e94,
https://doi.org/10.1016/j.sab.2014.09.009.
[167] E.I. Braun, P. Pantano, The importance of an extensive elemental analysis of
single-walled carbon nanotube soot, Carbon 77 (2014) 912e919, https://
doi.org/10.1016/j.carbon.2014.06.005.
[168] J.-H. Lim, V.G. Bairi, A. Fong, Quantification of impurities in carbon nano-
tubes: development of ICP-MS sample preparation methods, Mater. Chem.
Phys. 198 (2017) 324e330, https://doi.org/10.1016/
j.matchemphys.2017.06.014.
[169] L. Ayouni-Derouiche, M. Me
jean, P. Gay, M.-L. Milliand, P. Lante

ri, L. Gauthier,
et al., Development of efficient digestion procedures for quantitative deter-
mination of cobalt and molybdenum catalyst residues in carbon nanotubes,
Carbon 80 (2014) 59e67, https://doi.org/10.1016/j.carbon.2014.08.025.
[170] H. Lachas, R. Richaud, A.A. Herod, D.R. Dugwell, R. Kandiyoti, K.E. Jarvis,
Determination of 17 trace elements in coal and ash reference materials by
ICP-MS applied to milligram sample sizes, Analyst 124 (2) (1999) 177e184,
https://doi.org/10.1039/a807849a.
[171] K. Srogi, Microwave-assisted sample preparation of coal and coal fly ash for
subsequent metal determination, Anal. Lett. 40 (2) (2007) 199e232, https://
doi.org/10.1080/00032710600867713.
[172] H. Suzuki, T. Miyatani, O. Yoshimoto, Determination of impurities in graphite
by ICP-MS and AAS using a metal furnace, Bunseki Kagaku 42 (8) (1993)
485e489, https://doi.org/10.2116/bunsekikagaku.42.8_485.
[173] K. Watanabe, J. Inagawa, Determination of impurity elements in graphite by
acid decompositioneinductively coupled plasma atomic emission spec-
trometry, Analyst 121 (5) (1996) 623e625, https://doi.org/10.1039/
an9962100623.
[174] M. Watanabe, A. Narukawa, Determination of impurity elements in high
purity graphite by inductively coupled plasma atomic emission spectrom-
etry after microwave decomposition, Analyst 125 (6) (2000) 1189e1191,
https://doi.org/10.1039/b001608j.
[175] N. Mketo, P.N. Nomngongo, J.C. Ngila, An overview on analytical methods for
quantitative determination of multi-element in coal samples, TrAC, Trends
Anal. Chem. 85 (Part C) (2016) 107e116, https://doi.org/10.1016/
j.trac.2016.09.002.
[176] D.J. Swaine, Trace Elements in Coal, Butterworth-Heinemann, 1990, p. 292,
https://doi.org/10.1016/C2013-0-00949-8.
[177] L.S.F. Pereira, G.D. Iop, E.M.M. Flores, R.A. Burrow, P.A. Mello, F.A. Duarte,
Strategies for the determination of trace and toxic elements in pitch: eval-
uation of combustion and wet digestion methods for sample preparation,
Fuel Cell. Bull. 163 (2016) 175e179, https://doi.org/10.1016/
j.fuel.2015.09.050.
[178] R.R. Greenberg, P. Bode, E.A. De Nadai Fernandes, Neutron activation anal-
ysis: a primary method of measurement, Spectrochim. Acta B 66 (3e4)
(2011) 193e241, https://doi.org/10.1016/j.sab.2010.12.011.
[179] J. Ku cera, J.W. Bennett, R. Oflaz, R.L. Paul, E.A. De Nadai Fernandes,
M. Kubesova, et al., Elemental characterization of single-wall carbon nano-
tube certified reference material by neutron and prompt gamma activation
analysis, Anal. Chem. 87 (7) (2015) 3699e3705, https://doi.org/10.1021/
ac504094n.
[180] R.L. Paul, R.M. Lindstrom, Prompt gamma-ray activation analysis: funda-
mentals and applications, J. Radioanal. Nucl. Chem. 243 (1) (2000) 181e189,
https://doi.org/10.1023/a:1006796003933.
[181] R. Zeisler, R. Oflaz, R.L. Paul, J.A. Fagan, Use of neutron activation analysis for
the characterization of single-wall carbon nanotube materials, J. Radioanal.
Nucl. Chem. 291 (2) (2011) 561e567, https://doi.org/10.1007/s10967-011-
1290-9.
[182] J. Datta, D.P. Chowdhury, R. Verma, Determination of concentrations of trace
elements in nuclear grade graphite by charged particle activation analysis,
J. Radioanal. Nucl. Chem. 300 (1) (2014) 147e152, https://doi.org/10.1007/
s10967-014-2977-5.
[183] R. Plukiene, _ E. Lagzdina, L. Juodis, A. Plukis, A. Puzas, R. Gvozdaite, _ et al.,
Investigation of impurities of RBMK graphite by different methods, Radio-
carbon 60 (6) (2018) 1861e1870, https://doi.org/10.1017/rdc.2018.93.
[184] D. Spemann, P.D. Esquinazi, Evidence for magnetic order in graphite from
magnetization and transport measurements, in: P. Esquinazi (Ed.), Basic
Physics of Functionalized Graphite, Springer Series in Materials Science, vol.
244, Springer, Switzerland, 2016, pp. 45e76, https://doi.org/10.1007/978-3-
319-39355-1_3. Cham.
[185] A. Limbeck, M. Bonta, W. Nischkauer, Improvements in the direct analysis of
advanced materials using ICP-based measurement techniques, J. Anal. At.
Spectrom. 32 (2) (2017) 212e232, https://doi.org/10.1039/c6ja00335d.
[186] U. Scha €ffer, V. Krivan, Analysis of high purity graphite and silicon carbide by
direct solid sampling electrothermal atomic absorption spectrometry, Fre-
senius’ J. Anal. Chem. 371 (6) (2001) 859e866, https://doi.org/10.1007/
s002160100971.
[187] J. Bok-Badura, A. Jako
bik-Kolon, M. Turek, S. Boncel, K. Karon
, A versatile
method for direct determination of iron content in multi-wall carbon
nanotubes by inductively coupled plasma atomic emission spectrometry
with slurry sample introduction, RSC Adv. 5 (123) (2015) 101634e101640,
https://doi.org/10.1039/c5ra22269a.
[188] P.A. Mello, M.F. Pedrotti, S.M. Cruz, E.I. Muller, V.L. Dressler, E.M.M. Flores,
Determination of rare earth elements in graphite by solid sampling elec-
trothermal vaporization-inductively coupled plasma mass spectrometry,
J. Anal. At. Spectrom. 30 (10) (2015) 2048e2055, https://doi.org/10.1039/
c5ja00136f.
[189] C.-C. Chen, S.-J. Jiang, A.C. Sahayam, Determination of trace elements in
medicinal activated charcoal using slurry sampling electrothermal vapor-
ization inductively coupled plasma mass spectrometry with low vapor-
ization temperature, Talanta 131 (2015) 585e589, https://doi.org/10.1016/
j.talanta.2014.08.034.
[190] S.F. Boulyga, J. Heilmann, T. Prohaska, K.G. Heumann, Development of an

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
accurate, sensitive, and robust isotope dilution laser ablation ICP-MS method
for simultaneous multi-element analysis (chlorine, sulfur, and heavy metals)
in coal samples, Anal. Bioanal. Chem. 389 (3) (2007) 697e706, https://
doi.org/10.1007/s00216-007-1485-7. [211]
[191] R. Matschat, J. Hassler, S. Richter, M. Klewe, A. Dette, Multielement trace
analysis of pure graphite powders using optical emission spectrometry
coupled to a magnetically stabilized DC arc supplied with halogenating gases
as chemical modifiers e a rapid and robust methodology, J. Anal. At. Spec- [212]
trom. 33 (3) (2018) 468e480, https://doi.org/10.1039/c7ja00387k.
[192] T. K
antor, J. Hassler, O. Fo€rster, Determination of trace metals in industrial
boron carbide by solid sampling optical emission spectrometry. Optimiza-
tion of DC arc excitation (current, atmosphere and chemical modifier), [213]
Microchim Acta 156 (3e4) (2006) 231e243, https://doi.org/10.1007/s00604-
006-0636-4.
[193] M. Resano, M. Aramendía, M.A. Belarra, High-resolution continuum source
graphite furnace atomic absorption spectrometry for direct analysis of solid [214]
samples and complex materials: a tutorial review, J. Anal. At. Spectrom. 29
(12) (2014) 2229e2250, https://doi.org/10.1039/c4ja00176a.
[194] M. Resano, E. Bolea-Ferna
ndez, E. Mozas, M.R. Flo
rez, P. Grinberg, [215]
R.E. Sturgeon, Simultaneous determination of Co, Fe, Ni and Pb in carbon
nanotubes by means of solid sampling high-resolution continuum source
graphite furnace atomic absorption spectrometry, J. Anal. At. Spectrom. 28
(5) (2013) 657e665, https://doi.org/10.1039/c3ja30377b. [216]
[195] F.G. Lepri, D.L. Borges, R.G. Araujo, B. Welz, F. Wendler, M. Krieg, et al.,
Determination of heavy metals in activated charcoals and carbon black for
Lyocell fiber production using direct solid sampling high-resolution con- [217]
tinuum source graphite furnace atomic absorption and inductively coupled
plasma optical emission spectrometry, Talanta 81 (3) (2010) 980e987,
https://doi.org/10.1016/j.talanta.2010.01.050.
[196] A. Zacharia, S. Gucer, B. Izgi, A. Chebotarev, H. Karaaslan, Direct atomic ab- [218]
sorption spectrometry determination of tin, lead, cadmium and zinc in high-
purity graphite with flame furnace atomizer, Talanta 72 (2) (2007) 825e830,
https://doi.org/10.1016/j.talanta.2006.10.040.
[197]

C. Herrero-Latorre, J. Alvarez-M
ndez, J. Barciela-García, S. García-Martín,
e [219]
R.M. Pen ~ a-Crecente, Characterization of carbon nanotubes and analytical
methods for their determination in environmental and biological samples: a
review, Anal. Chim. Acta 853 (2015) 77e94, https://doi.org/10.1016/
j.aca.2014.10.008. [220]
[198] E. Pellicer, A.B. Gonza
lez-Guerrero, J. Nogue
s, L.M. Lechuga, E. Mendoza,
Assessment of catalyst particle removal in multi-wall carbon nanotubes by
highly sensitive magnetic measurements, Carbon 47 (3) (2009) 758e763,
https://doi.org/10.1016/j.carbon.2008.11.007. [221]
[199] B. Ballesteros, G. Tobias, L. Shao, E. Pellicer, J. Nogues, E. Mendoza, et al.,
Steam purification for the removal of graphitic shells coating catalytic par-
ticles and the shortening of single-walled carbon nanotubes, Small 4 (9)
(2008) 1501e1506, https://doi.org/10.1002/smll.200701283. [222]
[200] B. Pacakova, Z. Kominkova, J. Vejpravova, A. Mantlikova, M. Kalbac, Analysis
of metal catalyst content in magnetically filtered SWCNTs by SQUID
magnetometry, J. Mater. Sci. 50 (6) (2015) 2544e2553, https://doi.org/
10.1007/s10853-014-8813-z. [223]
[201] C. Bellouard, G. Mercier, S. Cahen, J. Ghanbaja, G. Medjahdi, J. Gleize, et al.,
Magnetism for understanding catalyst analysis of purified carbon nanotubes,
J. Magn. Magn Mater. 411 (2016) 39e48, https://doi.org/10.1016/
j.jmmm.2016.03.056.
[202] E. Remy, S. Cahen, B. Malaman, J. Ghanbaja, C. Bellouard, G. Medjahdi, et al., [224]
Quantitative investigation of mineral impurities of HiPco SWCNT samples:
chemical mechanisms for purification and annealing treatments, Carbon 93
(2015) 933e944, https://doi.org/10.1016/j.carbon.2015.06.015.
[203] A. Jamrozik, J. Przewo
znik, M. Mazurkiewicz, A. Małolepszy, L. Stobin
ski, [225]
G. Trykowski, et al., Influence of iron contaminations on local and bulk
magnetic properties of nonfunctionalized and functionalized multi-wall
carbon nanotubes, Phys. Status Solidi 211 (3) (2014) 661e669, https://
doi.org/10.1002/pssa.201330150. [226]
[204] U.I. Kramm, M. Lefe vre, P. Bogdanoff, D. Schmeisser, J.P. Dodelet, Analyzing
structural changes of Fe-N-C cathode catalysts in PEM fuel cell by Mo €ssbauer
spectroscopy of complete membrane electrode assemblies, J. Phys. Chem. [227]
Lett. 5 (21) (2014) 3750e3756, https://doi.org/10.1021/jz501955g.
[205] M.H. Rümmeli, M. Lo € ffler, C. Kramberger, F. Simon, F. Fülo €p, O. Jost, et al.,
Isotope-engineered single-wall carbon nanotubes; a key material for mag- [228]
netic studies, J. Phys. Chem. C 111 (11) (2007) 4094e4098, https://doi.org/
10.1021/jp066798b.
[206] N.A. Besley, J.J. Titman, M.D. Wright, Theoretical study of the 13C NMR
spectroscopy of single-walled carbon nanotubes, J. Am. Chem. Soc. 127 (50) [229]
(2005) 17948e17953, https://doi.org/10.1021/ja055888b.
[207] D.J. Nelson, C.N. Brammer, Pristine single-walled carbon nanotube purity
evaluation by using 1H NMR spectroscopy, Anal. Bioanal. Chem. 396 (3)
(2010) 1079e1086, https://doi.org/10.1007/s00216-009-3091-3. [230]
[208] X. Tang, A. Kleinhammes, H. Shimoda, L. Fleming, K.Y. Bennoune, S. Sinha, et
al., Electronic structures of single-walled carbon nanotubes determined by
NMR, Science 288 (5465) (2000) 492e494, https://doi.org/10.1126/
science.288.5465.492. [231]
[209] A.S. Claye, N.M. Nemes, A. J
anossy, J.E. Fischer, Structure and electronic
properties of potassium-doped single-wall carbon nanotubes, Phys. Rev. B 62
(8) (2000) R4845eR4848, https://doi.org/10.1103/PhysRevB.62.R4845. [232]
[210] E. Agustina, J. Goak, S. Lee, Y. Seo, J.Y. Park, N. Lee, Simple and precise
833
quantification of iron catalyst content in carbon nanotubes using UV/Visible
spectroscopy, ChemistryOpen 4 (5) (2015) 613e619, https://doi.org/
10.1002/open.201500096.
M. Barberio, P. Barone, A. Bonanno, M. Camarca, A. Oliva, V. Pingitore, et al.,
Visible cathodoluminescence from carbon nanotubes: the role of impurities,
Phys. Status Solidi 205 (6) (2008) 1391e1393, https://doi.org/10.1002/
pssa.200778109.
M. Barberio, D. Barca, P. Barone, V. Pingitore, A. Bonanno, Cathode-lumi-
nescence from extrinsic impurities in bundles of carbon nanotubes: a
possible role, J. Nanosci. Nanotechnol. 11 (10) (2011) 9196e9201, https://
doi.org/10.1166/jnn.2011.4280.
N. Vishnu, A.S. Kumar, A new strategy for simple and quick estimation of
redox active nickel impurity in pristine SWCNT as nickel hexacyanoferrate
by electrochemical technique, Sens. Actuators, B 238 (2017) 1111e1119,
https://doi.org/10.1016/j.snb.2016.07.148.
A. Ambrosi, M. Pumera, Redox-active nickel in carbon nanotubes and its
direct determination, Chem. Eur J. 18 (11) (2012) 3338e3344, https://
doi.org/10.1002/chem.201103266.
A. Schierz, B. Espinasse, M.R. Wiesner, J.H. Bisesi, T. Sabo-Attwood,
P.L. Ferguson, Fate of single walled carbon nanotubes in wetland ecosystems,
Environ. Sci.: Nano 1 (6) (2014) 574e583, https://doi.org/10.1039/
c4en00063c.
S. Arepalli, S.W. Freiman, S.A. Hooker, K.D. Migler, Measurement Issues in
Single-Wall Carbon Nanotubes, National Institute of Standards & Technol-
ogy, Department of Commerce, 2008.
R.R. Moore, C.E. Banks, R.G. Compton, Basal plane pyrolytic graphite modified
electrodes: comparison of carbon nanotubes and graphite powder as elec-
trocatalysts, Anal. Chem. 76 (10) (2004) 2677e2682, https://doi.org/10.1021/
ac040017q.
C.E. Banks, R.R. Moore, T.J. Davies, R.G. Compton, Investigation of modified
basal plane pyrolytic graphite electrodes: definitive evidence for the elec-
trocatalytic properties of the ends of carbon nanotubes, Chem. Commun. 16
(2004) 1804e1805, https://doi.org/10.1039/b406174h.
C.E. Banks, A. Crossley, C. Salter, S.J. Wilkins, R.G. Compton, Carbon nano-
tubes contain metal impurities which are responsible for the "electro-
catalysis" seen at some nanotube-modified electrodes, Angew. Chem. Int. Ed.
45 (16) (2006) 2533e2537, https://doi.org/10.1002/anie.200600033.

B. Sljuki

c, C.E. Banks, R.G. Compton, Iron oxide particles are the active sites
for hydrogen peroxide sensing at multiwalled carbon nanotube modified
electrodes, Nano Lett. 6 (7) (2006) 1556e1558, https://doi.org/10.1021/
nl060366v.
J. Kruusma, N. Mould, K. Jurkschat, A. Crossley, C.E. Banks, Single walled
carbon nanotubes contain residual iron oxide impurities which can domi-
nate their electrochemical activity, Electrochem. Commun. 9 (9) (2007)
2330e2333, https://doi.org/10.1016/j.elecom.2007.06.024.
X. Dai, G.G. Wildgoose, R.G. Compton, Apparent ’electrocatalytic’ activity of
multiwalled carbon nanotubes in the detection of the anaesthetic halothane:
occluded copper nanoparticles, Analyst 131 (8) (2006) 901e906, https://
doi.org/10.1039/b606197d.
C. Batchelor-McAuley, G.G. Wildgoose, R.G. Compton, L. Shao, M.L.H. Green,
Copper oxide nanoparticle impurities are responsible for the electroanalyt-
ical detection of glucose seen using multiwalled carbon nanotubes, Sens.
Actuators, B 132 (1) (2008) 356e360, https://doi.org/10.1016/
j.snb.2008.01.049.
C.P. Jones, K. Jurkschat, A. Crossley, C.E. Banks, Multi-walled carbon nanotube
modified basal plane pyrolytic graphite electrodes: exploring heterogeneity,
electro-catalysis and highlighting batch to batch variation, J. Iran. Chem. Soc.
5 (2) (2008) 279e285, https://doi.org/10.1007/bf03246119.
L. Siegert, D.K. Kampouris, J. Kruusma, V. Sammelselg, C.E. Banks, The het-
erogeneity of multiwalled and single-walled carbon nanotubes: iron oxide
impurities can catalyze the electrochemical oxidation of glucose, Electro-
analysis 21 (1) (2009) 48e51, https://doi.org/10.1002/elan.200804394.
K. Jurkschat, X. Ji, A. Crossley, R.G. Compton, C.E. Banks, Super-washing does
not leave single walled carbon nanotubes iron-free, Analyst 132 (1) (2007)
21e23, https://doi.org/10.1039/b615824b.
M. Merisalu, J. Kruusma, C.E. Banks, Metallic impurity free carbon nanotube
paste electrodes, Electrochem. Commun. 12 (1) (2010) 144e147, https://
doi.org/10.1016/j.elecom.2009.11.009.
C.P. Jones, K. Jurkschat, A. Crossley, R.G. Compton, B.L. Riehl, C.E. Banks, Use
of high-purity metal-catalyst-free multiwalled carbon nanotubes to avoid
potential experimental misinterpretations, Langmuir 23 (18) (2007)
9501e9504, https://doi.org/10.1021/la701522p.
J.P. Smith, C.W. Foster, J.P. Metters, O.B. Sutcliffe, C.E. Banks, Metallic impu-
rities in graphene screen-printed electrodes can influence their electro-
chemical properties, Electroanalysis 26 (11) (2014) 2429e2433, https://
doi.org/10.1002/elan.201400320.
M. Pumera, H. Iwai, Metallic impurities within residual catalyst metallic
nanoparticles are in some cases responsible for "electrocatalytic" effect of
carbon nanotubes, Chem. Asian J. 4 (4) (2009) 554e560, https://doi.org/
10.1002/asia.200800420.
M. Pumera, Voltammetry of carbon nanotubes and graphenes: excitement,
disappointment, and reality, Chem. Rec. 12 (1) (2012) 201e213, https://
doi.org/10.1002/tcr.201100027.
M. Pumera, Carbon nanotubes contain residual metal catalyst nanoparticles
even after washing with nitric acid at elevated temperature because these
834
ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
metal nanoparticles are sheathed by several graphene sheets, Langmuir 23
(11) (2007) 6453e6458, https://doi.org/10.1021/la070088v.
[233] M. Pumera, The electrochemistry of carbon nanotubes: fundamentals and
applications, Chem. Eur J. 15 (20) (2009) 4970e4978, https://doi.org/
10.1002/chem.200900421.
[234] M. Pumera, H. Iwai, Multicomponent metallic impurities and their influence
upon the electrochemistry of carbon nanotubes, J. Phys. Chem. C 113 (11)
(2009) 4401e4405, https://doi.org/10.1021/jp900069e.
[235] E.J.E. Stuart, M. Pumera, Electrochemistry of a whole group of compounds
affected by metallic impurities within carbon nanotubes, J. Phys. Chem. C
114 (49) (2010) 21296e21298, https://doi.org/10.1021/jp108819s.
[236] E.J. Stuart, M. Pumera, Impurities within carbon nanotubes govern the
electrochemical oxidation of substituted hydrazines, Phys. Chem. Chem.
Phys. 13 (22) (2011) 10818e10822, https://doi.org/10.1039/c1cp20176j.
[237] A. Ambrosi, M. Pumera, Regulatory peptides are susceptible to oxidation by
metallic impurities within carbon nanotubes, Chem. Eur J. 16 (6) (2010)
1786e1792, https://doi.org/10.1002/chem.200902534.
[238] M. Pumera, H. Iwai, Y. Miyahara, Bimetallic nickel-iron impurities within
single-walled carbon nanotubes exhibit redox activity towards the oxidation
of amino acids, ChemPhysChem 10 (11) (2009) 1770e1773, https://doi.org/
10.1002/cphc.200900355.
[239] E.L. Chng, M. Pumera, Metallic impurities are responsible for electrocatalytic
behavior of carbon nanotubes towards sulfides, Chem. Asian J. 6 (9) (2011)
2304e2307, https://doi.org/10.1002/asia.201100318.
[240] M. Pumera, Y. Miyahara, What amount of metallic impurities in carbon
nanotubes is small enough not to dominate their redox properties? Nano-
scale 1 (2) (2009) 260e265, https://doi.org/10.1039/b9nr00071b.
[241] J.L. Lyon, K.J. Stevenson, Anomalous electrochemical dissolution and
passivation of iron growth catalysts in carbon nanotubes, Langmuir 23 (22)
(2007) 11311e11318, https://doi.org/10.1021/la7019186.
[242] C.K. Chua, A. Ambrosi, Z. Sofer, A. Mackova
, V. Havra
nek, I. Tomandl, et al.,
Chemical preparation of graphene materials results in extensive uninten-
tional doping with heteroatoms and metals, Chem. Eur J. 20 (48) (2014)
15760e15767, https://doi.org/10.1002/chem.201404205.
[243] A. Ambrosi, C.K. Chua, N.M. Latiff, A.H. Loo, C.H. Wong, A.Y. Eng, et al., Gra-
phene and its electrochemistry - an update, Chem. Soc. Rev. 45 (9) (2016)
2458e2493, https://doi.org/10.1039/c6cs00136j.
[244] M. Pumera, A. Ambrosi, E.L.K. Chng, Impurities in graphenes and carbon
nanotubes and their influence on the redox properties, Chem. Sci. 3 (12)
(2012) 3347e3355, https://doi.org/10.1039/c2sc21374e.
[245] V. Mazanek, J. Luxa, S. Matejkova, J. Kucera, D. Sedmidubsky, M. Pumera, et
al., Ultrapure graphene is a poor electrocatalyst: definitive proof of the key
role of metallic impurities in graphene-based electrocatalysis, ACS Nano 13
(2) (2019) 1574e1582, https://doi.org/10.1021/acsnano.8b07534.
[246] A. Ambrosi, C.K. Chua, B. Khezri, Z. Sofer, R.D. Webster, M. Pumera, Chemi-
cally reduced graphene contains inherent metallic impurities present in
parent natural and synthetic graphite, Proc. Natl. Acad. Sci. U.S.A. 109 (32)
(2012) 12899e12904, https://doi.org/10.1073/pnas.1205388109.
[247] C.H. Wong, Z. Sofer, M. Kubesova, J. Kucera, S. Matejkova, M. Pumera, Syn-
thetic routes contaminate graphene materials with a whole spectrum of
unanticipated metallic elements, Proc. Natl. Acad. Sci. U.S.A. 111 (38) (2014)
13774e13779, https://doi.org/10.1073/pnas.1413389111.
[248] M. Zhou, S. Guo, Electrocatalytic interface based on novel carbon nano-
materials for advanced electrochemical sensors, ChemCatChem 7 (18) (2015)
2744e2764, https://doi.org/10.1002/cctc.201500198.
[249] L. Peng, Z. Xu, Z. Liu, Y. Wei, H. Sun, Z. Li, et al., An iron-based green approach
to 1-h production of single-layer graphene oxide, Nat. Commun. 6 (2015)
5716, https://doi.org/10.1038/ncomms6716.
[250] C. Su, M. Acik, K. Takai, J. Lu, S.J. Hao, Y. Zheng, et al., Probing the catalytic
activity of porous graphene oxide and the origin of this behaviour, Nat.
Commun. 3 (2012) 1298, https://doi.org/10.1038/ncomms2315.
[251] E. Roduner, Understanding catalysis, Chem. Soc. Rev. 43 (24) (2014)
8226e8239, https://doi.org/10.1039/c4cs00210e.
[252] R.H. Crabtree, Resolving heterogeneity problems and impurity artifacts in
operationally homogeneous transition metal catalysts, Chem. Rev. 112 (3)
(2012) 1536e1554, https://doi.org/10.1021/cr2002905.
[253] I. Thome, A. Nijs, C. Bolm, Trace metal impurities in catalysis, Chem. Soc. Rev.
41 (3) (2012) 979e987, https://doi.org/10.1039/c2cs15249e.
[254] J.O.M. Bockris, J. McHardy, Electrocatalysis of oxygen reduction by sodium
tungsten bronze, J. Electrochem. Soc. 120 (1) (1973) 61e66, https://doi.org/
10.1149/1.2403399.
[255] M.S. Burke, M.G. Kast, L. Trotochaud, A.M. Smith, S.W. Boettcher, Cobalt-iron
(oxy)hydroxide oxygen evolution electrocatalysts: the role of structure and
composition on activity, stability, and mechanism, J. Am. Chem. Soc. 137 (10)
(2015) 3638e3648, https://doi.org/10.1021/jacs.5b00281.
[256] A. Wuttig, Y. Surendranath, Impurity ion complexation enhances carbon
dioxide reduction catalysis, ACS Catal. 5 (7) (2015) 4479e4484, https://
doi.org/10.1021/acscatal.5b00808.
[257] Y. Hori, H. Konishi, T. Futamura, A. Murata, O. Koga, H. Sakurai, et al.,
“Deactivation of copper electrode” in electrochemical reduction of CO2,
Electrochim. Acta 50 (27) (2005) 5354e5369, https://doi.org/10.1016/
j.electacta.2005.03.015.
[258] G. Dong, M. Fang, H. Wang, S. Yip, H.-Y. Cheung, F. Wang, et al., Insight into
the electrochemical activation of carbon-based cathodes for hydrogen evo-
lution reaction, J. Mater. Chem. 3 (24) (2015) 13080e13086, https://doi.org/
10.1039/c5ta02551f.
[259] R. Chen, C. Yang, W. Cai, H.-Y. Wang, J. Miao, L. Zhang, et al., Use of platinum
as the counter electrode to study the activity of nonprecious metal catalysts
for the hydrogen evolution reaction, ACS Energy Lett. 2 (5) (2017)
1070e1075, https://doi.org/10.1021/acsenergylett.7b00219.
[260] J.G. Chen, C.W. Jones, S. Linic, V.R. Stamenkovic, Best practices in pursuit of
topics in heterogeneous electrocatalysis, ACS Catal. 7 (9) (2017) 6392e6393,
https://doi.org/10.1021/acscatal.7b02839.
[261] S.G. Ji, H. Kim, H. Choi, S. Lee, C.H. Choi, Overestimation of photo-
electrochemical hydrogen evolution reactivity induced by noble metal im-
purities dissolved from counter/reference electrodes, ACS Catal. 10 (5)
(2020) 3381e3389, https://doi.org/10.1021/acscatal.9b04229.
[262] T. Kylma €l €
a, A. Valkonen, K. Rissanen, Y. Xu, R. Franze
n, Retraction notice to
“trans-Tetrakis(pyridine)dichloroiron(II) as catalyst for Suzuki cross-
coupling in ethanol and water” [Tetrahedron Lett. 49 (2008) 6679], Tetra-
hedron Lett. 50 (40) (2009), https://doi.org/10.1016/j.tetlet.2009.07.103,
5692.
[263] R. Sitko, E. Turek, B. Zawisza, E. Malicka, E. Talik, J. Heimann, et al.,
Adsorption of divalent metal ions from aqueous solutions using graphene
oxide, Dalton Trans. 42 (16) (2013) 5682e5689, https://doi.org/10.1039/
c3dt33097d.
[264] I.C. Gerber, P. Serp, A theory/experience description of support effects in
carbon-supported catalysts, Chem. Rev. 120 (2) (2020) 1250e1349, https://
doi.org/10.1021/acs.chemrev.9b00209.
[265] Y.L. Cao, S.J. Mao, M.M. Li, Y.Q. Chen, Y. Wang, Metal/porous carbon com-
posites for heterogeneous catalysis: old catalysts with improved perfor-
mance promoted by N-doping, ACS Catal. 7 (12) (2017) 8090e8112, https://
doi.org/10.1021/acscatal.7b02335.
[266] L. He, F. Weniger, H. Neumann, M. Beller, Synthesis, characterization, and
application of metal nanoparticles supported on nitrogen-doped carbon:
catalysis beyond electrochemistry, Angew. Chem. Int. Ed. 55 (41) (2016)
12582e12594, https://doi.org/10.1002/anie.201603198.
[267] W. Xia, Interactions between metal species and nitrogen-functionalized
carbon nanotubes, Catal. Sci. 6 (3) (2016) 630e644, https://doi.org/
10.1039/c5cy01694k.
[268] O. Warburg, W. Brefeld, Über die aktivierung stickstoffhaltiger kohlen durch
eisen, Springer, Berlin, Heidelberg, 1928, pp. 166e185, https://doi.org/
10.1007/978-3-642-47774-4_12.
[269] E.K. Rideal, W.M. Wright, CCXL.dlow temperature oxidation at charcoal
surfaces. Part II. The behaviour of charcoal in the presence of promoters,
J. Chem. Soc. 129 (1926) 1813e1821, https://doi.org/10.1039/jr9262901813,
0.
[270] X. Lepro
, E. Terre
s, Y. Vega-Cantú, F.J. Rodríguez-Macías, H. Muramatsu,
Y.A. Kim, et al., Efficient anchorage of Pt clusters on N-doped carbon nano-
tubes and their catalytic activity, Chem. Phys. Lett. 463 (1e3) (2008)
124e129, https://doi.org/10.1016/j.cplett.2008.08.001.
[271] P. Chen, F. Yang, A. Kostka, W. Xia, Interaction of cobalt nanoparticles with
oxygen- and nitrogen-functionalized carbon nanotubes and impact on
nitrobenzene hydrogenation catalysis, ACS Catal. 4 (5) (2014) 1478e1486,
https://doi.org/10.1021/cs500173t.
[272] H. Xu, D. Cheng, D. Cao, X.C. Zeng, A universal principle for a rational design
of single-atom electrocatalysts, Nat. Catal. 1 (2018) 339e348, https://doi.org/
10.1038/s41929-018-0063-z.
[273] M.B. Gawande, P. Fornasiero, R. Zboril, Carbon-based single-atom catalysts
for advanced applications, ACS Catal. 10 (3) (2020) 2231e2259, https://
doi.org/10.1021/acscatal.9b04217.
[274] A. Li, S.A. Nicolae, M. Qiao, K. Preuss, P.A. Szila
gyi, A. Moores, et al., Ho-
mogenous meets heterogenous and electro-catalysis: iron-nitrogen molec-
ular complexes within carbon materials for catalytic applications,
ChemCatChem 11 (16) (2019) 3602e3625, https://doi.org/10.1002/
cctc.201900910.
[275] J. Masa, W. Xia, M. Muhler, W. Schuhmann, On the role of metals in nitrogen-
doped carbon electrocatalysts for oxygen reduction, Angew. Chem. Int. Ed.
54 (35) (2015) 10102e10120, https://doi.org/10.1002/anie.201500569.
[276] W.J. Jiang, L. Gu, L. Li, Y. Zhang, X. Zhang, L.J. Zhang, et al., Understanding the
high activity of Fe-N-C electrocatalysts in oxygen rduction: Fe/Fe3C nano-
particles boost the activity of Fe-N(x), J. Am. Chem. Soc. 138 (10) (2016)
3570e3578, https://doi.org/10.1021/jacs.6b00757.
[277] J. Xiao, X. Pan, S. Guo, P. Ren, X. Bao, Toward fundamentals of confined
catalysis in carbon nanotubes, J. Am. Chem. Soc. 137 (1) (2015) 477e482,
https://doi.org/10.1021/ja511498s.
[278] Y. Tong, X. Yu, H. Wang, B. Yao, C. Li, G. Shi, Trace level CoeN doped graphite
foams as high-performance self-standing electrocatalytic electrodes for
hydrogen and oxygen evolution, ACS Catal. 8 (5) (2018) 4637e4644, https://
doi.org/10.1021/acscatal.8b01131.
[279] S. Campisi, C. Chan-Thaw, A. Villa, Understanding heteroatom-mediated
metalesupport interactions in functionalized carbons: a perspective re-
view, Appl. Sci. 8 (7) (2018) 1159, https://doi.org/10.3390/app8071159.
[280] C. Kim, Y.-K. Choe, D.H. Won, U. Lee, H.-S. Oh, D.K. Lee, et al., Turning harmful
deposition of metal impurities into activation of nitrogen-doped carbon
catalyst toward durable electrochemical CO2 reduction, ACS Energy Lett. 4
(9) (2019) 2343e2350, https://doi.org/10.1021/acsenergylett.9b01581.
[281] Y. Jiang, L. Yang, T. Sun, J. Zhao, Z. Lyu, O. Zhuo, et al., Significant contribution
of intrinsic carbon defects to oxygen reduction activity, ACS Catal. 5 (11)
(2015) 6707e6712, https://doi.org/10.1021/acscatal.5b01835.

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
[282] X. Zhao, X. Zou, X. Yan, C.L. Brown, Z. Chen, G. Zhu, et al., Defect-driven
oxygen reduction reaction (ORR) of carbon without any element doping,
Inorg. Chem. Front. 3 (3) (2016) 417e421, https://doi.org/10.1039/
c5qi00236b.
[283] H.C. Choi, M. Shim, S. Bangsaruntip, H. Dai, Spontaneous reduction of metal
ions on the sidewalls of carbon nanotubes, J. Am. Chem. Soc. 124 (31) (2002)
9058e9059, https://doi.org/10.1021/ja026824t.
[284] R.K. Pandey, L. Chen, S. Teraji, H. Nakanishi, S. Soh, Eco-friendly, direct
deposition of metal nanoparticles on graphite for electrochemical energy
conversion and storage, ACS Appl. Mater. Interfaces 11 (40) (2019)
36525e36534, https://doi.org/10.1021/acsami.9b09273.
[285] Y. Qu, L. Wang, Z. Li, P. Li, Q. Zhang, Y. Lin, et al., Ambient synthesis of single-
atom catalysts from bulk metal via trapping of atoms by surface dangling
bonds, Adv. Mater. 31 (44) (2019) 1904496, https://doi.org/10.1002/
adma.201904496.
[286] D.-W. Shin, X. Meng, J.H. Lee, S.M. Yu, J.H. Yoo, K.S. Lim, et al., Doping and
dedoping in SWCNT film by the spontaneous redox process, J. Phys. Chem. C
115 (37) (2011) 18327e18332, https://doi.org/10.1021/jp204757u.
[287] K. Gong, F. Du, Z. Xia, M. Durstock, L. Dai, Nitrogen-doped carbon nanotube
arrays with high electrocatalytic activity for oxygen reduction, Science 323
(5915) (2009) 760e764, https://doi.org/10.1126/science.1168049.
[288] D. Malko, T. Lopes, E. Symianakis, A.R. Kucernak, The intriguing poison
tolerance of non-precious metal oxygen reduction reaction (ORR) catalysts,
J. Mater. Chem. 4 (1) (2016) 142e152, https://doi.org/10.1039/c5ta05794a.
[289] M.S. Thorum, J.M. Hankett, A.A. Gewirth, Poisoning the oxygen reduction
reaction on carbon-supported Fe and Cu electrocatalysts: evidence for
metal-centered activity, J. Phys. Chem. Lett. 2 (4) (2011) 295e298, https://
doi.org/10.1021/jz1016284.
[290] U. Martinez, S. Komini Babu, E.F. Holby, H.T. Chung, X. Yin, P. Zelenay,
Progress in the development of Fe-based PGM-free electrocatalysts for the
oxygen reduction reaction, Adv. Mater. 31 (31) (2019), e1806545, https://
doi.org/10.1002/adma.201806545.
[291] T. Sharifi, G. Hu, X. Jia, T. Wagberg, Formation of active sites for oxygen
reduction reactions by transformation of nitrogen functionalities in
nitrogen-doped carbon nanotubes, ACS Nano 6 (10) (2012) 8904e8912,
https://doi.org/10.1021/nn302906r.
[292] J. Li, M.-T. Sougrati, a Zitolo, J. Ablett, ic oguz, T. Mineva, et al., Identification
of durable and non-durable FeNx sites in Fe-N-C materials for proton ex-
change membrane fuel cells, ChemRxiv (2020), https://doi.org/10.26434/
chemrxiv.11842431.v1.
[293] D.H. Lee, W.J. Lee, W.J. Lee, S.O. Kim, Y.H. Kim, Theory, synthesis, and oxygen
reduction catalysis of Fe-porphyrin-like carbon nanotube, Phys. Rev. Lett.
106 (17) (2011) 175502, https://doi.org/10.1103/PhysRevLett.106.175502.
[294] A. Morozan, P. Jegou, M. Pinault, S. Campidelli, B. Jousselme, S. Palacin,
Metal-free nitrogen-containing carbon nanotubes prepared from triazole
and tetrazole derivatives show high electrocatalytic activity towards the
oxygen reduction reaction in alkaline media, ChemSusChem 5 (4) (2012)
647e651, https://doi.org/10.1002/cssc.201100675.
[295] P.P. Sharma, J. Wu, R.M. Yadav, M. Liu, C.J. Wright, C.S. Tiwary, et al., Nitro-
gen-doped carbon nanotube arrays for high-efficiency electrochemical
reduction of CO2: on the understanding of defects, defect density, and
selectivity, Angew. Chem. Int. Ed. 54 (46) (2015) 13701e13705, https://
doi.org/10.1002/anie.201506062.
[296] J. Wu, R.M. Yadav, M. Liu, P.P. Sharma, C.S. Tiwary, L. Ma, et al., Achieving
highly efficient, selective, and stable CO2 reduction on nitrogen-doped car-
bon nanotubes, ACS Nano 9 (5) (2015) 5364e5371, https://doi.org/10.1021/
acsnano.5b01079.
[297] C. Ma, P. Hou, X. Wang, Z. Wang, W. Li, P. Kang, Carbon nanotubes with rich
pyridinic nitrogen for gas phase CO2 electroreduction, Appl. Catal. B Environ.
250 (2019) 347e354, https://doi.org/10.1016/j.apcatb.2019.03.041.
[298] H. Wang, Y. Chen, X. Hou, C. Ma, T. Tan, Nitrogen-doped graphenes as effi-
cient electrocatalysts for the selective reduction of carbon dioxide to formate
in aqueous solution, Green Chem. 18 (2016) 3250e3256, https://doi.org/
10.1039/c6gc00410e.
[299] Q. Lv, W. Si, J. He, L. Sun, C. Zhang, N. Wang, et al., Selectively nitrogen-doped
carbon materials as superior metal-free catalysts for oxygen reduction, Nat.
Commun. 9 (2018) 3376, https://doi.org/10.1038/s41467-018-05878-y.
[300] J. Wu, S. Ma, J. Sun, J.I. Gold, C. Tiwary, B. Kim, et al., A metal-free electro-
catalyst for carbon dioxide reduction to multi-carbon hydrocarbons and
oxygenates, Nat. Commun. 7 (2016) 13869, https://doi.org/10.1038/
ncomms13869.
[301] J. Masa, A. Zhao, W. Xia, M. Muhler, W. Schuhmann, Metal-free catalysts for
oxygen reduction in alkaline electrolytes: influence of the presence of Co, Fe,
Mn and Ni inclusions, Electrochim. Acta 128 (2014) 271e278, https://
doi.org/10.1016/j.electacta.2013.11.026.
[302] J. Masa, A. Zhao, W. Xia, Z. Sun, B. Mei, M. Muhler, et al., Trace metal residues
promote the activity of supposedly metal-free nitrogen-modified carbon
catalysts for the oxygen reduction reaction, Electrochem. Commun. 34
(2013) 113e116, https://doi.org/10.1016/j.elecom.2013.05.032.
[303] H. Wang, R. Co ^ te

, G. Faubert, D. Guay, J.P. Dodelet, Effect of the pre-treatment
of carbon black supports on the activity of Fe-based electrocatalysts for the
reduction of oxygen, J. Phys. Chem. B 103 (12) (1999) 2042e2049, https://
doi.org/10.1021/jp9821735.
[304] J. Shui, M. Wang, F. Du, L. Dai, N-doped carbon nanomaterials are durable
catalysts for oxygen reduction reaction in acidic fuel cells, Sci. Adv. 1 (1)
835
(2015), https://doi.org/10.1126/sciadv.1400129 e1400129.
[305] X. Jin, G. Zhang, Y. Hao, Z. Chang, X. Sun, Residual metals present in "metal-
free" N-doped carbons, Chem. Commun. 51 (85) (2015) 15585e15587,
https://doi.org/10.1039/c5cc04322k.
[306] D. Guo, R. Shibuya, C. Akiba, S. Saji, T. Kondo, J. Nakamura, Active sites of
nitrogen-doped carbon materials for oxygen reduction reaction clarified
using model catalysts, Science 351 (6271) (2016) 361e365, https://doi.org/
10.1126/science.aad0832.
[307] L. Dai, Carbon-based catalysts for metal-free electrocatalysis, Curr. Opin.
Electrochem. 4 (1) (2017) 18e25, https://doi.org/10.1016/
j.coelec.2017.06.004.
[308] G. Faubert, R. Co ^ te

, J.P. Dodelet, M. Lefevre, P. Bertrand, Oxygen reduction
catalysts for polymer electrolyte fuel cells from the pyrolysis of FeII acetate
adsorbed on 3,4,9,10-perylenetetracarboxylic dianhydride, Electrochim. Acta
44 (15) (1999) 2589e2603, https://doi.org/10.1016/s0013-4686(98)00382-x.
[309] F. Jaouen, J.-P. Dodelet, Average turn-over frequency of O2 electro-reduction
for Fe/N/C and Co/N/C catalysts in PEFCs, Electrochim. Acta 52 (19) (2007)
5975e5984, https://doi.org/10.1016/j.electacta.2007.03.045.
[310] G. Zhang, R. Chenitz, M. Lefe vre, S. Sun, J.-P. Dodelet, Is iron involved in the
lack of stability of Fe/N/C electrocatalysts used to reduce oxygen at the
cathode of PEM fuel cells? Nano Energy 29 (2016) 111e125, https://doi.org/
10.1016/j.nanoen.2016.02.038.
[311] G. Tuci, L. Luconi, A. Rossin, E. Berretti, H. Ba, M. Innocenti, et al., Aziridine-
functionalized multiwalled carbon nanotubes: robust and versatile catalysts
for the oxygen reduction reaction and knoevenagel condensation, ACS Appl.
Mater. Interfaces 8 (44) (2016) 30099e30106, https://doi.org/10.1021/
acsami.6b09033.
[312] G. Tuci, J. Filippi, H. Ba, A. Rossin, L. Luconi, C. Pham-Huu, et al., How to teach
an old dog new (electrochemical) tricks: aziridine-functionalized CNTs as
efficient electrocatalysts for the selective CO2 reduction to CO, J. Mater.
Chem. 6 (2018) 16382e16389, https://doi.org/10.1039/c8ta04267e.
[313] G. Tuci, A. Rossin, L. Luconi, C. Pham-Huu, S. Cicchi, H. Ba, et al., Pyridine-
decorated carbon nanotubes as a metal-free heterogeneous catalyst for mild
CO2 reduction to methanol with hydroboranes, Catal. Sci. 7 (2017)
5833e5837, https://doi.org/10.1039/c7cy01772c.
[314] G. Tuci, C. Zafferoni, P. D’Ambrosio, S. Caporali, M. Ceppatelli, A. Rossin, et al.,
Tailoring carbon nanotube N-dopants while designing metal-free electro-
catalysts for the oxygen reduction reaction in alkaline medium, ACS Catal. 3
(9) (2013) 2108e2111, https://doi.org/10.1021/cs400379h.
[315] G. Tuci, C. Zafferoni, A. Rossin, A. Milella, L. Luconi, M. Innocenti, et al.,
Chemically functionalized carbon nanotubes with pyridine groups as easily
tunable N-decorated nanomaterials for the oxygen reduction reaction in
alkaline medium, Chem. Mater. 26 (11) (2014) 3460e3470, https://doi.org/
10.1021/cm500805c.
[316] G. Tuci, C. Zafferoni, A. Rossin, L. Luconi, A. Milella, M. Ceppatelli, et al.,
Chemical functionalization of N-doped carbon nanotubes: a powerful
approach to cast light on the electrochemical role of specific N-functional-
ities in the oxygen reduction reaction, Catal. Sci. 16 (2016) 6226e6236,
https://doi.org/10.1039/c6cy00796a.
[317] S. Wang, D. Yu, L. Dai, Polyelectrolyte functionalized carbon nanotubes as
efficient metal-free electrocatalysts for oxygen reduction, J. Am. Chem. Soc.
133 (14) (2011) 5182e5185, https://doi.org/10.1021/ja1112904.
[318] S. Zhang, P. Kang, S. Ubnoske, M.K. Brennaman, N. Song, R.L. House, et al.,
Polyethylenimine-enhanced electrocatalytic reduction of CO2 to formate at
nitrogen-doped carbon nanomaterials, J. Am. Chem. Soc. 136 (22) (2014)
7845e7848, https://doi.org/10.1021/ja5031529.
[319] F. Niu, J. Wu, L. Zhang, P. Li, J. Zhu, Z. Wu, et al., Hydroxyl group rich C60
fullerenol: an excellent hydrogen bond catalyst with superb activity, selec-
tivity, and stability, ACS Catal. 1 (10) (2011) 1158e1161, https://doi.org/
10.1021/cs200317d.
[320] D.-H. Lan, L. Chen, C.-T. Au, S.-F. Yin, One-pot synthesized multi-functional
graphene oxide as a water-tolerant and efficient metal-free heterogeneous
catalyst for cycloaddition reaction, Carbon 93 (2015) 22e31, https://doi.org/
10.1016/j.carbon.2015.05.023.
[321] Y. Jia, L. Zhang, L. Zhuang, H. Liu, X. Yan, X. Wang, et al., Identification of
active sites for acidic oxygen reduction on carbon catalysts with and without
nitrogen doping, Nat. Catal. 2 (2019) 688e695, https://doi.org/10.1038/
s41929-019-0297-4.
[322] L. Xue, Y. Li, X. Liu, Q. Liu, J. Shang, H. Duan, et al., Zigzag carbon as efficient
and stable oxygen reduction electrocatalyst for proton exchange membrane
fuel cells, Nat. Commun. 9 (2018) 3819, https://doi.org/10.1038/s41467-018-
06279-x.
[323] R. Daiyan, X. Tan, R. Chen, W.H. Saputera, H.A. Tahini, E. Lovell, et al., Elec-
troreduction of CO2 to CO on a mesoporous carbon catalyst with progres-
sively removed nitrogen moieties, ACS Energy Lett. 3 (9) (2018) 2292e2298,
https://doi.org/10.1021/acsenergylett.8b01409.
[324] R. Gao, Q. Dai, F. Du, D. Yan, L. Dai, C60-adsorbed single-walled carbon
nanotubes as metal-free, pH-universal, and multifunctional catalysts for
oxygen reduction, oxygen evolution, and hydrogen evolution, J. Am. Chem.
Soc. 141 (29) (2019) 11658e11666, https://doi.org/10.1021/jacs.9b05006.
[325] H. Jiang, J. Gu, X. Zheng, M. Liu, X. Qiu, L. Wang, et al., Defect-rich and ul-
trathin N doped carbon nanosheets as advanced trifunctional metal-free
electrocatalysts for the ORR, OER and HER, Energy Environ. Sci. 12 (2019)
322e333, https://doi.org/10.1039/c8ee03276a.
[326] N. Sreekanth, M.A. Nazrulla, T.V. Vineesh, K. Sailaja, K.L. Phani, Metal-free
836
ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
boron-doped graphene for selective electroreduction of carbon dioxide to
formic acid/formate, Chem. Commun. 51 (2015) 16061e16064, https://
doi.org/10.1039/c5cc06051f.
[327] J. Xie, X. Zhao, M. Wu, Q. Li, Y. Wang, J. Yao, Metal-free fluorine-doped carbon
electrocatalyst for CO2 reduction outcompeting hydrogen evolution, Angew.
Chem. Int. Ed. 57 (31) (2018) 9640e9644, https://doi.org/10.1002/
anie.201802055.
[328] T. Liu, S. Ali, Z. Lian, C. Si, D.S. Su, B. Li, Phosphorus-doped onion-like carbon
for CO2 electrochemical reduction: the decisive role of the bonding config-
uration of phosphorus, J. Mater. Chem. 6 (41) (2018) 19998e20004, https://
doi.org/10.1039/c8ta06649c.
[329] L. Wang, Z. Sofer, M. Pumera, Will any crap we put into graphene increase its
electrocatalytic effect? ACS Nano 14 (1) (2020) 21e25, https://doi.org/
10.1021/acsnano.9b00184.
[330] R.E. Schaak, Beyond guano-doped graphene, ACS Nano 14 (3) (2020)
2555e2556, https://doi.org/10.1021/acsnano.0c02181.
[331] C.H. Choi, C. Baldizzone, G. Polymeros, E. Pizzutilo, O. Kasian, A.K. Schuppert,
et al., Minimizing operando demetallation of Fe-N-C electrocatalysts in acidic
medium, ACS Catal. 6 (5) (2016) 3136e3146, https://doi.org/10.1021/
acscatal.6b00643.
[332] K.H. Kangasniemi, D.A. Condit, T.D. Jarvi, Characterization of vulcan elec-
trochemically oxidized under simulated PEM fuel cell conditions,
J. Electrochem. Soc. 151 (4) (2004) E125eE132, https://doi.org/10.1149/
1.1649756.
[333] R. Chenitz, U.I. Kramm, M. Lefe vre, V. Glibin, G. Zhang, S. Sun, et al., A specific
demetalation of FeeN4 catalytic sites in the micropores of NC_Ar þ NH3 is at
the origin of the initial activity loss of the highly active Fe/N/C catalyst used
for the reduction of oxygen in PEM fuel cells, Energy Environ. Sci. 11 (2)
(2018) 365e382, https://doi.org/10.1039/c7ee02302b.
[334] V.P. Glibin, J.-P. Dodelet, Thermodynamic stability in acid media of FeN4-
based catalytic sites used for the reaction of oxygen reduction in PEM fuel
cells, J. Electrochem. Soc. 164 (9) (2017) F948eF957, https://doi.org/10.1149/
2.1041709jes.
[335] J.A. Varnell, J.S. Sotiropoulos, T.M. Brown, K. Subedi, R.T. Haasch, C.E. Schulz,
et al., Revealing the role of the metal in non-precious-metal catalysts for
oxygen reduction via selective removal of Fe, ACS Energy Lett. 3 (4) (2018)
823e828, https://doi.org/10.1021/acsenergylett.8b00144.
[336] J.A. Varnell, E.C. Tse, C.E. Schulz, T.T. Fister, R.T. Haasch, J. Timoshenko, et al.,
Identification of carbon-encapsulated iron nanoparticles as active species in
non-precious metal oxygen reduction catalysts, Nat. Commun. 7 (2016)
12582, https://doi.org/10.1038/ncomms12582.
[337] C.K. Chua, M. Pumera, Carbocatalysis: the state of "metal-free" catalysis,
Chem. Eur J. 21 (36) (2015) 12550e12562, https://doi.org/10.1002/
chem.201501383.
[338] L. Wang, M. Pumera, Electrochemical catalysis at low dimensional carbons:
graphene, carbon nanotubes and beyond e a review, Appl. Mater. Today 5
(2016) 134e141, https://doi.org/10.1016/j.apmt.2016.09.011.
[339] I. Kruusenberg, N. Alexeyeva, K. Tammeveski, J. Kozlova, L. Matisen,
V. Sammelselg, et al., Effect of purification of carbon nanotubes on their
electrocatalytic properties for oxygen reduction in acid solution, Carbon 49
(12) (2011) 4031e4039, https://doi.org/10.1016/j.carbon.2011.05.048.
[340] L. Wang, A. Ambrosi, M. Pumera, Metal-free" catalytic oxygen reduction
reaction on heteroatom - doped graphene is caused by trace metal impu-
rities, Angew. Chem. Int. Ed. 52 (51) (2013) 13818e13821, https://doi.org/
10.1002/anie.201309171.
[341] L. Wang, C.K. Chua, B. Khezri, R.D. Webster, M. Pumera, Remarkable elec-
trochemical properties of electrochemically reduced graphene oxide to-
wards oxygen reduction reaction are caused by residual metal-based
impurities, Electrochem. Commun. 62 (2016) 17e20, https://doi.org/
10.1016/j.elecom.2015.10.020.
[342] R. Ye, J. Dong, L. Wang, R. Mendoza-Cruz, Y. Li, P.F. An, et al., Manganese
deception on graphene and implications in catalysis, Carbon 132 (2018)
623e631, https://doi.org/10.1016/j.carbon.2018.02.082.
[343] N. Garino, M. Castellino, A. Sacco, F. Risplendi, J.A. Mun ~ oz-Tabares,
M. Armandi, et al., Proving the existence of Mn porphyrin-like complexes
hosted in reduced graphene oxide with outstanding performance as oxygen
reduction reaction catalysts, 2D Mater. 6 (4) (2019), https://doi.org/10.1088/
2053-1583/ab2449, 045001.
[344] L. Wang, C.H.A. Wong, B. Kherzi, R.D. Webster, M. Pumera, So-called “metal-
free” oxygen reduction at graphene nanoribbons is in fact metal driven,
ChemCatChem 7 (11) (2015) 1650e1654, https://doi.org/10.1002/
cctc.201500262.
[345] C.H. Wong, C.K. Chua, B. Khezri, R.D. Webster, M. Pumera, Graphene oxide
nanoribbons from the oxidative opening of carbon nanotubes retain elec-
trochemically active metallic impurities, Angew. Chem. Int. Ed. 52 (33)
(2013) 8685e8688, https://doi.org/10.1002/anie.201303837.
[346] M. Liu, Y. Song, S. He, W.W. Tjiu, J. Pan, Y.Y. Xia, et al., Nitrogen-doped
graphene nanoribbons as efficient metal-free electrocatalysts for oxygen
reduction, ACS Appl. Mater. Interfaces 6 (6) (2014) 4214e4222, https://
doi.org/10.1021/am405900r.
[347] O. Jankovsky, A. Libanska, D. Bousa, D. Sedmidubsky, S. Matejkova, Z. Sofer,
Partially hydrogenated graphene materials exhibit high electrocatalytic ac-
tivities related to unintentional doping with metallic impurities, Chem. Eur J.
22 (25) (2016) 8627e8634, https://doi.org/10.1002/chem.201600811.
[348] L. Wang, Z. Sofer, M. Pumera, Catalytic hydrogen evolution reaction on
"metal-free" graphene: key role of metallic impurities, Nanoscale 11 (23)
(2019) 11083e11085, https://doi.org/10.1039/c9nr03557e.
[349] V. Mazanek, S. Matejkova, D. Sedmidubsky, M. Pumera, Z. Sofer, One-step
synthesis of B/N Co-doped graphene as highly efficient electrocatalyst for the
oxygen reduction reaction: synergistic effect of impurities, Chem. Eur J. 24
(4) (2018) 928e936, https://doi.org/10.1002/chem.201704515.
[350] Y. Lum, Y. Kwon, P. Lobaccaro, L. Chen, E.L. Clark, A.T. Bell, et al., Trace levels
of copper in carbon materials show significant electrochemical CO2 reduc-
tion activity, ACS Catal. 6 (1) (2015) 202e209, https://doi.org/10.1021/
acscatal.5b02399.
[351] Y. Dong, J. Li, L. Shi, Z. Guo, Iron impurities as the active sites for peroxidase-
like catalytic reaction on graphene and its derivatives, ACS Appl. Mater. In-
terfaces 7 (28) (2015) 15403e15413, https://doi.org/10.1021/
acsami.5b03486.
[352] Y. Song, X. Wang, C. Zhao, K. Qu, J. Ren, X. Qu, Label-free colorimetric
detection of single nucleotide polymorphism by using single-walled carbon
nanotube intrinsic peroxidase-like activity, Chem. Eur J. 16 (12) (2010)
3617e3621, https://doi.org/10.1002/chem.200902643.
[353] Y. Song, K. Qu, C. Zhao, J. Ren, X. Qu, Graphene oxide: intrinsic peroxidase
catalytic activity and its application to glucose detection, Adv. Mater. 22 (19)
(2010) 2206e2210, https://doi.org/10.1002/adma.200903783.
[354] B. Dong, Y. Li, X. Ning, H. Wang, H. Yu, F. Peng, Trace iron impurities deac-
tivate palladium supported on nitrogen-doped carbon nanotubes for nitro-
benzene hydrogenation, Appl. Catal. A Gen. 545 (2017) 54e63, https://
doi.org/10.1016/j.apcata.2017.07.035.
[355] P. Chen, L.M. Chew, W. Xia, The influence of the residual growth catalyst in
functionalized carbon nanotubes on supported Pt nanoparticles applied in
selective olefin hydrogenation, J. Catal. 307 (2013) 84e93, https://doi.org/
10.1016/j.jcat.2013.06.030.
[356] Y. Zhao, L. Yang, S. Chen, X. Wang, Y. Ma, Q. Wu, et al., Can boron and ni-
trogen co-doping improve oxygen reduction reaction activity of carbon
nanotubes? J. Am. Chem. Soc. 135 (4) (2013) 1201e1204, https://doi.org/
10.1021/ja310566z.
[357] L. Wang, M. Pumera, Residual metallic impurities within carbon nanotubes
play a dominant role in supposedly "metal-free" oxygen reduction reactions,
Chem. Commun. 50 (84) (2014) 12662e12664, https://doi.org/10.1039/
c4cc03271c.
[358] A. Sims, M. Jeffers, S. Talapatra, K. Mondal, S. Pokhrel, L. Liang, et al., Hydro-
deoxygenation of CO on functionalized carbon nanotubes for liquid fuels
production, Carbon 121 (2017) 274e284, https://doi.org/10.1016/
j.carbon.2017.05.094.
[359] M.P. Browne, M. Pumera, Impurities in graphene/PLA 3D-printing filaments
dramatically influence the electrochemical properties of the devices, Chem.
Commun. 55 (58) (2019) 8374e8377, https://doi.org/10.1039/c9cc03774h.
[360] A. Nel, T. Xia, L. Madler, N. Li, Toxic potential of materials at the nanolevel,
Science 311 (5761) (2006) 622e627, https://doi.org/10.1126/
science.1114397.
[361] M.E. Vance, T. Kuiken, E.P. Vejerano, S.P. McGinnis, M.F. Hochella Jr.,
D. Rejeski, et al., Nanotechnology in the real world: redeveloping the
nanomaterial consumer products inventory, Beilstein J. Nanotechnol. 6
(2015) 1769e1780, https://doi.org/10.3762/bjnano.6.181.
[362] M. Levy, F. Lagarde, V.A. Maraloiu, M.G. Blanchin, F. Gendron, C. Wilhelm, et
al., Degradability of superparamagnetic nanoparticles in a model of intra-
cellular environment: follow-up of magnetic, structural and chemical
properties, Nanotechnology 21 (39) (2010) 395103, https://doi.org/10.1088/
0957-4484/21/39/395103.
[363] S. Steiner, C. Bisig, A. Petri-Fink, B. Rothen-Rutishauser, Diesel exhaust:
current knowledge of adverse effects and underlying cellular mechanisms,
Arch. Toxicol. 90 (7) (2016) 1541e1553, https://doi.org/10.1007/s00204-
016-1736-5.
[364] M. Ema, K.S. Hougaard, A. Kishimoto, K. Honda, Reproductive and develop-
mental toxicity of carbon-based nanomaterials: a literature review, Nano-
toxicology 10 (4) (2016) 391e412, https://doi.org/10.3109/
17435390.2015.1073811.
[365] M. Chen, S. Zhou, Y. Zhu, Y. Sun, G. Zeng, C. Yang, et al., Toxicity of carbon
nanomaterials to plants, animals and microbes: recent progress from 2015-
present, Chemosphere 206 (2018) 255e264, https://doi.org/10.1016/
j.chemosphere.2018.05.020.
[366] K.D. Patel, R.K. Singh, H.-W. Kim, Carbon-based nanomaterials as an
emerging platform for theranostics, Mater. Horiz. 6 (3) (2019) 434e469,
https://doi.org/10.1039/c8mh00966j.
[367] X. Yuan, X. Zhang, L. Sun, Y. Wei, X. Wei, Cellular toxicity and immunological
effects of carbon-based nanomaterials, Part. Fibre Toxicol. 16 (2019) 18,
https://doi.org/10.1186/s12989-019-0299-z.
[368] A.A. Shvedova, V. Castranova, E.R. Kisin, D. Schwegler-Berry, A.R. Murray,
V.Z. Gandelsman, et al., Exposure to carbon nanotube material: assessment
of nanotube cytotoxicity using human keratinocyte cells, J. Toxicol. Environ.
Health, Part A 66 (20) (2003) 1909e1926, https://doi.org/10.1080/
713853956.
[369] Y. Liu, Y. Zhao, B. Sun, C. Chen, Understanding the toxicity of carbon nano-
tubes, Acc. Chem. Res. 46 (3) (2013) 702e713, https://doi.org/10.1021/
ar300028m.
[370] A.A. Shvedova, A. Pietroiusti, B. Fadeel, V.E. Kagan, Mechanisms of carbon
nanotube-induced toxicity: focus on oxidative stress, Toxicol. Appl. Phar-
macol. 261 (2) (2012) 121e133, https://doi.org/10.1016/j.taap.2012.03.023.

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
[371] H.J. Johnston, G.R. Hutchison, F.M. Christensen, S. Peters, S. Hankin,
K. Aschberger, et al., A critical review of the biological mechanisms under-
lying the in vivo and in vitro toxicity of carbon nanotubes: the contribution of
physico-chemical characteristics, Nanotoxicology 4 (2) (2010) 207e246,
https://doi.org/10.3109/17435390903569639.
[372] M. Ema, M. Gamo, K. Honda, A review of toxicity studies of single-walled
carbon nanotubes in laboratory animals, Regul. Toxicol. Pharmacol. 74
(2016) 42e63, https://doi.org/10.1016/j.yrtph.2015.11.015.
[373] A.A. Shvedova, E.R. Kisin, D. Porter, P. Schulte, V.E. Kagan, B. Fadeel, et al.,
Mechanisms of pulmonary toxicity and medical applications of carbon
nanotubes: two faces of Janus? Pharmacol. Ther. 121 (2) (2009) 192e204,
https://doi.org/10.1016/j.pharmthera.2008.10.009.
[374] C.W. Lam, J.T. James, R. McCluskey, R.L. Hunter, Pulmonary toxicity of single-
wall carbon nanotubes in mice 7 and 90 days after intratracheal instillation,
Toxicol. Sci. 77 (1) (2004) 126e134, https://doi.org/10.1093/toxsci/kfg243.
[375] D.K. Lee, S. Jeon, J. Jeong, I.J. Yu, K.S. Song, A. Kang, et al., Potential role of
soluble metal impurities in the acute lung inflammogenicity of multi-walled
carbon nanotubes, Nanomaterials 10 (2) (2020) 379, https://doi.org/10.3390/
nano10020379.
[376] L. Pascolo, G. Zabucchi, A. Gianoncelli, G. Kourousias, E. Trevisan, E. Pascotto,
et al., Synchrotron X-ray microscopy reveals early calcium and iron inter-
action with crocidolite fibers in the lung of exposed mice, Toxicol. Lett. 241
(2016) 111e120, https://doi.org/10.1016/j.toxlet.2015.11.016.
[377] A.B. Kane, R.H. Hurt, H. Gao, The asbestos-carbon nanotube analogy: an
update, Toxicol. Appl. Pharmacol. 361 (2018) 68e80, https://doi.org/
10.1016/j.taap.2018.06.027.
[378] A. Gianoncelli, F. Cammisuli, M. Altissimo, M. Salome
, O. Radillo, G. Ricci, et
al., Iron-related toxicity effects of single-walled carbon nanotubes in human
placental cells (BeWo) investigated by X-ray fluorescence microscopy, X Ray
Spectrom. 48 (5) (2019) 413e421, https://doi.org/10.1002/xrs.2994.
[379] E. Aldieri, I. Fenoglio, F. Cesano, E. Gazzano, G. Gulino, D. Scarano, et al., The
role of iron impurities in the toxic effects exerted by short multiwalled
carbon nanotubes (MWCNT) in murine alveolar macrophages, J. Toxicol.
Environ. Health, Part A 76 (18) (2013) 1056e1071, https://doi.org/10.1080/
15287394.2013.834855.
[380] C. Darne, A. Desforges, N. Berrada, C. Fontana, Y. Guichard, L. Gate
, et al.,
A non-damaging purification method: decoupling the toxicity of multi-
walled carbon nanotubes and their associated metal impurities, Environ.
Sci.: Nano 6 (6) (2019) 1852e1865, https://doi.org/10.1039/c8en01276h.
[381] C. Darne, F. Terzetti, C. Coulais, C. Fontana, S. Binet, L. Gate, et al., Cytotoxicity
and genotoxicity of panel of single- and multiwalled carbon nanotubes:
in vitro effects on normal Syrian hamster embryo and immortalized V79
hamster lung cells, J. Toxicol. 2014 (2014) 872195, https://doi.org/10.1155/
2014/872195.
[382] A. Shinde, C.S.J. Tsai, Toxicity mechanism in fetal lung fibroblast cells for
multi-walled carbon nanotubes defined by chemical impurities and dis-
persibility, Toxicol. Res. 5 (1) (2016) 248e258, https://doi.org/10.1039/
c5tx00211g.
[383] A. Hirano, M. Wada, T. Tanaka, H. Kataura, Oxidative stress of carbon
nanotubes on proteins is mediated by metals originating from the catalyst
remains, ACS Nano 13 (2) (2019) 1805e1816, https://doi.org/10.1021/
acsnano.8b07936.
[384] C. Ge, Y. Li, J.-J. Yin, Y. Liu, L. Wang, Y. Zhao, et al., The contributions of metal
impurities and tube structure to the toxicity of carbon nanotube materials,
NPG Asia Mater. 4 (2012) e32, https://doi.org/10.1038/am.2012.60.
[385] V.E. Kagan, Y.Y. Tyurina, V.A. Tyurin, N.V. Konduru, A.I. Potapovich,
A.N. Osipov, et al., Direct and indirect effects of single walled carbon nano-
tubes on RAW 264.7 macrophages: role of iron, Toxicol. Lett. 165 (1) (2006)
88e100, https://doi.org/10.1016/j.toxlet.2006.02.001.
[386] K. Pulskamp, S. Diabate
, H.F. Krug, Carbon nanotubes show no sign of acute
toxicity but induce intracellular reactive oxygen species in dependence on
contaminants, Toxicol. Lett. 168 (1) (2007) 58e74, https://doi.org/10.1016/
j.toxlet.2006.11.001.
[387] F. Cammisuli, S. Giordani, A. Gianoncelli, C. Rizzardi, L. Radillo, M. Zweyer, et
al., Iron-related toxicity of single-walled carbon nanotubes and crocidolite
fibres in human mesothelial cells investigated by synchrotron XRF micro-
scopy, Sci. Rep. 8 (2018) 706, https://doi.org/10.1038/s41598-017-19076-1.
[388] L. Meng, A. Jiang, R. Chen, C.Z. Li, L. Wang, Y. Qu, et al., Inhibitory effects of
multiwall carbon nanotubes with high iron impurity on viability and
neuronal differentiation in cultured PC12 cells, Toxicology 313 (1) (2013)
49e58, https://doi.org/10.1016/j.tox.2012.11.011.
[389] T.I. Vitkina, V.I. Yankova, T.A. Gvozdenko, V.L. Kuznetsov, D.V. Krasnikov,
A.V. Nazarenko, et al., The impact of multi-walled carbon nanotubes with
different amount of metallic impurities on immunometabolic parameters in
healthy volunteers, Food Chem. Toxicol. 87 (2016) 138e147, https://doi.org/
10.1016/j.fct.2015.11.023.
[390] S. Koyama, Y.A. Kim, T. Hayashi, K. Takeuchi, C. Fujii, N. Kuroiwa, et al., In vivo
immunological toxicity in mice of carbon nanotubes with impurities, Carbon
47 (5) (2009) 1365e1372, https://doi.org/10.1016/j.carbon.2009.01.028.
[391] A. Figarol, J. Pourchez, D. Boudard, V. Forest, J.-M. Tulliani, J.-P. Lecompte, et
al., Biological response to purification and acid functionalization of carbon
nanotubes, J. Nanoparticle Res. 16 (2014) 2507, https://doi.org/10.1007/
s11051-014-2507-y.
[392] L. Guo, D.G. Morris, X. Liu, C. Vaslet, R.H. Hurt, A.B. Kane, Iron bioavailability
and redox activity in diverse carbon nanotube samples, Chem. Mater. 19 (14)
837
(2007) 3472e3478, https://doi.org/10.1021/cm062691p.
[393] X. Liu, V. Gurel, D. Morris, D.W. Murray, A. Zhitkovich, A.B. Kane, et al.,
Bioavailability of nickel in single-wall carbon nanotubes, Adv. Mater. 19 (19)
(2007) 2790e2796, https://doi.org/10.1002/adma.200602696.
[394] Y. Tabei, H. Fukui, A. Nishioka, Y. Hagiwara, K. Sato, T. Yoneda, et al., Effect of
iron overload from multi walled carbon nanotubes on neutrophil-like
differentiated HL-60 cells, Sci. Rep. 9 (2019) 2224, https://doi.org/10.1038/
s41598-019-38598-4.
[395] R.J. Toh, A. Ambrosi, M. Pumera, Bioavailability of metallic impurities in
carbon nanotubes is greatly enhanced by ultrasonication, Chem. Eur J. 18
(37) (2012) 11593e11596, https://doi.org/10.1002/chem.201201955.
[396] C. Bussy, E. Paineau, J. Cambedouzou, N. Brun, C. Mory, B. Fayard, et al.,
Intracellular fate of carbon nanotubes inside murine macrophages: pH-
dependent detachment of iron catalyst nanoparticles, Part. Fibre Toxicol.
10 (2013) 24, https://doi.org/10.1186/1743-8977-10-24.
[397] X. Liu, L. Guo, D. Morris, A.B. Kane, R.H. Hurt, Targeted removal of bioavail-
able metal as a detoxification strategy for carbon nanotubes, Carbon 46 (3)
(2008) 489e500, https://doi.org/10.1016/j.carbon.2007.12.018.
[398] G. Visalli, A. Facciola, D. Iannazzo, A. Piperno, A. Pistone, A. Di Pietro, The role
of the iron catalyst in the toxicity of multi-walled carbon nanotubes
(MWCNTs), J. Trace Elem. Med. Biol. 43 (2017) 153e160, https://doi.org/
10.1016/j.jtemb.2017.01.005.
[399] L. Ou, B. Song, H. Liang, J. Liu, X. Feng, B. Deng, et al., Toxicity of graphene-
family nanoparticles: a general review of the origins and mechanisms,
Part. Fibre Toxicol. 13 (2016) 57, https://doi.org/10.1186/s12989-016-0168-
y.
[400] I. Barbolina, C.R. Woods, N. Lozano, K. Kostarelos, K.S. Novoselov, I.S. Roberts,
Purity of graphene oxide determines its antibacterial activity, 2D Mater. 3
(2016), https://doi.org/10.1088/2053-1583/3/2/025025, 025025.
[401] H. Ali-Boucetta, D. Bitounis, R. Raveendran-Nair, A. Servant, J. Van den Bos-
sche, K. Kostarelos, Purified graphene oxide dispersions lack in vitro cyto-
toxicity and in vivo pathogenicity, Adv. Healthc. Mater. 2 (3) (2013)
433e441, https://doi.org/10.1002/adhm.201200248.
[402] M.S. Hull, A.J. Kennedy, J.A. Steevens, A.J. Bednar, C.A. Weiss Jr., P.J. Vikesland,
Release of metal impurities from carbon nanomaterials influences aquatic
toxicity, Environ. Sci. Technol. 43 (11) (2009) 4169e4174, https://doi.org/
10.1021/es802483p.
[403] D.R. Johnson, R.E. Boyd, A.J. Bednar, C.A. Weiss Jr., M.S. Hull, J.G. Coleman, et
al., Effects of soot by-product from the synthesis of engineered metal-
lofullerene nanomaterials on terrestrial invertebrates, Environ. Toxicol.
Chem. 37 (6) (2018) 1594e1605, https://doi.org/10.1002/etc.4118.
[404] J.N. Mwangi, N. Wang, C.G. Ingersoll, D.K. Hardesty, E.L. Brunson, H. Li, et al.,
Toxicity of carbon nanotubes to freshwater aquatic invertebrates, Environ.
Toxicol. Chem. 31 (8) (2012) 1823e1830, https://doi.org/10.1002/etc.1888.
[405] S.W. Bennett, A. Adeleye, Z. Ji, A.A. Keller, Stability, metal leaching, photo-
activity and toxicity in freshwater systems of commercial single wall carbon
nanotubes, Water Res. 47 (12) (2013) 4074e4085, https://doi.org/10.1016/
j.watres.2012.12.039.
[406] A.S. Adeleye, A.A. Keller, Long-term colloidal stability and metal leaching of
single wall carbon nanotubes: effect of temperature and extracellular poly-
meric substances, Water Res. 49 (2014) 236e250, https://doi.org/10.1016/
j.watres.2013.11.032.
[407] X. Wang, R. Qu, J. Liu, Z. Wei, L. Wang, S. Yang, et al., Effect of different carbon
nanotubes on cadmium toxicity to Daphnia magna: the role of catalyst im-
purities and adsorption capacity, Environ. Pollut. 208 (Part B) (2016)
732e738, https://doi.org/10.1016/j.envpol.2015.10.053.
[408] S.M. Lee, P.M.V. Raja, G.L. Esquenazi, A.R. Barron, Effect of raw and purified
carbon nanotubes and iron oxide nanoparticles on the growth of wheatgrass
prepared from the cotyledons of common wheat (triticum aestivum), Envi-
ron. Sci.: Nano 5 (1) (2018) 103e114, https://doi.org/10.1039/c7en00680b.
[409] O.V. Yazyev, Emergence of magnetism in graphene materials and nano-
structures, Rep. Prog. Phys. 73 (5) (2010), https://doi.org/10.1088/0034-
4885/73/5/056501, 056501.
[410] J. Barzola-Quiquia, P. Esquinazi, M. Lindel, D. Spemann, M. Muallem,
G.D. Nessim, Magnetic order and superconductivity observed in bundles of
double-wall carbon nanotubes, Carbon 88 (2015) 16e25, https://doi.org/
10.1016/j.carbon.2015.02.062.
[411] J.S. Friedman, A. Girdhar, R.M. Gelfand, G. Memik, H. Mohseni, A. Taflove, et
al., Cascaded spintronic logic with low-dimensional carbon, Nat. Commun. 8
(2017) 15635, https://doi.org/10.1038/ncomms15635.
[412] Y. Nakai, R. Tsukada, Y. Miyata, T. Saito, K. Hata, Y. Maniwa, Observation of
the intrinsic magnetic susceptibility of highly purified single-wall carbon
nanotubes, Phys. Rev. B 92 (4) (2015), https://doi.org/10.1103/Phys-
RevB.92.041402, 041402(R).
[413] J.P. Salvetat, T. Fehe
r, C. L’Huillier, F. Beuneu, L. Forro
, Anomalous electron
spin resonance behavior of single-walled carbon nanotubes, Phys. Rev. B 72
(7) (2005), https://doi.org/10.1103/PhysRevB.72.075440, 075440.
[414] M. Venkatesan, P. Dunne, Y.H. Chen, H.Z. Zhang, J.M.D. Coey, Structural and
magnetic properties of iron in graphite, Carbon 56 (2013) 279e287, https://
doi.org/10.1016/j.carbon.2013.01.009.
[415] H. Ohldag, T. Tyliszczak, R. Hohne, D. Spemann, P. Esquinazi, M. Ungureanu,
et al., p-electron ferromagnetism in metal-free carbon probed by soft x-ray
dichroism, Phys. Rev. Lett. 98 (18) (2007) 187204, https://doi.org/10.1103/
PhysRevLett.98.187204.
[416] C.N.R. Rao, H.S.S.R. Matte, K.S. Subrahmanyam, U. Maitra, Unusual magnetic
838
ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
properties of graphene and related materials, Chem. Sci. 3 (1) (2012) 45e52,
https://doi.org/10.1039/c1sc00726b.
[417] M. Sepioni, R.R. Nair, S. Rablen, J. Narayanan, F. Tuna, R. Winpenny, et al.,
Limits on intrinsic magnetism in graphene, Phys. Rev. Lett. 105 (20) (2010)
207205, https://doi.org/10.1103/PhysRevLett.105.207205.
[418] M. Sepioni, R.R. Nair, I.L. Tsai, A.K. Geim, I.V. Grigorieva, Revealing common
artifacts due to ferromagnetic inclusions in highly oriented pyrolytic
graphite, Europhys. Lett. 97 (2012) 47001, https://doi.org/10.1209/0295-
5075/97/47001.
[419] D. Spemann, P. Esquinazi, A. Setzer, W. Bo €hlmann, Trace element content
and magnetic properties of commercial Hopg samples studied by ion beam
microscopy and SQUID magnetometry, AIP Adv. 4 (2014) 107142, https://
doi.org/10.1063/1.4900613.
[420] B. Bittova, J.P. Vejpravova, M. Kalbac, S. Burianova, A. Mantlikova, S. Danis, et
al., Magnetic properties of iron catalyst particles in HiPco single wall carbon
nanotubes, J. Phys. Chem. C 115 (35) (2011) 17303e17309, https://doi.org/
10.1021/jp203365g.
[421] K. Lipert, M. Ritschel, A. Leonhardt, Y. Krupskaya, B. Büchner, R. Klingeler,
Magnetic properties of carbon nanotubes with and without catalyst, J. Phys.
Conf. Ser. 200 (7) (2010), https://doi.org/10.1088/1742-6596/200/7/072061,
072061.
[422] K. Lipert, F. Kretzschmar, M. Ritschel, A. Leonhardt, R. Klingeler, B. Büchner,
Nonmagnetic carbon nanotubes, J. Appl. Phys. 105 (2009), https://doi.org/
10.1063/1.3077177, 063906.
[423] R. Scho€ nfelder, M.H. Rümmeli, W. Gruner, M. Lo € ffler, J. Acker, V. Hoffmann, et
al., Purification-induced sidewall functionalization of magnetically pure
single-walled carbon nanotubes, Nanotechnology 18 (37) (2007) 375601,
https://doi.org/10.1088/0957-4484/18/37/375601.
[424] C. Goze-Bac, S. Latil, P. Lauginie, V. Jourdain, J. Conard, L. Duclaux, et al.,
Magnetic interactions in carbon nanostructures, Carbon 40 (10) (2002)
1825e1842, https://doi.org/10.1016/S0008-6223(02)00061-1.
[425] M. Zaka, Y. Ito, H. Wang, W. Yan, A. Robertson, Y.A. Wu, et al., Electron
paramagnetic resonance investigation of purified catalyst-free single-walled
carbon nanotubes, ACS Nano 4 (12) (2010) 7708e7716, https://doi.org/
10.1021/nn102602a.
[426] N.A. Kumar, S. Gambarelli, F. Duclairoir, G. Bidan, L. Dubois, Synthesis of high
quality reduced graphene oxide nanosheets free of paramagnetic metallic
impurities, J. Mater. Chem. 1 (8) (2013) 2789e2794, https://doi.org/10.1039/
c2ta01036d.
[427] Y. Kim, O.N. Torrens, J.M. Kikkawa, E. Abou-Hamad, C. Goze-Bac, D.E. Luzzi,
High-purity diamagnetic single-wall carbon nanotube buckypaper, Chem.
Mater. 19 (12) (2007) 2982e2986, https://doi.org/10.1021/cm063006h.
[428] N. Tit, M.W.C. Dharma-wardana, Superconductivity in carbon nanotubes
coupled to transition metal atoms, Europhys. Lett. 62 (3) (2003) 405e411,
https://doi.org/10.1209/epl/i2003-00410-4.
[429] L. Grigorian, G.U. Sumanasekera, A.L. Loper, S.L. Fang, J.L. Allen, P.C. Eklund,
Giant thermopower in carbon nanotubes: a one-dimensional Kondo system,
Phys. Rev. B 60 (16) (1999) R11309eR11312, https://doi.org/10.1103/
PhysRevB.60.R11309.
[430] R. Faccio, H. Pardo, F.M. Araújo-Moreira, A.W. Mombrú, Influence of iron
impurities on defected graphene, Chem. Phys. 449 (2015) 14e22, https://
doi.org/10.1016/j.chemphys.2015.01.008.
[431] L. Wang, Z. Sofer, D. Bousa, D. Sedmidubsky, S. Huber, S. Matejkova, et al.,
Graphane nanostripes, Angew. Chem. Int. Ed. 55 (2016) 13965e13969,
https://doi.org/10.1002/anie.201606852.
[432] J.C. Lasjaunias, K. Biljakovi

c, Z. Benes, J.E. Fischer, P. Monceau, Low-temper-
ature specific heat of single-wall carbon nanotubes, Phys. Rev. B 65 (2002)
113409, https://doi.org/10.1103/PhysRevB.65.113409.
[433] X. Tian, S. Zhou, Z. Zhang, X. He, M. Yu, D. Lin, Metal impurities dominate the
sorption of a commercially available carbon nanotube for Pb(II) from water,
Environ. Sci. Technol. 44 (21) (2010) 8144e8149, https://doi.org/10.1021/
es102156u.
[434] W. Peng, Y. Hu, C. Wang, H. Li, Y. Liu, S. Song, Enhanced adsorption perfor-
mance of the graphene oxide with metallic ion impurities by elution, Surf.
Interface Anal. 49 (8) (2017) 728e734, https://doi.org/10.1002/sia.6215.
[435] K. Atkinson, S. Roth, M. Hirscher, W. Grünwald, Carbon nanostructures: an
efficient hydrogen storage medium for fuel cells, Fuel Cell. Bull. 4 (38) (2001)
9e12, https://doi.org/10.1016/S1464-2859(01)80733-1.
[436] A.C. Dillon, K.M. Jones, T.A. Bekkedahl, C.H. Kiang, D.S. Bethune, M.J. Heben,
Storage of hydrogen in single-walled carbon nanotubes, Nature 386 (1997)
377e379, https://doi.org/10.1038/386377a0.
[437] C. Liu, Y.Y. Fan, M. Liu, H.T. Cong, H.M. Cheng, M.S. Dresselhaus, Hydrogen
storage in single-walled carbon nanotubes at room temperature, Science 286
(5442) (1999) 1127e1129, https://doi.org/10.1126/science.286.5442.1127.
[438] G.G. Tibbetts, G.P. Meisner, C.H. Olk, Hydrogen storage capacity of carbon
nanotubes, filaments, and vapor-grown fibers, Carbon 39 (15) (2001)
2291e2301, https://doi.org/10.1016/s0008-6223(01)00051-3.
[439] D.P. Broom, M. Hirscher, Irreproducibility in hydrogen storage material
research, Energy Environ. Sci. 9 (11) (2016) 3368e3380, https://doi.org/
10.1039/c6ee01435f.
[440] M. Hirscher, M. Becher, M. Haluska, U. Dettlaff-Weglikowska, A. Quintel,
G.S. Duesberg, et al., Hydrogen storage in sonicated carbon materials, Appl.
Phys. A 72 (2) (2001) 129e132, https://doi.org/10.1007/s003390100816.
[441] P.M.F.J. Costa, K.S. Coleman, M.L.H. Green, Influence of catalyst metal parti-
cles on the hydrogen sorption of single-walled carbon nanotube materials,
Nanotechnology 16 (4) (2005) 512e517, https://doi.org/10.1088/0957-4484/
16/4/030.
[442] D.P. Broom, C.J. Webb, Pitfalls in the characterisation of the hydrogen
sorption properties of materials, Int. J. Hydrogen Energy 42 (49) (2017)
29320e29343, https://doi.org/10.1016/j.ijhydene.2017.10.028.
[443] K. Wright, A. Barron, C, Catalyst Residue and Oxygen Species Inhibition of the
Formation of Hexahapto-Metal Complexes of Group 6 Metals on Single-
Walled Carbon Nanotubes, vol. 3, 2017, p. 17, https://doi.org/10.3390/
c3020017 (2).
[444] K.S. Zhang, D. Pham, O. Lawal, S. Ghosh, V.S. Gangoli, P. Smalley, et al.,
Overcoming catalyst residue inhibition of the functionalization of single-
walled carbon nanotubes via the Billups-Birch reduction, ACS Appl. Mater.
Interfaces 9 (43) (2017) 37972e37980, https://doi.org/10.1021/
acsami.7b12857.
[445] L.S. Cividanes, E.A.N. Simonetti, M.B. Moraes, F.W. Fernandes, G.P. Thim, In-
fluence of carbon nanotubes on epoxy resin cure reaction using different
techniques: a comprehensive review, Polym. Eng. Sci. 54 (11) (2014)
2461e2469, https://doi.org/10.1002/pen.23775.
[446] L.S. Cividanes, W. Franceschi, F.V. Ferreira, B.R.C. Menezes, R.C.M. Sales,
G.P. Thim, How do CNT affect the branch and crosslink reactions in CNT-
epoxy, Mater. Res. Express 4 (10) (2017) 105101, https://doi.org/10.1088/
2053-1591/aa8d31.
[447] J. Chen, X. Gao, W. Song, Epoxy matrix composites reinforced with purified
carbon nanotubes for thermal management applications, Polym. Adv.
Technol. 30 (11) (2019) 2770e2780, https://doi.org/10.1002/pat.4709.
[448] A. Maio, L. Botta, A.C. Tito, L. Pellegrino, M. Daghetta, R. Scaffaro, Statistical
study of the influence of CNTs purification and plasma functionalization on
the properties of polycarbonate-CNTs nanocomposites, Plasma Process.
Polym. 11 (7) (2014) 664e677, https://doi.org/10.1002/ppap.201400008.
[449] D.-H. Kim, S.-Y. Park, J. Kim, M. Park, Preparation and properties of the
single-walled carbon nanotube/cellulose nanocomposites using N-methyl-
morpholine-N-oxide monohydrate, J. Appl. Polym. Sci. 117 (6) (2010)
3588e3594, https://doi.org/10.1002/app.32247.
[450] S.C. Zhang, W.G. Fahrenholtz, G.E. Hilmas, E.J. Yadlowsky, Pressureless sin-
tering of carbon nanotubeeAl2O3 composites, J. Eur. Ceram. Soc. 30 (6)
(2010) 1373e1380, https://doi.org/10.1016/j.jeurceramsoc.2009.12.005.
[451] J. Zheng, R. Bao, J-h Yi, P. Yang, Microwave purification of multi-wall carbon
nanotubes in gas phase, Diam. Relat. Mater. 68 (2016) 93e101, https://
doi.org/10.1016/j.diamond.2016.06.006.
[452] A. Ostadhossein, K. Yoon, A.C.T. van Duin, J.W. Seo, D. Seveno, Do nickel and
iron catalyst nanoparticles affect the mechanical strength of carbon nano-
tubes? Extreme Mech. Lett. 20 (2018) 29e37, https://doi.org/10.1016/
j.eml.2017.12.007.
[453] C. Zhang, A.C.T. van Duin, J.W. Seo, D. Seveno, Weakening effect of nickel
catalyst particles on the mechanical strength of the carbon nanotube/carbon
fiber junction, Carbon 115 (2017) 589e599, https://doi.org/10.1016/
j.carbon.2017.01.042.
[454] H. Yang, X. Huang, W. Liang, A.C.T. van Duin, M. Raju, S. Zhang, Self-weak-
ening in lithiated graphene electrodes, Chem. Phys. Lett. 563 (2013) 58e62,
https://doi.org/10.1016/j.cplett.2013.01.048.
[455] J. Smits, B. Wincheski, M. Namkung, R. Crooks, R. Louie, Response of Fe
powder, purified and as-produced HiPco single-walled carbon nanotubes to
flash exposure, Mater. Sci. Eng., A 358 (1e2) (2003) 384e389, https://
doi.org/10.1016/s0921-5093(03)00282-x.
[456] J. Zhang, H. Chen, Y. Liu, H. Elledge, C.V. Mashuga, M.S. Mannan, Dust ex-
plosion of carbon nanofibers promoted by iron nanoparticles, Ind. Eng.
Chem. Res. 54 (15) (2015) 3989e3995, https://doi.org/10.1021/
acs.iecr.5b00341.
[457] D. Ogrin, J. Chattopadhyay, A.K. Sadana, W.E. Billups, A.R. Barron, Epoxida-
tion and deoxygenation of single-walled carbon nanotubes: quantification of
epoxide defects, J. Am. Chem. Soc. 128 (35) (2006) 11322e11323, https://
doi.org/10.1021/ja061680u.
[458] T.-J. Park, S. Banerjee, T. Hemraj-Benny, S.S. Wong, Purification strategies and
purity visualization techniques for single-walled carbon nanotubes, J. Mater.
Chem. 16 (2) (2006) 141e154, https://doi.org/10.1039/b510858f.
[459] S.K. Pillai, S.S. Ray, M. Moodley, Purification of single-walled carbon nano-
tubes, J. Nanosci. Nanotechnol. 7 (9) (2007) 3011e3047, https://doi.org/
10.1166/jnn.2007.921.
[460] P.-X. Hou, C. Liu, H.-M. Cheng, Purification of carbon nanotubes, Carbon 46
(15) (2008) 2003e2025, https://doi.org/10.1016/j.carbon.2008.09.009.
[461] A.F. Ismail, P.S. Goh, J.C. Tee, S.M. Sanip, M. Aziz, A review of purification
techniques for carbon nanotubes, Nano 3 (3) (2011) 127e143, https://
doi.org/10.1142/s1793292008000927.
[462] K. MacKenzie, O. Dunens, A.T. Harris, A review of carbon nanotube purifi-
cation by microwave assisted acid digestion, Separ. Purif. Technol. 66 (2)
(2009) 209e222, https://doi.org/10.1016/j.seppur.2009.01.017.
[463] M. Adamska, U. Narkiewicz, Purification of carbon nanotubesda review of
methodology, Nanosci. Nanotechnol. Lett. 10 (10) (2018) 1329e1342,
https://doi.org/10.1166/nnl.2018.2804.
[464] Q. Zhang, J.Q. Huang, W.Z. Qian, Y.Y. Zhang, F. Wei, The road for nano-
materials industry: a review of carbon nanotube production, post-treatment,
and bulk applications for composites and energy storage, Small 9 (8) (2013)
1237e1265, https://doi.org/10.1002/smll.201203252.
[465] A. Eatemadi, H. Daraee, H. Karimkhanloo, M. Kouhi, N. Zarghami,
A. Akbarzadeh, et al., Carbon nanotubes: properties, synthesis, purification,

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
and medical applications, Nanoscale Res. Lett. 9 (2014) 393, https://doi.org/
10.1186/1556-276X-9-393.
[466] A.B. Makama, A. Salmiaton, N. Abdullah, T.S.Y. Choong, E.B. Saion, Recent
developments in purification of single wall carbon nanotubes, Separ. Sci.
Technol. 49 (17) (2014) 2797e2812, https://doi.org/10.1080/
01496395.2013.815628.
[467] _
S. Zarska, D. Kulawik, J. Drabowicz, W. Ciesielski, A review of procedures of
purification and chemical modification of carbon nanotubes with bromine,
Fullerenes, Nanotub. Carbon Nanostruct. 25 (10) (2017) 563e569, https://
doi.org/10.1080/1536383x.2017.1330266.
[468] E.M. do Nascimento Martins, C.A. Furtado, A.P. Santos, L.M. de Andrade,
L.O. Ladeira, Synthesis, purification and functionalization of carbon nano-
tubes for biotechnological applications, in: A. Jorio (Ed.), Bioengineering
Applications of Carbon Nanostructures, Nanomedicine and Nanotoxicology,
Springer, Cham, 2016, pp. 139e163, https://doi.org/10.1007/978-3-319-
25907-9_8.
[469] P. Chaturvedi, P. Verma, A. Singh, P.K. Chaudhary, Basu PK. Harsh, Carbon
nanotubeepurification and sorting protocols, Defence Sci. J. 58 (5) (2008)
591e599, https://doi.org/10.14429/dsj.58.1694.
[470] D. Chattopadhyay, I. Galeska, F. Papadimitrakopoulos, Complete elimination
of metal catalysts from single wall carbon nanotubes, Carbon 40 (7) (2002)
985e988, https://doi.org/10.1016/s0008-6223(01)00234-2.
[471] P. Nikolaev, M.J. Bronikowski, R.K. Bradley, F. Rohmund, D.T. Colbert,
K.A. Smith, et al., Gas-phase catalytic growth of single-walled carbon
nanotubes from carbon monoxide, Chem. Phys. Lett. 313 (1e2) (1999)
91e97, https://doi.org/10.1016/s0009-2614(99)01029-5.
[472] B. Kitiyanan, W.E. Alvarez, J.H. Harwell, D.E. Resasco, Controlled production
of single-wall carbon nanotubes by catalytic decomposition of CO on
bimetallic CoeMo catalysts, Chem. Phys. Lett. 317 (3e5) (2000) 497e503,
https://doi.org/10.1016/s0009-2614(99)01379-2.
[473] Q. Zhang, J.Q. Huang, M.Q. Zhao, W.Z. Qian, F. Wei, Carbon nanotube mass
production: principles and processes, ChemSusChem 4 (7) (2011) 864e889,
https://doi.org/10.1002/cssc.201100177.
[474] M.F. De Volder, S.H. Tawfick, R.H. Baughman, A.J. Hart, Carbon nanotubes:
present and future commercial applications, Science 339 (6119) (2013)
535e539, https://doi.org/10.1126/science.1222453.
[475] K. Hata, D.N. Futaba, K. Mizuno, T. Namai, M. Yumura, S. Iijima, Water-
assisted highly efficient synthesis of impurity-free single-walled carbon
nanotubes, Science 306 (5700) (2004) 1362e1364, https://doi.org/10.1126/
science.1104962.
[476] Z.J. Pan, R.T. Yang, Catalytic behavior of transition metal oxide in graphite
gasification by oxygen, water, and carbon dioxide, J. Catal. 130 (1) (1991)
161e172, https://doi.org/10.1016/0021-9517(91)90100-i.
[477] R. Brukh, O. Sae-Khow, S. Mitra, Stabilizing single-walled carbon nanotubes
by removal of residual metal catalysts, Chem. Phys. Lett. 459 (1e6) (2008)
149e152, https://doi.org/10.1016/j.cplett.2008.05.026.
[478] I.W. Chiang, B.E. Brinson, R.E. Smalley, J.L. Margrave, R.H. Hauge, Purification
and characterization of single-wall carbon nanotubes, J. Phys. Chem. B 105
(6) (2001) 1157e1161, https://doi.org/10.1021/jp003453z.
[479] J. Ma, J.N. Wang, Purification of single-walled carbon nanotubes by a highly
efficient and nondestructive approach, Chem. Mater. 20 (9) (2008)
2895e2902, https://doi.org/10.1021/cm8001699.
[480] I.W. Chiang, B.E. Brinson, A.Y. Huang, P.A. Willis, M.J. Bronikowski,
J.L. Margrave, et al., Purification and characterization of single-wall carbon
nanotubes (SWNTs) obtained from the gas-phase decomposition of CO
(HiPco process), J. Phys. Chem. B 105 (35) (2001) 8297e8301, https://doi.org/
10.1021/jp0114891.
[481] S.H. Tan, J.C. Goak, S.C. Hong, N. Lee, Purification of single-walled carbon
nanotubes using a fixed bed reactor packed with zirconia beads, Carbon 46
(2) (2008) 245e254, https://doi.org/10.1016/j.carbon.2007.11.013.
[482] A.M. Dimiev, J.M. Tour, Mechanism of graphene oxide formation, ACS Nano 8
(3) (2014) 3060e3068, https://doi.org/10.1021/nn500606a.
[483] G. Charron, S. Mazerat, M. Erdogan, A. Gloter, A. Filoramo, J. Cambedouzou, et
al., Insights into the mechanism of the gas-phase purification of HiPco
SWNTs through a comprehensive multi-technique study, New J. Chem. 33
(6) (2009) 1211e1223, https://doi.org/10.1039/b900373h.
[484] J. Tang, L.C. Qin, T. Sasaki, M. Yudasaka, A. Matsushita, S. Iijima, Compress-
ibility and polygonization of single-walled carbon nanotubes under hydro-
static pressure, Phys. Rev. Lett. 85 (9) (2000) 1887e1889, https://doi.org/
10.1103/PhysRevLett.85.1887.
[485] C. Ge, W. Li, Y. Li, B. Li, J. Du, Y. Qiu, et al., Significance and systematic analysis
of metallic impurities of carbon nanotubes produced by different manufac-
turers, J. Nanosci. Nanotechnol. 11 (3) (2011) 2389e2397, https://doi.org/
10.1166/jnn.2011.3520.
[486] D.L. Plata, P.M. Gschwend, C.M. Reddy, Industrially synthesized single-walled
carbon nanotubes: compositional data for users, environmental risk as-
sessments, and source apportionment, Nanotechnology 19 (18) (2008)
185706, https://doi.org/10.1088/0957-4484/19/18/185706.
[487] J.-P. Tessonnier, D. Rosenthal, T.W. Hansen, C. Hess, M.E. Schuster, R. Blume,
et al., Analysis of the structure and chemical properties of some commercial
carbon nanostructures, Carbon 47 (7) (2009) 1779e1798, https://doi.org/
10.1016/j.carbon.2009.02.032.
[488] C.M. White, R. Banks, I. Hamerton, J.F. Watts, Characterisation of commer-
cially CVD grown multi-walled carbon nanotubes for paint applications,
Prog. Org. Coating 90 (2016) 44e53, https://doi.org/10.1016/
839
j.porgcoat.2015.09.020.
[489] K.E. Levine, L. Han, A.C. McWilliams, A.S. Essader, K.E. Amato, R.A. Fernando,
et al., Characterization of an assortment of commercially available multi-
walled carbon nanotubes, Microchim Acta 181 (1e2) (2013) 171e179,
https://doi.org/10.1007/s00604-013-1088-2.
[490] A. Kovtun, E. Treossi, N. Mirotta, A. Scida , A. Liscio, M. Christian, et al.,
Benchmarking of graphene-based materials: real commercial products
versus ideal graphene, 2D Mater. 6 (2) (2019), https://doi.org/10.1088/2053-
1583/aafc6e, 025006.
[491] B. Vigolo, C. He
rold, J.-F. Mare ^che

, J. Ghanbaja, M. Gulas, F.L. Normand, et al.,
A comprehensive scenario for commonly used purification procedures of
arc-discharge as-produced single-walled carbon nanotubes, Carbon 48 (4)
(2010) 949e963, https://doi.org/10.1016/j.carbon.2009.10.044.
[492] W.T. Borden, R. Hoffmann, T. Stuyver, B. Chen, Dioxygen: what makes this
triplet diradical kinetically persistent? J. Am. Chem. Soc. 139 (26) (2017)
9010e9018, https://doi.org/10.1021/jacs.7b04232.
[493] Y.Q. Xu, H. Peng, R.H. Hauge, R.E. Smalley, Controlled multistep purification
of single-walled carbon nanotubes, Nano Lett. 5 (1) (2005) 163e168, https://
doi.org/10.1021/nl048300s.
[494] H.G. Cho, S.W. Kim, H.J. Lim, C.H. Yun, H.S. Lee, C.R. Park, A simple and highly
effective process for the purification of single-walled carbon nanotubes
synthesized with arc-discharge, Carbon 47 (15) (2009) 3544e3549, https://
doi.org/10.1016/j.carbon.2009.08.017.
[495] X. Ling, Y. Wei, L. Zou, S. Xu, The effect of different order of purification
treatments on the purity of multiwalled carbon nanotubes, Appl. Surf. Sci.
276 (2013) 159e166, https://doi.org/10.1016/j.apsusc.2013.03.056.
[496] F. Rodríguez-Reinoso, M. Molina-Sabio, M.T. Gonz
alez, The use of steam and
CO2 as activating agents in the preparation of activated carbons, Carbon 33
(1) (1995) 15e23, https://doi.org/10.1016/0008-6223(94)00100-e.
[497] Y.S. Min, E.J. Bae, W. Park, Sulfidative purification of carbon nanotubes in-
tegrated in transistors, J. Am. Chem. Soc. 127 (23) (2005) 8300e8301,
https://doi.org/10.1021/ja052320u.
[498] W. Kicin
ski, B. Budner, M. Norek, M. Szala, M. Polan
ski, S. Dyjak, Origin of
microporosity in chalcogen-doped carbon materials: the case of selenium-
doped carbogels, Microporous Mesoporous Mater. 272 (2018) 260e264,
https://doi.org/10.1016/j.micromeso.2018.06.047.
[499] N. Galland, F. Caralp, M.-T. Rayez, Y. Hannachi, J.-C. Loison, G. Dorthe, et al.,
Reaction of carbon atoms, C (2p2,3P), with hydrogen sulfide, H2S (X1A1):
overall rate constant and product channels, J Phys Chem A 105 (43) (2001)
9893e9900, https://doi.org/10.1021/jp011713m.
[500] T.-C. Chen, M.-Q. Zhao, Q. Zhang, G.-L. Tian, J.-Q. Huang, F. Wei, In situ
monitoring the role of working metal catalyst nanoparticles for ultrahigh
purity single-walled carbon nanotubes, Adv Funct Mater 23 (40) (2013)
5066e5073, https://doi.org/10.1002/adfm.201300614.
[501] L. Cabana, X. Ke, D. Kepi
c, J. Oro-Sole
, E. Tobías-Rossell, G. Van Tendeloo, et
al., The role of steam treatment on the structure, purity and length distri-
bution of multi-walled carbon nanotubes, Carbon 93 (2015) 1059e1067,
https://doi.org/10.1016/j.carbon.2015.06.027.
[502] B.R. Stanmore, J.F. Brilhac, P. Gilot, The oxidation of soot: a review of ex-
periments, mechanisms and models, Carbon 39 (15) (2001) 2247e2268,
https://doi.org/10.1016/s0008-6223(01)00109-9.
[503] J.A. Mene
ndez, J. Phillips, B. Xia, L.R. Radovic, On the modification and
characterization of chemical surface properties of activated carbon: in the
search of carbons with stable basic properties, Langmuir 12 (18) (1996)
4404e4410, https://doi.org/10.1021/la9602022.
[504] M. Brzhezinskaya, E.A. Belenkov, V.A. Greshnyakov, G.E. Yalovega,
I.O. Bashkin, New aspects in the study of carbon-hydrogen interaction in
hydrogenated carbon nanotubes for energy storage applications, J Alloys
Compd 792 (2019) 713e720, https://doi.org/10.1016/j.jallcom.2019.04.107.
[505] Y. Liu, L. Gao, J. Sun, S. Zheng, L. Jiang, Y. Wang, et al., A multi-step strategy
for cutting and purification of single-walled carbon nanotubes, Carbon 45
(10) (2007) 1972e1978, https://doi.org/10.1016/j.carbon.2007.06.009.
[506] S.R. Vivekchand, R. Jayakanth, A. Govindaraj, C.N. Rao, The problem of pur-
ifying single-walled carbon nanotubes, Small 1 (10) (2005) 920e923, https://
doi.org/10.1002/smll.200500092.
[507] L. Sheng, L. Shi, K. An, L. Yu, Y. Ando, X. Zhao, Effective and efficient purifi-
cation of single-wall carbon nanotubes based on hydrogen treatment, Chem
Phys Lett 502 (1e3) (2011) 101e106, https://doi.org/10.1016/
j.cplett.2010.12.034.
[508] A.V. Talyzin, S. Luzan, I.V. Anoshkin, A.G. Nasibulin, H. Jiang, E.I. Kauppinen,
et al., Hydrogenation, purification, and unzipping of carbon nanotubes by
reaction with molecular hydrogen: road to graphane nanoribbons, ACS Nano
5 (6) (2011) 5132e5140, https://doi.org/10.1021/nn201224k.
[509] S. Luidold, H. Antrekowitsch, Hydrogen as a reducing agent: thermodynamic
possibilities, JOM 59 (10) (2007) 58e62, https://doi.org/10.1007/s11837-
007-0133-1.
[510] S. Luidold, H. Antrekowitsch, Hydrogen as a reducing agent: state-of-the-art
science and technology, JOM 59 (6) (2007) 20e26, https://doi.org/10.1007/
s11837-007-0072-x.
[511] C.J. Im, T. Durney, M.L. Matuszak, Halogen treatment of char for the removal
of sulfur and mineral matter, Fuel Process Technol 33 (1) (1993) 49e60,
https://doi.org/10.1016/0378-3820(93)90057-b.
[512] T. Thoms, Developments for the precombustion removal of inorganic sulfur
from coal, Fuel Process Technol 43 (2) (1995) 123e128, https://doi.org/
10.1016/0378-3820(95)00008-u.
840
ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
[513] U. Helmut, Process of purifying graphite (1959) 2914383.
[514] S. Dyjak, W. Kicin
ski, M. Norek, M. Dyjak, S. Cudziło, Carbide-derived carbon
obtained via bromination of titanium carbide: comparative analysis with
chlorination and hydrogen storage studies, Microporous Mesoporous Mater
273 (2019) 26e34, https://doi.org/10.1016/j.micromeso.2018.06.037.
[515] V. Presser, M. Heon, Y. Gogotsi, Carbide-derived carbons - from porous
networks to nanotubes and graphene, Adv Funct Mater 21 (5) (2011)
810e833, https://doi.org/10.1002/adfm.201002094.
[516] Y.N. Chang, F.I. Wei, High-temperature chlorine corrosion of metals and al-
loys, J Mater Sci 26 (14) (1991) 3693e3698, https://doi.org/10.1007/
bf01184958.
[517] S. Dimovski, A. Nikitin, H. Ye, Y. Gogotsi, Synthesis of graphite by chlorina-
tion of iron carbide at moderate temperatures, J Mater Chem 14 (2) (2004)
238e243, https://doi.org/10.1039/b311938f.
[518] V.O. Nyamori, S.D. Mhlanga, N.J. Coville, The use of organometallic transition
metal complexes in the synthesis of shaped carbon nanomaterials,
J Organomet Chem 693 (13) (2008) 2205e2222, https://doi.org/10.1016/
j.jorganchem.2008.04.003.
[519] D. Avila-Brande, E. Urones-Garrote, N.A. Katcho, E. Lomba, A. Gomez-Her-
rero, A.R. Landa-Canovas, et al., Electron microscopy characterization of
nanostructured carbon obtained from chlorination of metallocenes and
metal carbides, Micron 38 (4) (2007) 335e345, https://doi.org/10.1016/
j.micron.2006.06.002.
[520] E. Urones-Garrote, A. Go


mez-Herrero, D. Avila-Brande, N.A. Katcho,
E. Lomba, A.R. Landa-Ca
novas, et al., Transmission electron microscopy
characterization of nanostructured carbon derived from Cr3C2 and
Cr(C5H7O2)3, Carbon 48 (5) (2010) 1425e1433, https://doi.org/10.1016/
j.carbon.2009.12.035.
[521] P. Gonza


lez-García, E. Urones-Garrote, D. Avila-Brande, L.C. Otero-Díaz,
Carbon particles of variable shape produced by the chlorination of bis(ben-
zene)chromium, J Organomet Chem 740 (2013) 141e147, https://doi.org/
10.1016/j.jorganchem.2013.05.011.
[522] J.L. Zimmerman, R.K. Bradley, C.B. Huffman, R.H. Hauge, J.L. Margrave, Gas-
phase purification of single-wall carbon nanotubes, Chem Mater 12 (5)
(2000) 1361e1366, https://doi.org/10.1021/cm990693m.
[523] G. Mercier, C. He
rold, J.-F. Mare ^che

, S. Cahen, J. Gleize, J. Ghanbaja, et al.,
Selective removal of metal impurities from single walled carbon nanotube
samples, New J Chem 37 (3) (2013) 790e795, https://doi.org/10.1039/
c2nj41057e.
[524] A. Desforges, G. Mercier, C. He
rold, J. Gleize, F.L. Normand, B. Vigolo,
Improvement of carbon nanotube stability by high temperature oxygen/
chlorine gas treatment, Carbon 76 (2014) 275e284, https://doi.org/10.1016/
j.carbon.2014.04.078.
[525] A. Desforges, A.V. Bridi, J. Kadok, E. Flahaut, F. Le Normand, J. Gleize, et al.,
Dramatic enhancement of double-walled carbon nanotube quality through a
one-pot tunable purification method, Carbon 110 (2016) 292e303, https://
doi.org/10.1016/j.carbon.2016.09.033.
[526] N. Berrada, A. Desforges, C. Bellouard, E. Flahaut, J. Gleize, J. Ghanbaja, et al.,
Protecting carbon nanotubes from oxidation for selective carbon impurity
elimination, J Phys Chem C 123 (23) (2019) 14725e14733, https://doi.org/
10.1021/acs.jpcc.8b12554.
[527] E.L. Chng, H.L. Poh, Z. Sofer, M. Pumera, Purification of carbon nanotubes by
high temperature chlorine gas treatment, Phys Chem Chem Phys 15 (15)
(2013) 5615e5619, https://doi.org/10.1039/c3cp50348h.
[528] E. Andreoli, R. Suzuki, A.W. Orbaek, M.S. Bhutani, R.H. Hauge, W. Adams, et
al., Preparation and evaluation of polyethyleneimine-single walled carbon
nanotube conjugates as vectors for pancreatic cancer treatment, J Mater
Chem B 2 (29) (2014) 4740e4747, https://doi.org/10.1039/c4tb00778f.
[529] V. Gomez, S. Irusta, O.B. Lawal, W. Adams, R.H. Hauge, C.W. Dunnill, et al.,
Enhanced purification of carbon nanotubes by microwave and chlorine
cleaning procedures, RSC Adv 6 (14) (2016) 11895e11902, https://doi.org/
10.1039/c5ra24854j.
[530] J. Barkauskas, I. Stankevi _ A. Selskis, A novel purification method of
ciene,
carbon nanotubes by high-temperature treatment with tetrachloromethane,
Sep Purif Technol 71 (3) (2010) 331e336, https://doi.org/10.1016/
j.seppur.2009.12.019.
[531] J.C. Goak, C.J. Lim, Y. Hyun, E. Cho, Y. Seo, N. Lee, Efficient gas-phase purifi-
cation using chloroform for metal-free multi-walled carbon nanotubes,
Carbon 148 (2019) 258e266, https://doi.org/10.1016/j.carbon.2019.03.077.
[532] F. Yang, P. Pranda, V. Hlavacek, Recovery of fly ash carbon by carbo-
chlorination via phosgene route, Powder Technol 131 (2e3) (2003)
206e211, https://doi.org/10.1016/s0032-5910(03)00002-0.
[533] Y.K. Chen, M.L.H. Green, J.L. Griffin, J. Hammer, R.M. Lago, S.C. Tsang, Puri-
fication and opening of carbon nanotubes via bromination, Adv Mater 8 (12)
(1996) 1012e1015, https://doi.org/10.1002/adma.19960081216.
[534] P.X. Hou, S. Bai, Q.H. Yang, C. Liu, H.M. Cheng, Multi-step purification of
carbon nanotubes, Carbon 40 (1) (2002) 81e85, https://doi.org/10.1016/
s0008-6223(01)00075-6.
[535] Y. Mackeyev, S. Bachilo, K.B. Hartman, L.J. Wilson, The purification of HiPco
SWCNTs with liquid bromine at room temperature, Carbon 45 (5) (2007)
1013e1017, https://doi.org/10.1016/j.carbon.2006.12.026.
[536] K. Shen, H. Xu, Y. Jiang, T. Pietraß, The role of carbon nanotube structure in
purification and hydrogen adsorption, Carbon 42 (11) (2004) 2315e2322,
https://doi.org/10.1016/j.carbon.2004.05.014.
[537] E. Stupnisec-Lisac, M. Karsulin, H. Takeouti, Passivation of iron, nickel and
cobalt in concentrated nitric acid solutions, Passivity Met Semicond (1883)
327e334, https://doi.org/10.1016/B978-0-444-42252-1.50054-0.
[538] H.H. Uhlig, T.L. O’Connor, Nature of the passive film on iron in concentrated
nitric acid, J Electrochem Soc 102 (10) (1955) 562e572, https://doi.org/
10.1149/1.2429913.
[539] J. Bana
s, B. Mazurkiewicz, B. Stypuła, Passivity of metals in concentrated and
anhydrous solutions of sulphuric acid, Electrochim Acta 37 (6) (1992)
1069e1073, https://doi.org/10.1016/0013-4686(92)85224-9.
[540] K. Domagała, M. Borlaf, J. Traber, D. Kata, T. Graule, Purification and func-
tionalisation of multi-walled carbon nanotubes, Mater Lett 253 (2019)
272e275, https://doi.org/10.1016/j.matlet.2019.06.085.
[541] E.R. Edwards, E.F. Antunes, E.C. Botelho, M.R. Baldan, E.J. Corat, Evaluation of
residual iron in carbon nanotubes purified by acid treatments, Appl Surf Sci
258 (2) (2011) 641e648, https://doi.org/10.1016/j.apsusc.2011.07.032.
[542] V. Datsyuk, M. Kalyva, K. Papagelis, J. Parthenios, D. Tasis, A. Siokou, et al.,
Chemical oxidation of multiwalled carbon nanotubes, Carbon 46 (6) (2008)
833e840, https://doi.org/10.1016/j.carbon.2008.02.012.
[543] K.A. Wepasnick, B.A. Smith, K.E. Schrote, H.K. Wilson, S.R. Diegelmann,
D.H. Fairbrother, Surface and structural characterization of multi-walled
carbon nanotubes following different oxidative treatments, Carbon 49 (1)
(2011) 24e36, https://doi.org/10.1016/j.carbon.2010.08.034.
[544] G. Cravotto, D. Garella, E.C. Gaudino, F. Turci, S. Bertarione, G. Agostini, et al.,
Rapid purification/oxidation of multi-walled carbon nanotubes under 300
kHz-ultrasound and microwave irradiation, New J Chem 35 (4) (2011)
915e919, https://doi.org/10.1039/c0nj00892c.
[545] I. Pełech, U. Narkiewicz, A. Kaczmarek, A. Je˛ drzejewska, R. Pełech, Removal of
metal particles from carbon nanotubes using conventional and microwave
methods, Sep Purif Technol 136 (2014) 105e110, https://doi.org/10.1016/
j.seppur.2014.08.036.
[546] R. Pelalak, M. Baniadam, M. Maghrebi, Controllable purification, cutting and
unzipping of multi-walled carbon nanotubes with a microwave method,
Appl Phys A 111 (2012) 951e957, https://doi.org/10.1007/s00339-012-
7320-9.
[547] C. Wu, J. Li, G. Dong, L. Guan, Removal of ferromagnetic metals for the large-
scale purification of single-walled carbon nanotubes, J Phys Chem C 113 (9)
(2009) 3612e3616, https://doi.org/10.1021/jp810163u.
[548] Y. Wang, H. Shan, R.H. Hauge, M. Pasquali, R.E. Smalley, A highly selective,
one-pot purification method for single-walled carbon nanotubes, J Phys
Chem B 111 (6) (2007) 1249e1252, https://doi.org/10.1021/jp068229þ.
[549] J. Scho€nherr, J. Buchheim, P. Scholz, M. Stelter, Oxidation of carbon nano-
tubes with ozone and hydroxyl radicals, Carbon 111 (2017) 631e640,
https://doi.org/10.1016/j.carbon.2016.10.013.
[550] N. Karatepe, N. Yuca, Hydrogen adsorption on carbon nanotubes purified by
different methods, Int J Hydrogen Energy 36 (17) (2011) 11467e11473,
https://doi.org/10.1016/j.ijhydene.2011.01.128.
[551] R. Das, Carbon nanotube purification, in: Nanohybrid Catalyst Based on
Carbon Nanotube, Carbon Nanostructures, Springer, Cham, 2017, https://
doi.org/10.1007/978-3-319-58151-4_3.
[552] Y. Feng, H. Zhang, Y. Hou, T.P. McNicholas, D. Yuan, S. Yang, et al., Room
temperature purification of few-walled carbon nanotubes with high yield,
ACS Nano 2 (8) (2008) 1634e1638, https://doi.org/10.1021/nn800388g.
[553] M. Sanchez-Polo, U. von Gunten, J. Rivera-Utrilla, Efficiency of activated
carbon to transform ozone into *OH radicals: influence of operational pa-
rameters, Water Res 39 (14) (2005) 3189e3198, https://doi.org/10.1016/
j.watres.2005.05.026.
[554] S. Li, Y. Shang, W. Zhao, Y. Wang, X. Li, A. Cao, Efficient purification of single-
walled carbon nanotube fibers by instantaneous current injection and acid
washing, RSC Adv 6 (100) (2016) 97865e97872, https://doi.org/10.1039/
c6ra20967j.
[555] T.Q. Tran, R.J. Headrick, E.A. Bengio, S. Myo Myint, H. Khoshnevis, V. Jamali, et
al., Purification and dissolution of carbon nanotube fibers spun from the
floating catalyst method, ACS Appl Mater Interfaces 9 (42) (2017)
37112e37119, https://doi.org/10.1021/acsami.7b09287.
[556] P. Chungchamroenkit, S. Chavadej, U. Yanatatsaneejit, B. Kitiyanan, Residue
catalyst support removal and purification of carbon nanotubes by NaOH
leaching and froth flotation, Sep Purif Technol 60 (2) (2008) 206e214,
https://doi.org/10.1016/j.seppur.2007.08.009.
[557] S. Porro, S. Musso, M. Vinante, L. Vanzetti, M. Anderle, F. Trotta, et al., Pu-
rification of carbon nanotubes grown by thermal CVD, Physica E 37 (1e2)
(2007) 58e61, https://doi.org/10.1016/j.physe.2006.07.014.
[558] J. Liu, A.T. Harris, Microwave-assisted acid digestion of alumina-supported
carbon nanotubes, Sep Purif Technol 62 (3) (2008) 602e608, https://
doi.org/10.1016/j.seppur.2008.03.016.
[559] H. Rong, Z. Liu, Q. Wu, Y.-H. Lee, A facile and efficient gas phase process for
purifying single-walled carbon nanotubes, Curr Appl Phys 10 (4) (2010)
1231e1235, https://doi.org/10.1016/j.cap.2010.02.049.
[560] X.S. Zhang, L.W. Yang, H.T. Liu, M. Zu, Mechanical and electrical properties of
direct spun carbon nanotube fibers exposed to ultrahigh temperatures in
vacuum, J Nanosci Nanotechnol 18 (6) (2018) 4264e4269, https://doi.org/
10.1166/jnn.2018.15203.
[561] M. Endo, Y.A. Kim, T. Hayashi, K. Nishimura, T. Matusita, K. Miyashita, et al.,
Vapor-grown carbon fibers (VGCFs): basic properties and their battery ap-
plications, Carbon 39 (9) (2001) 1287e1297, https://doi.org/10.1016/S0008-
6223(00)00295-5.
[562] J.M. Lambert, P.M. Ajayan, P. Bernier, J.M. Planeix, V. Brotons, B. Coq, et al.,

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
Improving conditions towards isolating single-shell carbon nanotubes, Chem
Phys Lett 226 (3e4) (1994) 364e371, https://doi.org/10.1016/0009-
2614(94)00739-X.
[563] W. Huang, Y. Wang, G. Luo, F. Wei, 99.9% purity multi-walled carbon
nanotubes by vacuum high-temperature annealing, Carbon 41 (13) (2003)
2585e2590, https://doi.org/10.1016/S0008-6223(03)00330-0.
[564] E.F. Antunes, V.G. de Resende, U.A. Mengui, J.B.M. Cunha, E.J. Corat, M. Massi,
Analyses of residual iron in carbon nanotubes produced by camphor/ferro-
cene pyrolysis and purified by high temperature annealing, Appl Surf Sci 257
(18) (2011) 8038e8043, https://doi.org/10.1016/j.apsusc.2011.04.090.
[565] Y.A. Kim, H. Muramatsu, T. Hayashi, M. Endo, M. Terrones, M.S. Dresselhaus,
Thermal stability and structural changes of double-walled carbon nanotubes
by heat treatment, Chem Phys Lett 398 (1e3) (2004) 87e92, https://doi.org/
10.1016/j.cplett.2004.09.024.
[566] M. Yudasaka, H. Kataura, T. Ichihashi, L.C. Qin, S. Kar, S. Iijima, Diameter
enlargement of HiPco single-wall carbon nanotubes by heat treatment, Nano
Lett 1 (9) (2001) 487e489, https://doi.org/10.1021/nl010037x.
[567] M. Yudasaka, T. Ichihashi, D. Kasuya, H. Kataura, S. Iijima, Structure changes
of single-wall carbon nanotubes and single-wall carbon nanohorns caused
by heat treatment, Carbon 41 (6) (2003) 1273e1280, https://doi.org/
10.1016/S0008-6223(03)00076-9.
[568] K. Behler, S. Osswald, H. Ye, S. Dimovski, Y. Gogotsi, Effect of thermal
treatment on the structure of multi-walled carbon nanotubes, J Nanopart Res
8 (2006) 615e625, https://doi.org/10.1007/s11051-006-9113-6.
[569] R. Andrews, D. Jacques, D. Qian, E.C. Dickey, Purification and structural
annealing of multiwalled carbon nanotubes at graphitization temperatures,
Carbon 39 (11) (2001) 1681e1687, https://doi.org/10.1016/S0008-6223(00)
00301-8.
[570] J. Chen, A. Kuno, M. Matsuo, T. Tsukada, T. Tamura, K. Osato, et al., Removal of
entrapped iron compounds from isothermally treated catalytic chemical
vapor deposition derived multi-walled carbon nanotubes, Carbon 46 (3)
(2008) 391e396, https://doi.org/10.1016/j.carbon.2007.11.040.
[571] J. Chen, J.Y. Shan, T. Tsukada, F. Munekane, A. Kuno, M. Matsuo, et al., The
structural evolution of thin multi-walled carbon nanotubes during
isothermal annealing, Carbon 45 (2) (2007) 274e280, https://doi.org/
10.1016/j.carbon.2006.09.028.
[572] I. Srikanth, N. Padmavathi, P.S.R. Prasad, P. Ghosal, R.K. Jain,
C.H. Subrahmanyam, Effect of high-temperature heat treatment duration on
the purity and microstructure of MWCNTs, Bull Mater Sci 39 (2016) 41e46,
https://doi.org/10.1007/s12034-015-0891-2.
[573] S. Boncel, K.K.K. Koziol, Enhanced graphitization of c-CVD grown multi-wall
carbon nanotube arrays assisted by removal of encapsulated iron-based
phases under thermal treatment in argon, Appl Surf Sci 301 (2014)
488e491, https://doi.org/10.1016/j.apsusc.2014.02.108.
[574] V.L. Kuznetsov, K.V. Elumeeva, A.V. Ishchenko, N.Y. Beylina, A.A. Stepashkin,
S.I. Moseenkov, et al., Multi-walled carbon nanotubes with ppm level of
impurities, Physica Status Solidi (B) 247 (11e12) (2010) 2695e2699, https://
doi.org/10.1002/pssb.201000211.
[575] N. Jeong, Y.C. Park, J.H. Yoo, Preparation of highly pure and crystalline carbon
nanotubes and their infiltration by paraffin wax, Carbon 63 (2013) 240e252,
https://doi.org/10.1016/j.carbon.2013.06.077.
[576] A. Meyer-Plath, G. Orts-Gil, S. Petrov, F. Oleszak, H.-E. Maneck, I. Do€rfel, et al.,
Plasma-thermal purification and annealing of carbon nanotubes, Carbon 50
(10) (2012) 3934e3942, https://doi.org/10.1016/j.carbon.2012.04.049.
[577] C. Gupta, P.H. Maheshwari, D. Sachdev, A.K. Sahu, S.R. Dhakate, Highly pu-
rified CNTs: an exceedingly efficient catalyst support for PEM fuel cell, RSC
Adv 6 (38) (2016) 32258e32271, https://doi.org/10.1039/c5ra28029j.
[578] P.H. Maheshwari, R. Singh, R.B. Mathur, Effect of heat treatment on the
structure and stability of multiwalled carbon nanotubes produced by cata-
lytic chemical vapor deposition technique, Mater Chem Phys 134 (1) (2012)
412e416, https://doi.org/10.1016/j.matchemphys.2012.03.010.
[579] X.R. Ye, L.H. Chen, C. Wang, J.F. Aubuchon, I.C. Chen, A.I. Gapin, et al., Elec-
trochemical modification of vertically aligned carbon nanotube arrays, J Phys
Chem B 110 (26) (2006) 12938e12942, https://doi.org/10.1021/jp057507m.
[580] A. Heras, A. Colina, J. Lo
pez-Palacios, P. Ayala, J. Sainio, V. Ruiz, et al., Elec-
trochemical purification of carbon nanotube electrodes, Electrochem Com-
mun 11 (7) (2009) 1535e1538, https://doi.org/10.1016/
j.elecom.2009.05.052.
[581] X. Yang, M. Yang, H. Zhang, J. Zhao, X. Zhang, Q. Li, Electro-purification of
carbon nanotube networks without damaging the assembly structure and
crystallinity, Appl Surf Sci 442 (2018) 232e238, https://doi.org/10.1016/
j.apsusc.2018.02.169.
[582] S.M. Tan, A. Ambrosi, B. Khezri, R.D. Webster, M. Pumera, Towards electro-
chemical purification of chemically reduced graphene oxide from redox
accessible impurities, Phys Chem Chem Phys 16 (15) (2014) 7058e7065,
https://doi.org/10.1039/C4CP00371C.
[583] S. Ghosh, S.M. Bachilo, R.B. Weisman, Removing aggregates from single-
walled carbon nanotube samples by magnetic purification, J Phys Chem C
118 (8) (2014) 4489e4494, https://doi.org/10.1021/jp411941k.
[584] Y. Kim, D.E. Luzzi, Purification of pulsed laser synthesized single wall carbon
nanotubes by magnetic filtration, J Phys Chem B 109 (35) (2005)
16636e16643, https://doi.org/10.1021/jp0522359.
[585] J.H. Kang, J.K. Park, Magnetophoretic continuous purification of single-walled
carbon nanotubes from catalytic impurities in a microfluidic device, Small 3
(10) (2007) 1784e1791, https://doi.org/10.1002/smll.200700334.
841
[586] O.A. Gurova, V.E. Arhipov, V.O. Koroteev, T.Y. Guselnikova, I.P. Asanov,
O.V. Sedelnikova, et al., Purification of single-walled carbon nanotubes using
acid treatment and magnetic separation, Phys Status Solidi B 256 (9) (2019)
1800742, https://doi.org/10.1002/pssb.201800742.
[587] J.S. Wang, C.M. Wai, K. Shimizu, F. Cheng, J.J. Boeckl, B. Maruyama, et al.,
Purification of single-walled carbon nanotubes using a supercritical fluid
extraction method, J Phys Chem C 111 (35) (2007) 13007e13012, https://
doi.org/10.1021/jp073374o.
[588] M. Bertoncini, L.A.F. Coelho, I.O. Maciel, S.H. Pezzin, Purification of single-
wall carbon nanotubes by heat treatment and supercritical extraction,
Mater Res 14 (3) (2011) 380e383, https://doi.org/10.1590/S1516-
14392011005000051.
[589] B.H.R. Suryanto, T. Fang, S. Cheong, R.D. Tilley, C. Zhao, From the inside-out:
leached metal impurities in multiwall carbon nanotubes for purification or
electrocatalysis, J Mater Chem A 6 (11) (2018) 4686e4694, https://doi.org/
10.1039/c7ta11257b.
[590] A.J. Clancy, E.R. White, H.H. Tay, H.C. Yau, M.S.P. Shaffer, Systematic com-
parison of conventional and reductive single-walled carbon nanotube puri-
fications, Carbon 108 (2016) 423e432, https://doi.org/10.1016/
j.carbon.2016.07.034.
[591] S. Fogden, C.A. Howard, R.K. Heenan, N.T. Skipper, M.S. Shaffer, Scalable
method for the reductive dissolution, purification, and separation of single-
walled carbon nanotubes, ACS Nano 6 (1) (2012) 54e62, https://doi.org/
10.1021/nn2041494.
[592] C.A. Furtado, U.J. Kim, H.R. Gutierrez, L. Pan, E.C. Dickey, P.C. Eklund,
Debundling and dissolution of single-walled carbon nanotubes in amide
solvents, J Am Chem Soc 126 (19) (2004) 6095e6105, https://doi.org/
10.1021/ja039588a.
[593] X. Li, G. Yuan, A. Brown, A. Westwood, R. Brydson, B. Rand, The removal of
encapsulated catalyst particles from carbon nanotubes using molten salts,
Carbon 44 (9) (2006) 1699e1705, https://doi.org/10.1016/
j.carbon.2006.01.006.
[594] Y. Yan, S. Raychaudhuri, Highly Purified Carbon Nanotubes and Method of
Their Preparation, 2018. US9926200B1.
[595] X. Yang, Y. Wan, Y. Zheng, F. He, Z. Yu, J. Huang, et al., Surface functional
groups of carbon-based adsorbents and their roles in the removal of heavy
metals from aqueous solutions: a critical review, Chem Eng J 366 (2019)
608e621, https://doi.org/10.1016/j.cej.2019.02.119.
[596] I. Ali, A.A. Basheer, X.Y. Mbianda, A. Burakov, E. Galunin, I. Burakova, et al.,
Graphene based adsorbents for remediation of noxious pollutants from
wastewater, Environ Int 127 (2019) 160e180, https://doi.org/10.1016/
j.envint.2019.03.029.
[597] A. Dimiev, D.V. Kosynkin, L.B. Alemany, P. Chaguine, J.M. Tour, Pristine
graphite oxide, J Am Chem Soc 134 (5) (2012) 2815e2822, https://doi.org/
10.1021/ja211531y.
[598] W. Peng, H. Li, Y. Liu, S. Song, A review on heavy metal ions adsorption from
water by graphene oxide and its composites, J Mol Liq 230 (2017) 496e504,
https://doi.org/10.1016/j.molliq.2017.01.064.
[599] K. Klímova
, M. Pumera, J. Luxa, O. Jankovský, D. Sedmidubský, S. Mate jkov

a,
et al., Graphene oxide sorption capacity toward elements over the whole
periodic table: a comparative study, J Phys Chem C 120 (42) (2016)
24203e24212, https://doi.org/10.1021/acs.jpcc.6b08088.
[600] R.R. Amirov, J. Shayimova, Z. Nasirova, A. Solodov, A.M. Dimiev, Analysis of
competitive binding of several metal cations by graphene oxide reveals the
quantity and spatial distribution of carboxyl groups on its surface, Phys
Chem Chem Phys 20 (4) (2018) 2320e2329, https://doi.org/10.1039/
c7cp07055a.
[601] F.E. Sarac Oztuna, M.B. Yagci, U. Unal, First-row transition-metal cations
(Co2þ, Ni2þ, Mn2þ, Fe2þ) and graphene (oxide) composites: from structural
properties to electrochemical applications, Chem - Eur J 25 (12) (2019)
3131e3140, https://doi.org/10.1002/chem.201806309.
[602] X. Wang, P. Huang, L. Feng, M. He, S. Guo, G. Shen, et al., Green controllable
synthesis of silver nanomaterials on graphene oxide sheets via spontaneous
reduction, RSC Adv 2 (9) (2012) 3816e3822, https://doi.org/10.1039/
c2ra00008c.
[603] B.S. Kong, J. Geng, H.T. Jung, Layer-by-layer assembly of graphene and gold
nanoparticles by vacuum filtration and spontaneous reduction of gold ions,
Chem Commun 16 (2009) 2174e2176, https://doi.org/10.1039/b821920f.
[604] W. Yu, F. Lian, G. Cui, Z. Liu, N-doping effectively enhances the adsorption
capacity of biochar for heavy metal ions from aqueous solution, Chemo-
sphere 193 (2018) 8e16, https://doi.org/10.1016/
j.chemosphere.2017.10.134.
[605] Y.F. Jia, B. Xiao, K.M. Thomas, Adsorption of metal ions on nitrogen surface
functional groups in activated carbons, Langmuir 18 (2) (2002) 470e478,
https://doi.org/10.1021/la011161z.
[606] R.C. Atkins, Colorimetric determination of iron in vitamin supplement tab-
lets. A general chemistry experiment, J Chem Educ 52 (8) (1975) 550, https://
doi.org/10.1021/ed052p550.
[607] B. Choi, H. Yoon, I.-S. Park, J. Jang, Y.-E. Sung, Highly dispersed Pt nano-
particles on nitrogen-doped magnetic carbon nanoparticles and their
enhanced activity for methanol oxidation, Carbon 45 (13) (2007)
2496e2501, https://doi.org/10.1016/j.carbon.2007.08.028.
[608] R. Arrigo, M.E. Schuster, Z. Xie, Y. Yi, G. Wowsnick, L.L. Sun, et al., Nature of
the NePd interaction in nitrogen-doped carbon nanotube catalysts, ACS
Catal 5 (5) (2015) 2740e2753, https://doi.org/10.1021/acscatal.5b00094.
842
ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
[609] E. Castillejos, B. Bachiller-Baeza, E. Asedegbega-Nieto, A. Guerrero-Ruiz,
I. Rodríguez-Ramos, Selective 1,3-butadiene hydrogenation by gold nano-
particles deposited & precipitated onto nano-carbon materials, RSC Adv 5
(99) (2015) 81583e81598, https://doi.org/10.1039/c5ra17388d.
[610] T.R. Hupp, I.C. Lewis, J.M. Criscione, R.L. Reddy, C.F. Fulgenzi, D.J. Page, et al.,
Graphite, Artificial. Kirk-Othmer Encyclopedia of Chemical Technology, John
Wiley & Sons, Inc, 2003, pp. 713e771, https://doi.org/10.1002/
0471238961.0201110512052309.a01.pub2.
[611] R.S. Kalyoncu, H.A. Taylor Jr., Natural Graphite. Kirk-Othmer Encyclopedia of
Chemical Technology, John Wiley & Sons, Inc, 2014, pp. 1e21, https://
doi.org/10.1002/0471238961.1401202120012512.a01.pub3.
[612] A.H.R. Palser, Interlayer interactions in graphite and carbon nanotubes, Phys
Chem Chem Phys 1 (18) (1999) 4459e4464, https://doi.org/10.1039/
a905154f.
[613] S. Chehreh Chelgani, M. Rudolph, R. Kratzsch, D. Sandmann, J. Gutzmer,
A review of graphite beneficiation techniques, Miner Process Extr Metall Rev
37 (1) (2015) 58e68, https://doi.org/10.1080/08827508.2015.1115992.
[614] A.D. Jara, A. Betemariam, G. Woldetinsae, J.Y. Kim, Purification, application
and current market trend of natural graphite: a review, Int J Min Sci Technol
29 (5) (2019) 671e689, https://doi.org/10.1016/j.ijmst.2019.04.003.
[615] M. Wissler, Graphite and carbon powders for electrochemical applications,
J Power Sources 156 (2) (2006) 142e150, https://doi.org/10.1016/
j.jpowsour.2006.02.064.
[616] S.-M. Lee, D.-S. Kang, J.-S. Roh, Bulk graphite: materials and manufacturing
process, Carbon Lett 16 (3) (2015) 135e146, https://doi.org/10.5714/
cl.2015.16.3.135.
[617] W. Xie, Z. Wang, J. Kuang, H. Xu, S. Yi, Y. Deng, et al., Fixed carbon content
and reaction mechanism of natural microcrystalline graphite purified by
hydrochloric acid and sodium fluoride, Int J Miner Process 155 (2016)
45e54, https://doi.org/10.1016/j.minpro.2016.08.002.
[618] X.J. Lu, E. Forssberg, Preparation of high-purity and low-sulphur graphite
from Woxna fine graphite concentrate by alkali roasting, Miner Eng 15 (10)
(2002) 755e757, https://doi.org/10.1016/s0892-6875(02)00172-3.
[619] H. Wang, Q. Feng, X. Tang, K. Liu, Preparation of high-purity graphite from a
fine microcrystalline graphite concentrate: effect of alkali roasting pre-
treatment and acid leaching process, Sep Sci Technol 51 (14) (2016)
2465e2472, https://doi.org/10.1080/01496395.2016.1206933.
[620] H. Wang, Q. Feng, K. Liu, K. Zuo, X. Tang, A novel technique for microcrys-
talline graphite beneficiation based on alkali-acid leaching process, Sep Sci
Technol 53 (6) (2017) 982e989, https://doi.org/10.1080/
01496395.2017.1405986.
[621] A.E. Karu, M. Beer, Pyrolytic formation of highly crystalline graphite films,
J Appl Phys 37 (1966) 2179e2181, https://doi.org/10.1063/1.1708759.
[622] Y.S. Virgil’ev, Impurities in and serviceability of reactor graphite, At Energ 84
(1) (1998) 6e13, https://doi.org/10.1007/bf02430647.
[623] A.V. Bushuev, V.N. Zubarev, I.M. Proshin, Impurity composition and content
in graphite from commercial reactors, At Energ 92 (4) (2002) 331e335,
https://doi.org/10.1023/a:1016506110872.
[624] V.V. Goncharov, Graphite in nuclear reactors, J Nucl Energy 7 (1e2) (1958)
115e124, https://doi.org/10.1016/0891-3919(58)90243-2.
[625] A.V. Bushuev, A.F. Kozhin, V.N. Zubarev, T.B. Aleeva, E.V. Petrova,
E.M. Glagovskii, et al., Radioactive contamination of spent reactor graphite,
At Energ 117 (3) (2014) 196e200, https://doi.org/10.1007/s10512-014-
9910-4.
[626] J. Fachinger, W. von Lensa, T. Podruhzina, Decontamination of nuclear
graphite, Nucl Eng Des 238 (11) (2008) 3086e3091, https://doi.org/10.1016/
j.nucengdes.2008.02.010.
[627] K.N. Tran, A.J. Berkovich, A. Tomsett, S.K. Bhatia, Influence of sulfur and metal
microconstituents on the reactivity of carbon anodes, Energy Fuels 23 (4)
(2009) 1909e1924, https://doi.org/10.1021/ef8009519.
[628] E. Mahmoudi, W.L. Ang, C.Y. Ng, L.Y. Ng, A.W. Mohammad, A. Benamor,
Distinguishing characteristics and usability of graphene oxide based on
different sources of graphite feedstock, J Colloid Interface Sci 542 (2019)
429e440, https://doi.org/10.1016/j.jcis.2019.02.023.
[629] D.A. Jasim, N. Lozano, K. Kostarelos, Synthesis of few-layered, high-purity
graphene oxide sheets from different graphite sources for biology, 2D Mater
3 (1) (2016), https://doi.org/10.1088/2053-1583/3/1/014006, 014006.
[630] C.H. Wong, Z. Sofer, M. Pumera, Geographical and geological origin of natural
graphite heavily influence the electrical and electrochemical properties of
chemically modified graphenes, Chem - Eur J 21 (23) (2015) 8435e8440,
https://doi.org/10.1002/chem.201500116.
[631] S.A. Kazaryan, G.G. Kharisov, S.V. Litvinenko, V.I. Kogan, Self-discharge
related to iron ions and its effect on the parameters of HES PbO2rH2SO4rC
systems, J Electrochem Soc 154 (8) (2007), https://doi.org/10.1149/
1.2742335. A751-A9.
[632] S.A. Kazaryan, S.V. Litvinenko, G.G. Kharisov, Self-discharge of heterogeneous
electrochemical supercapacitor of PbO2rH2SO4rC related to manganese and
titanium ions, J Electrochem Soc 155 (6) (2008) A464, https://doi.org/
10.1149/1.2904456.
[633] H.A. Andreas, K. Lussier, A.M. Oickle, Effect of Fe-contamination on rate of
self-discharge in carbon-based aqueous electrochemical capacitors, J Power
Sources 187 (1) (2009) 275e283, https://doi.org/10.1016/
j.jpowsour.2008.10.096.
[634] X. Zeng, M. Li, D. Abd El-Hady, W. Alshitari, A.S. Al-Bogami, J. Lu, et al.,
Commercialization of lithium battery technologies for electric vehicles, Adv
Energy Mater 9 (27) (2019) 1900161, https://doi.org/10.1002/
aenm.201900161.
[635] T.H.N.G. Amaraweera, N.W.B. Balasooriya, H.W.M.A.C. Wijayasinghe,
A.N.B. Attanayake, B.E. Mellander, M.A.K.L. Dissanayake, Surface modification
of natural vein graphite for the anode application in Li-ion rechargeable
batteries, Ionics 24 (11) (2018) 3423e3429, https://doi.org/10.1007/s11581-
018-2523-5.
[636] L. Weimer, T. Braun, Av Hemdt, Design of a systematic value chain for
lithium-ion batteries from the raw material perspective, Resour Policy 64
(2019) 101473, https://doi.org/10.1016/j.resourpol.2019.101473.
[637] H. Zhao, J. Ren, X. He, J. Li, C. Jiang, C. Wan, Purification and carbon-film-
coating of natural graphite as anode materials for Li-ion batteries, Electro-
chim Acta 52 (19) (2007) 6006e6011, https://doi.org/10.1016/
j.electacta.2007.03.050.
[638] K. Zaghib, X. Song, A. Guerfi, R. Rioux, K. Kinoshita, Purification process of
natural graphite as anode for Li-ion batteries: chemical versus thermal,
J Power Sources 119e121 (2003) 8e15, https://doi.org/10.1016/s0378-
7753(03)00116-2.
[639] K. Adham, G. Bowes, Natural graphite purification through chlorination in
fluidized bed reactor, in: B. Dawis, et al. (Eds.), Extraction 2018, the Minerals,
Metals & Materials Series, Springer, Cham, 2018, https://doi.org/10.1007/
978-3-319-95022-8_211.
[640] S. Jiao, H. Lei, J. Tu, J. Zhu, J. Wang, X. Mao, An industrialized prototype of the
rechargeable Al/AlCl3-[EMIm]Cl/graphite battery and recycling of the
graphitic cathode into graphene, Carbon 109 (2016) 276e281, https://
doi.org/10.1016/j.carbon.2016.08.027.
[641] S. Wang, K.V. Kravchyk, F. Krumeich, M.V. Kovalenko, Kish graphite flakes as
a cathode material for an aluminum chloride-graphite battery, ACS Appl
Mater Interfaces 9 (34) (2017) 28478e28485, https://doi.org/10.1021/
acsami.7b07499.
[642] I.-Y. Jeon, S.-H. Shin, S.-M. Jung, H.-J. Choi, J. Xu, J.-B. Baek, One-pot purifi-
cation and iodination of waste kish graphite into high-quality electro-
catalyst, Part Part Syst Charact 34 (9) (2017) 1600426, https://doi.org/
10.1002/ppsc.201600426.
[643] J. Zhang, X. Li, D. Song, Y. Miao, J. Song, L. Zhang, Effective regeneration of
anode material recycled from scrapped Li-ion batteries, J Power Sources 390
(2018) 38e44, https://doi.org/10.1016/j.jpowsour.2018.04.039.
[644] I.S. Ike, I. Sigalas, S. Iyuke, The effects of self-discharge on the performance of
asymmetric/hybrid electrochemical capacitors with redox-active electro-
lytes: insights from modeling and simulation, J Electron Mater 47 (1) (2018)
470e492, https://doi.org/10.1007/s11664-017-5796-y.
[645] J.P. Rourke, P.A. Pandey, J.J. Moore, M. Bates, I.A. Kinloch, R.J. Young, et al., The
real graphene oxide revealed: stripping the oxidative debris from the
graphene-like sheets, Angew Chem Int Ed 50 (14) (2011) 3173e3177,
https://doi.org/10.1002/anie.201007520.
[646] G. Ceriotti, A.Y. Romanchuk, A.S. Slesarev, S.N. Kalmykov, Rapid method for
the purification of graphene oxide, RSC Adv 5 (62) (2015) 50365e50371,
https://doi.org/10.1039/c5ra07604h.
[647] W. Tan, Y. Liu, L. Liu, R. Xing, G. Zhu, Optimization of operating conditions in
the purification of graphite oxide dispersions, Korean J Chem Eng 33 (11)
(2016) 3251e3257, https://doi.org/10.1007/s11814-016-0164-9.
[648] F.J. To€ lle, K. Gamp, R. Mülhaupt, Scale-up and purification of graphite oxide
as intermediate for functionalized graphene, Carbon 75 (2014) 432e442,
https://doi.org/10.1016/j.carbon.2014.04.022.
[649] A.T. Abdel-Motagaly, W.M.A. El Rouby, S.I. El-Dek, I.M. El-Sherbiny,
A.A. Farghali, Fast technique for the purification of as-prepared graphene
oxide suspension, Diamond Relat Mater 86 (2018) 20e28, https://doi.org/
10.1016/j.diamond.2018.04.006.
[650] P. Bhunia, M. Kumar, S. De, Rapid and efficient removal of ionic impurities
from graphene oxide through hollow fiber diafiltration, Sep Purif Technol
209 (2019) 103e111, https://doi.org/10.1016/j.seppur.2018.07.025.
[651] P. Bhunia, M. Kumar, S. De, Fast purification of graphene oxide solution by
continuous counter current hollow fibre dialysis: a step towards large scale
production, Can J Chem Eng 97 (S1) (2019) 1596e1604, https://doi.org/
10.1002/cjce.23380.
[652] B.D. Keller, N. Ferralis, J.C. Grossman, Rethinking coal: thin films of solution
processed natural carbon nanoparticles for electronic devices, Nano Lett 16
(5) (2016) 2951e2957, https://doi.org/10.1021/acs.nanolett.5b04735.
[653] V.C. Hoang, M. Hassan, V.G. Gomes, Coal derived carbon nanomaterials e
recent advances in synthesis and applications, Appl Mater Today 12 (2018)
342e358, https://doi.org/10.1016/j.apmt.2018.06.007.
[654] R. Ye, C. Xiang, J. Lin, Z. Peng, K. Huang, Z. Yan, et al., Coal as an abundant
source of graphene quantum dots, Nat Commun 4 (2013) 2943, https://
doi.org/10.1038/ncomms3943.
[655] J.P. Mathews, A.L. Chaffee, The molecular representations of coal e a review,
Fuel 96 (2012) 1e14, https://doi.org/10.1016/j.fuel.2011.11.025.
[656] C.E. Burgess-Clifford, D.L. Narayanan, D.T. Van Essendelft, P. Jain, A. Sakti,
A.D. Lueking, The effect of calcination on reactive milling of anthracite as
potential precursor for graphite production, Fuel Process Technol 90 (12)
(2009) 1515e1523, https://doi.org/10.1016/j.fuproc.2009.07.017.
[657] T. Qiu, J.-G. Yang, X.-J. Bai, Preparation of coal-based graphite with different
microstructures by adjusting the content of ash and volatile matter in raw
coal, Energy Sources, Part A (2019) 1e8, https://doi.org/10.1080/
15567036.2019.1604900.
[658] M.W. Ryberg, M. Owsianiak, A. Laurent, M.Z. Hauschild, Power generation

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
from chemically cleaned coals: do environmental benefits of firing cleaner
coal outweigh environmental burden of cleaning? Energy Environ Sci 8 (8)
(2015) 2435e2447, https://doi.org/10.1039/c5ee01799h.
[659] M. Dudek, P. Tomczyk, R. Socha, M. Hamaguchi, Use of ash-free “Hyper-coal”
as a fuel for a direct carbon fuel cell with solid oxide electrolyte, Int J
Hydrogen Energy 39 (23) (2014) 12386e12394, https://doi.org/10.1016/
j.ijhydene.2014.04.057.
[660] M. Rahman, D. Pudasainee, R. Gupta, Review on chemical upgrading of coal:
production processes, potential applications and recent developments, Fuel
Process Technol 158 (2017) 35e56, https://doi.org/10.1016/
j.fuproc.2016.12.010.
[661] N. Wijaya, L. Zhang, A critical review of coal demineralization and its
implication on understanding the speciation of organically bound metals and
submicrometer mineral grains in coal, Energy Fuels 25 (1) (2011) 1e16,
https://doi.org/10.1021/ef1008192.
[662] K.M. Steel, J. Besida, T.A. O’Donnell, D.G. Wood, Production of ultra clean
coal: part IIdionic equilibria in solution when mineral matter from black
coal is treated with aqueous hydrofluoric acid, Fuel Process Technol 70 (3)
(2001) 193e219, https://doi.org/10.1016/s0378-3820(01)00173-4.
[663] K.M. Steel, J.W. Patrick, The production of ultra clean coal by chemical
demineralisation, Fuel 80 (14) (2001) 2019e2023, https://doi.org/10.1016/
S0016-2361(01)00092-8.
[664] S.K. Behera, S. Chakraborty, B.C. Meikap, Chemical demineralization of high
ash Indian coal by using alkali and acid solutions, Fuel 196 (2017) 102e109,
https://doi.org/10.1016/j.fuel.2017.01.088.
[665] K. Renganathan, J.W. Zondlo, E.A. Mintz, P. Kneisl, A.H. Stiller, Preparation of
an ultra-low ash coal extract under mild conditions, Fuel Process Technol 18
(3) (1988) 273e278, https://doi.org/10.1016/0378-3820(88)90051-3.
[666] Y. Hernandez, V. Nicolosi, M. Lotya, F.M. Blighe, Z. Sun, S. De, et al., High-yield
production of graphene by liquid-phase exfoliation of graphite, Nat Nano-
technol 3 (9) (2008) 563e568, https://doi.org/10.1038/nnano.2008.215.
[667] A.C. Jenifer, P. Sharon, A. Prakash, P.C. Sande, A review of the unconventional
methods used for the demetallization of petroleum fractions over the past
decade, Energy Fuels 29 (12) (2015) 7743e7752, https://doi.org/10.1021/
acs.energyfuels.5b00826.
[668] J.T. Miller, R.B. Fisher, A.M.J. van der Eerden, D.C. Koningsberger, Structural
determination by XAFS spectroscopy of non-porphyrin nickel and vanadium
in Maya residuum, hydrocracked residuum, and toluene-insoluble solid,
Energy Fuels 13 (3) (1999) 719e727, https://doi.org/10.1021/ef9802328.
[669] M.F. Ali, S. Abbas, A review of methods for the demetallization of residual
fuel oils, Fuel Process Technol 87 (7) (2006) 573e584, https://doi.org/
10.1016/j.fuproc.2006.03.001.
[670] R.N. Magomedov, A.Z. Popova, T.A. Maryutina, K.M. Kadiev, S.N. Khadzhiev,
Current status and prospects of demetallization of heavy petroleum feed-
stock (review), Pet Chem 55 (6) (2015) 423e443, https://doi.org/10.1134/
s0965544115060092.
[671] D.K. Lavallee, Complexation and demetalation reactions of porphyrins,
Comments Inorg Chem 5 (3) (1986) 155e174, https://doi.org/10.1080/
02603598608072281.
[672] J. Reynolds, Nickel in petroleum refining, Pet Sci Technol 19 (7e8) (2001)
979e1007, https://doi.org/10.1081/lft-100106915.
[673] G.H.C. Prado, A. de Klerk, Demetalation of metallophthalocyanines by mild
halogenation without disrupting the tetrapyrrole macrocycle, Fuel 161
(2015) 43e48, https://doi.org/10.1016/j.fuel.2015.08.013.
[674] L. Jiao, H. Yan, Y. Wu, W. Gu, C. Zhu, D. Du, et al., When nanozymes meet
single-atom catalysis, Angew Chem Int Ed 59 (7) (2020) 2565e2576, https://
doi.org/10.1002/anie.201905645.
[675] I. Yruela, Transition metals in plant photosynthesis, Metallomics 5 (9) (2013)
1090e1109, https://doi.org/10.1039/c3mt00086a.
[676] L.P. Ma, W. Ren, H.M. Cheng, Transfer methods of graphene from metal
substrates: a review, Small Methods 3 (7) (2019) 1900049, https://doi.org/
10.1002/smtd.201900049.
[677] S. Bhaviripudi, X. Jia, M.S. Dresselhaus, J. Kong, Role of kinetic factors in
chemical vapor deposition synthesis of uniform large area graphene using
copper catalyst, Nano Lett 10 (10) (2010) 4128e4133, https://doi.org/
10.1021/nl102355e.
[678] G. Lupina, J. Kitzmann, I. Costina, M. Lukosius, C. Wenger, A. Wolff, et al.,
Residual metallic contamination of transferred chemical vapor deposited
graphene, ACS Nano 9 (5) (2015) 4776e4785, https://doi.org/10.1021/
acsnano.5b01261.
[679] X. Liang, B.A. Sperling, I. Calizo, G. Cheng, C.A. Hacker, Q. Zhang, et al., Toward
clean and crackless transfer of graphene, ACS Nano 5 (11) (2011)
9144e9153, https://doi.org/10.1021/nn203377t.
[680] J. Ng, Y.-H. Xie, Source identification and method for drastic reduction of Fe
contamination on wet transferred graphene, Thin Solid Films 639 (2017)
36e41, https://doi.org/10.1016/j.tsf.2017.08.017.
[681] Z.T. Wu, W.W. Zhao, W.Y. Chen, J. Jiang, H.Y. Nan, X.T. Guo, et al., The in-
fluence of chemical solvents on the properties of CVD graphene, J Raman
Spectrosc 46 (1) (2015) 21e24, https://doi.org/10.1002/jrs.4582.
[682] M. Wang, E.H. Yang, R. Vajtai, J. Kono, P.M. Ajayan, Effects of etchants in the
transfer of chemical vapor deposited graphene, J Appl Phys 123 (2018)
195103, https://doi.org/10.1063/1.5009253.
[683] A. Ambrosi, M. Pumera, The CVD graphene transfer procedure introduces
metallic impurities which alter the graphene electrochemical properties,
Nanoscale 6 (1) (2014) 472e476, https://doi.org/10.1039/c3nr05230c.
843
[684] C.H.A. Wong, M. Pumera, Electrochemical delamination and chemical
etching of chemical vapor deposition graphene: contrasting properties,
J Phys Chem C 120 (8) (2016) 4682e4690, https://doi.org/10.1021/
acs.jpcc.6b00329.
[685] R.M. Iost, F.N. Crespilho, L. Zuccaro, H.K. Yu, A.M. Wodtke, K. Kern, et al.,
Enhancing the electrochemical and electronic performance of CVD-grown
graphene by minimizing trace metal impurities, ChemElectroChem 1 (12)
(2014) 2070e2074, https://doi.org/10.1002/celc.201402325.
[686] L. Gao, W. Ren, H. Xu, L. Jin, Z. Wang, T. Ma, et al., Repeated growth and
bubbling transfer of graphene with millimetre-size single-crystal grains
using platinum, Nat Commun 3 (2012) 699, https://doi.org/10.1038/
ncomms1702.
[687] L. Lin, J. Zhang, H. Su, J. Li, L. Sun, Z. Wang, et al., Towards super-clean gra-
phene, Nat Commun 10 (2019) 1912, https://doi.org/10.1038/s41467-019-
09565-4.
[688] Y.C. Lin, C.C. Lu, C.H. Yeh, C. Jin, K. Suenaga, P.W. Chiu, Graphene annealing:
how clean can it be? Nano Lett 12 (1) (2012) 414e419, https://doi.org/
10.1021/nl203733r.
[689] L.H. Karlsson, J. Birch, A. Mockute, A.S. Ingason, H.Q. Ta, M.H. Rummeli, et al.,
Residue reduction and intersurface interaction on single graphene sheets,
Carbon 100 (2016) 345e350, https://doi.org/10.1016/j.carbon.2016.01.007.
[690] J. Zhang, K. Jia, L. Lin, W. Zhao, H.T. Quang, L. Sun, et al., Large-area synthesis
of superclean graphene via selective etching of amorphous carbon with
carbon dioxide, Angew Chem Int Ed 58 (41) (2019) 14446e14451, https://
doi.org/10.1002/anie.201905672.
[691] T. Yasunishi, Y. Takabayashi, S. Kishimoto, R. Kitaura, H. Shinohara, Y. Ohno,
Origin of residual particles on transferred graphene grown by CVD, Jpn J Appl
Phys 55 (2016), https://doi.org/10.7567/jjap.55.080305, 080305.
[692] N. Lisi, T. Dikonimos, F. Buonocore, M. Pittori, R. Mazzaro, R. Rizzoli, et al.,
Contamination-free graphene by chemical vapor deposition in quartz fur-
naces, Sci Rep 7 (2017) 9927, https://doi.org/10.1038/s41598-017-09811-z.
[693] S. Al-Kamiyani, T. Mohiuddin, Improved control in elimination of white
impurities on graphene by chemical vapor deposition (CVD), AIP Adv 8
(2018) 125325, https://doi.org/10.1063/1.5051693.
[694] A.T. Murdock, C.D. van Engers, J. Britton, V. Babenko, S.S. Meysami, H. Bishop,
et al., Targeted removal of copper foil surface impurities for improved syn-
thesis of CVD graphene, Carbon 122 (2017) 207e216, https://doi.org/
10.1016/j.carbon.2017.06.075.
[695] H. Jeong, W.-T. Hwang, Y. Song, J.-K. Kim, Y. Kim, J. Hihath, et al., Highly
uniform monolayer graphene synthesis via a facile pretreatment of copper
catalyst substrates using an ammonium persulfate solution, RSC Adv 9 (36)
(2019) 20871e20878, https://doi.org/10.1039/c9ra02689d.
[696] S.M. Kim, A. Hsu, Y.H. Lee, M. Dresselhaus, T. Palacios, K.K. Kim, et al., The
effect of copper pre-cleaning on graphene synthesis, Nanotechnology 24 (36)
(2013) 365602, https://doi.org/10.1088/0957-4484/24/36/365602.
[697] D.T. Nguyen, W.Y. Chiang, Y.H. Su, M. Hofmann, Y.P. Hsieh, Solid-diffusion-
facilitated cleaning of copper foil improves the quality of CVD graphene, Sci
Rep 9 (1) (2019) 257, https://doi.org/10.1038/s41598-018-36390-4.
[698] P. Braeuninger-Weimer, B. Brennan, A.J. Pollard, S. Hofmann, Understanding
and controlling Cu-catalyzed graphene nucleation: the role of impurities,
roughness, and oxygen scavenging, Chem Mater 28 (24) (2016) 8905e8915,
https://doi.org/10.1021/acs.chemmater.6b03241.
[699] R.J. Toh, M. Pumera, Metallic impurities availability in reduced graphene is
greatly enhanced by its ultrasonication, Faraday Discuss 164 (2013)
275e282, https://doi.org/10.1039/c3fd00005b.
[700] C.K. Chua, Z. Sofer, B. Khezri, R.D. Webster, M. Pumera, Ball-milled sulfur-
doped graphene materials contain metallic impurities originating from
ball-milling apparatus: their influence on the catalytic properties, Phys Chem
Chem Phys 18 (27) (2016) 17875e17880, https://doi.org/10.1039/
c6cp03004a.
[701] D.V. Badami, Graphitization of a-silicon carbide, Nature 193 (4815) (1962)
569e570, https://doi.org/10.1038/193569a0.
[702] M. Kusunoki, M. Rokkaku, T. Suzuki, Epitaxial carbon nanotube film self-
organized by sublimation decomposition of silicon carbide, Appl Phys Lett
71 (18) (1997) 2620e2622, https://doi.org/10.1063/1.120158.
[703] M. Cheng, B.-W. Wang, P.-X. Hou, J.-C. Li, F. Zhang, J. Luan, et al., Selective
growth of semiconducting single-wall carbon nanotubes using SiC as a
catalyst, Carbon 135 (2018) 195e201, https://doi.org/10.1016/
j.carbon.2018.04.047.
[704] J.J. Schneider, N.I. Maksimova, J. Engstler, R. Joshi, R. Schierholz, R. Feile,
Catalyst free growth of a carbon nanotubeealumina composite structure,
Inorg Chim Acta 361 (6) (2008) 1770e1778, https://doi.org/10.1016/
j.ica.2006.10.025.
[705] M.H. Rümmeli, C. Kramberger, A. Grüneis, P. Ayala, T. Gemming, B. Büchner,
et al., On the graphitization nature of oxides for the formation of carbon
nanostructures, Chem Mater 19 (17) (2007) 4105e4107, https://doi.org/
10.1021/cm0712220.
[706] A. Hirsch, Growth of single-walled carbon nanotubes without a metal cata-
lyst - a surprising discovery, Angew Chem Int Ed 48 (30) (2009) 5403e5404,
https://doi.org/10.1002/anie.200901980.
[707] B. Liu, W. Ren, L. Gao, S. Li, S. Pei, C. Liu, et al., Metal-catalyst-free growth of
single-walled carbon nanotubes, J Am Chem Soc 131 (6) (2009) 2082e2083,
https://doi.org/10.1021/ja8093907.
[708] S. Huang, Q. Cai, J. Chen, Y. Qian, L. Zhang, Metal-catalyst-free growth of
single-walled carbon nanotubes on substrates, J Am Chem Soc 131 (6) (2009)
844
ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
2094e2095, https://doi.org/10.1021/ja809635s.
[709] A. Bachmatiuk, F. Borrnert, M. Grobosch, F. Schaffel, U. Wolff, A. Scott, et al.,
Investigating the graphitization mechanism of SiO2 nanoparticles in chem-
ical vapor deposition, ACS Nano 3 (12) (2009) 4098e4104, https://doi.org/
10.1021/nn9009278.
[710] H. Liu, D. Takagi, S. Chiashi, Y. Homma, The growth of single-walled carbon
nanotubes on a silica substrate without using a metal catalyst, Carbon 48 (1)
(2010) 114e122, https://doi.org/10.1016/j.carbon.2009.08.039.
[711] L. Zhang, D.M. Sun, P.X. Hou, C. Liu, T. Liu, J. Wen, et al., Selective growth of
metal-free metallic and semiconducting single-wall carbon nanotubes, Adv
Mater 29 (32) (2017) 1605719, https://doi.org/10.1002/adma.201605719.
[712] X. Xu, S. Huang, Y. Hu, J. Lu, Z. Yang, Continuous synthesis of carbon nano-
tubes using a metal-free catalyst by CVD, Mater Chem Phys 133 (1) (2012)
95e102, https://doi.org/10.1016/j.matchemphys.2011.12.059.
[713] A. Khan, S.M. Islam, S. Ahmed, R.R. Kumar, M.R. Habib, K. Huang, et al., Direct
CVD growth of graphene on technologically important dielectric and semi-
conducting substrates, Adv Sci 5 (11) (2018) 1800050, https://doi.org/
10.1002/advs.201800050.
[714] J.H. Lee, S.G. Kang, H.S. Jang, J.Y. Moon, D. Whang, Graphene on group-IV
elementary semiconductors: the direct growth approach and its applica-
tions, Adv Mater 31 (34) (2019) 1803469, https://doi.org/10.1002/
adma.201803469.
[715] G. Hong, Q.-H. Wu, J. Ren, S.-T. Lee, Mechanism of non-metal catalytic
growth of graphene on silicon, Appl Phys Lett 100 (23) (2012) 231604,
https://doi.org/10.1063/1.4726114.
[716] L. Tai, D. Zhu, X. Liu, T. Yang, L. Wang, R. Wang, et al., Direct growth of
graphene on silicon by metal-free chemical vapor deposition, Nano-Micro
Lett 10 (2018) 20, https://doi.org/10.1007/s40820-017-0173-1.
[717] J.H. Lee, E.K. Lee, W.J. Joo, Y. Jang, B.S. Kim, J.Y. Lim, et al., Wafer-scale growth
of single-crystal monolayer graphene on reusable hydrogen-terminated
germanium, Science 344 (6181) (2014) 286e289, https://doi.org/10.1126/
science.1252268.
[718] Y. Ueda, J. Yamada, T. Ono, T. Maruyama, S. Naritsuka, Crystal orientation
effects of sapphire substrate on graphene direct growth by metal catalyst-
free low-pressure CVD, Appl Phys Lett 115 (2019), https://doi.org/10.1063/
1.5098806, 013103.
[719] N. Muradov, F. Smith, A. T-Raissi, Catalytic activity of carbons for methane
decomposition reaction, Catal Today 102e103 (2005) 225e233, https://
doi.org/10.1016/j.cattod.2005.02.018.
[720] C.-H. Tu, C.-H. Wu, C.-H. Chen, Y.-C. Li, S.-T. Wang, Y.-C. Chen, et al., Direct
growth of hollow carbon nanorods on porous graphenic carbon film without
catalysts, Carbon 84 (2015) 272e279, https://doi.org/10.1016/
j.carbon.2014.11.059.
[721] J.-H. Lin, C.-S. Chen, H.-L. Ma, C.-W. Chang, C.-Y. Hsu, H.-W. Chen, Self-
assembling of multi-walled carbon nanotubes on a porous carbon surface by
catalyst-free chemical vapor deposition, Carbon 46 (12) (2008) 1619e1623,
https://doi.org/10.1016/j.carbon.2008.06.050.
[722] J.H. Lin, C.S. Chen, M.H. Rümmeli, A. Bachmatiuk, Z.Y. Zeng, H.L. Ma, et al.,
Growth of carbon nanotubes catalyzed by defect-rich graphite surfaces,
Chem Mater 23 (7) (2011) 1637e1639, https://doi.org/10.1021/cm103526s.
[723] J.K. Seo, W.S. Choi, H.D. Kim, J.H. Lee, E.C. Choi, H.J. Kim, et al., Growth of
metal-free carbon nanotubes on glass substrate with an amorphous carbon
catalyst layer, J Nanosci Nanotechnol 11 (12) (2011) 11032e11036, https://
doi.org/10.1166/jnn.2011.4022.
[724] D. Takagi, Y. Kobayashi, Y. Homma, Carbon nanotube growth from diamond,
J Am Chem Soc 131 (20) (2009) 6922e6923, https://doi.org/10.1021/
ja901295j.
[725] X. Yu, J. Zhang, W. Choi, J.Y. Choi, J.M. Kim, L. Gan, et al., Cap formation
engineering: from opened C60 to single-walled carbon nanotubes, Nano Lett
10 (9) (2010) 3343e3349, https://doi.org/10.1021/nl1010178.
[726] Y. Yao, C. Feng, J. Zhang, Z. Liu, Cloning" of single-walled carbon nanotubes
via open-end growth mechanism, Nano Lett 9 (4) (2009) 1673e1677,
https://doi.org/10.1021/nl900207v.
[727] J. Liu, C. Wang, X. Tu, B. Liu, L. Chen, M. Zheng, et al., Chirality-controlled
synthesis of single-wall carbon nanotubes using vapor-phase epitaxy, Nat
Commun 3 (2012) 1199, https://doi.org/10.1038/ncomms2205.
[728] X. Xu, C. Yang, Z. Yang, K. Yang, S. Huang, Carbon nanotube growth from
alkali metal salt nanoparticles, Carbon 80 (2014) 490e495, https://doi.org/
10.1016/j.carbon.2014.08.088.
[729] J. Xu, X. Qi, Q. Hu, Y. Jiang, W. Zhong, Y. Du, Fabrication, characterization,
purification and photoluminescence properties of carbon nanomaterials over
water-soluble alkali salts, Mater Res Bull 74 (2016) 218e225, https://doi.org/
10.1016/j.materresbull.2015.10.045.
[730] X. Qi, Q. Ding, W. Zhong, C.-T. Au, Y. Du, Controllable synthesis and purifi-
cation of carbon nanofibers and nanocoils over water-soluble NaNO3, Carbon
56 (2013) 383e385, https://doi.org/10.1016/j.carbon.2012.12.009.
[731] Q. Ding, X. Song, X. Yao, X. Qi, C.T. Au, W. Zhong, et al., Large-scale and
controllable synthesis of metal-free nitrogen-doped carbon nanofibers and
nanocoils over water-soluble Na2CO3, Nanoscale Res Lett 8 (2013) 545,
https://doi.org/10.1186/1556-276X-8-545.
[732] X. Qi, J. Xu, Q. Hu, Y. Deng, R. Xie, Y. Jiang, et al., Metal-free carbon nano-
tubes: synthesis, and enhanced intrinsic microwave absorption properties,
Sci Rep 6 (2016) 28310, https://doi.org/10.1038/srep28310.
[733] H.L. Poh, Z. Sofer, J. Luxa, M. Pumera, Transition metal-depleted graphenes
for electrochemical applications via reduction of CO2 by lithium, Small 10 (8)
(2014) 1529e1535, https://doi.org/10.1002/smll.201303002.
[734] Y. Segawa, A. Yagi, K. Matsui, K. Itami, Design and synthesis of carbon
nanotube segments, Angew Chem Int Ed 55 (17) (2016) 5136e5158, https://
doi.org/10.1002/anie.201508384.
[735] J. Wu, W. Pisula, K. Mullen, Graphenes as potential material for electronics,
Chem Rev 107 (3) (2007) 718e747, https://doi.org/10.1021/cr068010r.
[736] E.H. Fort, P.M. Donovan, L.T. Scott, Diels-Alder reactivity of polycyclic aro-
matic hydrocarbon bay regions: implications for metal-free growth of single-
chirality carbon nanotubes, J Am Chem Soc 131 (44) (2009) 16006e16007,
https://doi.org/10.1021/ja907802g.
[737] B. Liu, J. Liu, H.B. Li, R. Bhola, E.A. Jackson, L.T. Scott, et al., Nearly exclusive
growth of small diameter semiconducting single-wall carbon nanotubes
from organic chemistry synthetic end-cap molecules, Nano Lett 15 (1) (2015)
586e595, https://doi.org/10.1021/nl504066f.
[738] L.-L. Tan, W.-J. Ong, S.-P. Chai, A.R. Mohamed, Growth of carbon nanotubes
over non-metallic based catalysts: a review on the recent developments,
Catal Today 217 (2013) 1e12, https://doi.org/10.1016/j.cattod.2012.10.023.
[739] M. Terrones, A.R. Botello-Me
ndez, J. Campos-Delgado, F. Lo
pez-Urías,
Y.I. Vega-Cantú, F.J. Rodríguez-Macías, et al., Graphene and graphite nano-
ribbons: morphology, properties, synthesis, defects and applications, Nano
Today 5 (4) (2010) 351e372, https://doi.org/10.1016/j.nantod.2010.06.010.
[740] M.E. Birch, B.K. Ku, D.E. Evans, T.A. Ruda-Eberenz, Exposure and emissions
monitoring during carbon nanofiber production - part I: elemental carbon
and iron-soot aerosols, Ann Occup Hyg 55 (9) (2011) 1016e1036, https://
doi.org/10.1093/annhyg/mer073.
[741] P.E. Rasmussen, I. Jayawardene, H.D. Gardner, M. Che
nier, C. Levesque, J. Niu,
Metal impurities provide useful tracers for identifying exposures to airborne
single-wall carbon nanotubes released from work-related processes, J Phys
Conf Ser 429 (2013), https://doi.org/10.1088/1742-6596/429/1/012007,
012007.
[742] P.E. Rasmussen, M.L. Avramescu, I. Jayawardene, H.D. Gardner, Detection of
carbon nanotubes in indoor workplaces using elemental impurities, Environ
Sci Technol 49 (21) (2015) 12888e12896, https://doi.org/10.1021/
acs.est.5b02578.
[743] M.L. Avramescu, P.E. Rasmussen, M. Chenier, Determination of metal im-
purities in carbon nanotubes sampled using surface wipes, J Anal Methods
Chem 2016 (2016) 3834292, https://doi.org/10.1155/2016/3834292.
[744] A.D. Maynard, P.A. Baron, M. Foley, A.A. Shvedova, E.R. Kisin, V. Castranova,
Exposure to carbon nanotube material: aerosol release during the handling
of unrefined single-walled carbon nanotube material, J Toxicol Environ
Health, Part A 67 (1) (2004) 87e107, https://doi.org/10.1080/
15287390490253688.
[745] T. Nosaka, R.S. Lankone, Y. Bi, D.H. Fairbrother, P. Westerhoff, P. Herckes,
Quantification of carbon nanotubes in polymer composites, Anal Methods 10
(9) (2018) 1032e1037, https://doi.org/10.1039/c7ay02654d.
[746] N. Kato, T. Nagaya, Y. Matsui, M. Yoneda, Exposure assessment of carbon
nanotubes at pilot factory focusing on quantitative determination of catalytic
metals, J Occup Health 59 (6) (2017) 521e528, https://doi.org/10.1539/
joh.17-0002-OA.
[747] W. Wohlleben, C. Kingston, J. Carter, E. Sahle-Demessie, S. Vazquez-Campos,
B. Acrey, et al., NanoRelease: pilot interlaboratory comparison of a weath-
ering protocol applied to resilient and labile polymers with and without
embedded carbon nanotubes, Carbon 113 (2017) 346e360, https://doi.org/
10.1016/j.carbon.2016.11.011.
[748] P.C. Tromp, E. Kuijpers, C. Bekker, L. Godderis, Q. Lan, A.D. Jedynska, et al.,
A new approach combining analytical methods for workplace exposure
assessment of inhalable multi-walled carbon nanotubes, Ann Work Expo-
sures Health 61 (7) (2017) 759e772, https://doi.org/10.1093/annweh/
wxx053.
[749] R.B. Reed, D.G. Goodwin, K.L. Marsh, S.S. Capracotta, C.P. Higgins,
D.H. Fairbrother, et al., Detection of single walled carbon nanotubes by
monitoring embedded metals, Environ Sci: Processes Impacts 15 (1) (2013)
204e213, https://doi.org/10.1039/c2em30717k.
[750] J. Wang, R.S. Lankone, R.B. Reed, D.H. Fairbrother, J.F. Ranville, Analysis of
single-walled carbon nanotubes using spICP-MS with microsecond dwell
time, NanoImpact 1 (2016) 65e72, https://doi.org/10.1016/
j.impact.2016.04.004.
[751] J. Kidd, Y. Bi, D. Hanigan, P. Herckes, P. Westerhoff, Yttrium residues in
MWCNT enable assessment of MWCNT removal during wastewater treat-
ment, Nanomaterials 9 (5) (2019) 670, https://doi.org/10.3390/
nano9050670.
[752] N. Neubauer, G. Kasper, Detection of airborne carbon nanotubes based on the
reactivity of the embedded catalyst, J Occup Environ Hyg 12 (3) (2015)
182e188, https://doi.org/10.1080/15459624.2014.960574.
[753] A.D. Shinde, R. Acharya, R. Verma, A.V.R. Reddy, Chemical characterization of
graphite by instrumental neutron activation analysis, J Radioanal Nucl Chem
294 (3) (2011) 409e412, https://doi.org/10.1007/s10967-011-1467-2.
[754] S.Y. Chee, M. Pumera, Metal-based impurities in graphenes: application for
electroanalysis, Analyst 137 (9) (2012) 2039e2041, https://doi.org/10.1039/
c2an00022a.
[755] Y. Li, W. Zhou, H. Wang, L. Xie, Y. Liang, F. Wei, et al., An oxygen reduction
electrocatalyst based on carbon nanotube-graphene complexes, Nat Nano-
technol 7 (2012) 394e400, https://doi.org/10.1038/nnano.2012.72.
[756] D.M. Morales, J. Masa, C. Andronescu, W. Schuhmann, Promotional effect of
Fe impurities in graphene precursors on the activity of MnOX/graphene

ski, S. Dyjak / Carbon 168 (2020) 748e845
W. Kicin
electrocatalysts for the oxygen evolution and oxygen reduction reactions,
ChemElectroChem 4 (11) (2017) 2835e2841, https://doi.org/10.1002/
celc.201700496.
[757] J. Zhang, M. Comotti, F. Schuth, R. Schlogl, D.S. Su, Commercial Fe- or Co-
containing carbon nanotubes as catalysts for NH3 decomposition, Chem
Commun 19 (2007) 1916e1918, https://doi.org/10.1039/b700969k.
[758] N. Vishnu, A.S. Kumar, Intrinsic iron-containing multiwalled carbon nano-
tubes as electro-fenton catalyst for the conversion of benzene to redox-
active surface-confined quinones, ChemElectroChem 3 (6) (2016)
986e992, https://doi.org/10.1002/celc.201600052.
[759] J.S. Stefano, D.P. Rocha, R.M. Dornellas, L.C.D. Narciso, S.R. Krzyzaniak,
P.A. Mello, et al., Highly sensitive amperometric detection of drugs and an-
tioxidants on non-functionalized multi-walled carbon nanotubes: effect of
metallic impurities? Electrochim Acta 240 (2017) 80e89, https://doi.org/
10.1016/j.electacta.2017.04.050.
[760] P. Mayuri, A.S. Kumar, In situ derivatization of an intrinsic iron impurity as a
surface-confined Iron(II)tris(2,2’-bipyridine) complex on MWCNT and its
application to selective electrochemical sensing of DNA’s purine bases,
Langmuir 31 (21) (2015) 5945e5951, https://doi.org/10.1021/
acs.langmuir.5b00491.
[761] P. Kanagavalli, S. Senthil Kumar, Stable and sensitive amperometric deter-
mination of endocrine disruptor bisphenol A at residual metal impurities
within SWCNT, Electroanalysis 30 (3) (2018) 445e452, https://doi.org/
10.1002/elan.201700596.
[762] S. Sornambikai, M.R. Abdul Kadir, A.S. Kumar, N. Ponpandian,
C. Viswanathan, Selective and low potential electrocatalytic oxidation and
sensing of l-cysteine using metal impurity containing carbon black modified
electrode, Anal Methods 9 (48) (2017) 6791e6800, https://doi.org/10.1039/
c7ay02251d.
[763] N. Vishnu, A.S. Kumar, S. Badhulika, Selective in-situ derivatization of
intrinsic nickel to nickel hexacyanoferrate on carbon nanotube and its
application for electrochemical sensing of hydrazine, J Electroanal Chem 837
(2019) 60e66, https://doi.org/10.1016/j.jelechem.2019.02.015.
[764] S. Boopathi, R. Sudha, S. Senthil Kumar, K. Lakshminarasimha Phani, Residual
metal impurity aids facile in situ electrochemical surface derivatization of
single-walled carbon nanotubes, Chem - Asian J 9 (11) (2014) 3264e3268,
https://doi.org/10.1002/asia.201402657.
[765] R.K. Emmett, M. Karakaya, R. Podila, M.R. Arcila-Velez, J. Zhu, A.M. Rao, et al.,
Can faradaic processes in residual iron catalyst help overcome intrinsic EDLC
limits of carbon nanotubes? J Phys Chem C 118 (46) (2014) 26498e26503,
https://doi.org/10.1021/jp5097184.
[766] R.K. Emmett, M.J. Kowalske, H. Mou, M. Grady, H. Jiang, M.E. Roberts,
Creating faradaic carbon nanotube electrodes with mild chemical oxidation,
Batteries Supercaps 2 (10) (2019) 858e866, https://doi.org/10.1002/
batt.201900049.
[767] L. Yang, Y. Yang, X. Zhao, M. Zou, S. Wu, R. Zhao, et al., Exposing residual
catalyst in a carbon nanotube sponge, RSC Adv 6 (51) (2016) 45103e45111,
https://doi.org/10.1039/c6ra05775f.
[768] N. Vishnu, A. Gopalakrishnan, S. Badhulika, Impact of intrinsic iron on
electrochemical oxidation of pencil graphite and its application as super-
capacitors, Electrochim Acta 269 (2018) 274e281, https://doi.org/10.1016/
j.electacta.2018.03.024.
[769] Y. Gao, Carbon nano-allotrope/magnetic nanoparticle hybrid nanomaterials
as T2 contrast agents for magnetic resonance imaging applications, J Funct
Biomater 9 (1) (2018), https://doi.org/10.3390/jfb9010016.
[770] Y. Zhang, M. Wu, M. Wu, J. Zhu, X. Zhang, Multifunctional carbon-based
nanomaterials: applications in biomolecular imaging and therapy, ACS
Omega 3 (8) (2018) 9126e9145, https://doi.org/10.1021/acsomega.8b01071.
[771] M. Mohajeri, B. Behnam, A. Sahebkar, Biomedical applications of carbon
nanomaterials: drug and gene delivery potentials, J Cell Physiol 234 (1)
(2018) 298e319, https://doi.org/10.1002/jcp.26899.
[772] A. Al Faraj, K. Cieslar, G. Lacroix, S. Gaillard, E. Canet-Soulas, Y. Cremillieux,
In vivo imaging of carbon nanotube biodistribution using magnetic reso-
nance imaging, Nano Lett 9 (3) (2009) 1023e1027, https://doi.org/10.1021/
nl8032608.
[773] B.T. Doan, J. Seguin, M. Breton, R. Le Beherec, M. Bessodes, J.A. Rodriguez-
Manzo, et al., Functionalized single-walled carbon nanotubes containing
traces of iron as new negative MRI contrast agents for in vivo imaging,
Contrast Media Mol Imaging 7 (2) (2012) 153e159, https://doi.org/10.1002/
cmmi.474.
[774] X. Ding, R. Singh, A. Burke, H. Hatcher, J. Olson, R.A. Kraft, et al., Development
of iron-containing multiwalled carbon nanotubes for MR-guided laser-
845
induced thermotherapy, Nanomedicine 6 (8) (2011) 1341e1352, https://
doi.org/10.2217/nnm.11.37.
[775] B.M. Maciejewska, A. Warowicka, A. Baranowska-Korczyc, K. Załe˛ ski,
T. Zalewski, K.K. Kozioł, et al., Magnetic and hydrophilic MWCNT/Fe com-
posites as potential T2-weighted MRI contrast agents, Carbon 94 (2015)
1012e1020, https://doi.org/10.1016/j.carbon.2015.07.091.
[776] J.S. Ananta, M.L. Matson, A.M. Tang, T. Mandal, S. Lin, K. Wong, et al., Single-
walled carbon nanotube materials as T2-weighted MRI contrast agents,
J Phys Chem C 113 (45) (2009) 19369e19372, https://doi.org/10.1021/
jp907891n.
[777] F. Syed, C. Riggio, M. Masini, M. Bugliani, V. Battaglia, M. Novelli, et al., La-
beling and tracking of human pancreatic islets using carbon nanotubes,
J Biomed Nanotechnol 11 (4) (2015) 730e738, https://doi.org/10.1166/
jbn.2015.1952.
[778] C. Wang, X. Ma, S. Ye, L. Cheng, K. Yang, L. Guo, et al., Protamine function-
alized single-walled carbon nanotubes for stem cell labeling and in vivo
Raman/magnetic resonance/photoacoustic triple-modal imaging, Adv Funct
Mater 22 (11) (2012) 2363e2375, https://doi.org/10.1002/adfm.201200133.
[779] J.H. Choi, F.T. Nguyen, P.W. Barone, D.A. Heller, A.E. Moll, D. Patel, et al.,
Multimodal biomedical imaging with asymmetric single-walled carbon
nanotube/iron oxide nanoparticle complexes, Nano Lett 7 (4) (2007)
861e867, https://doi.org/10.1021/nl062306v.
[780] H. Jin, D.A. Heller, M.S. Strano, Single-particle tracking of endocytosis and
exocytosis of single-walled carbon nanotubes in NIH-3T3 cells, Nano Lett 8
(6) (2008) 1577e1585, https://doi.org/10.1021/nl072969s.
[781] D. Cai, J.M. Mataraza, Z.H. Qin, Z. Huang, J. Huang, T.C. Chiles, et al., Highly
efficient molecular delivery into mammalian cells using carbon nanotube
spearing, Nat Methods 2 (6) (2005) 449e454, https://doi.org/10.1038/
nmeth761.
[782] O. Vittorio, S.L. Duce, A. Pietrabissa, A. Cuschieri, Multiwall carbon nanotubes
as MRI contrast agents for tracking stem cells, Nanotechnology 22 (9) (2011),
https://doi.org/10.1088/0957-4484/22/9/095706, 095706.
[783] S.Y. Madani, A. Mandel, A.M. Seifalian, A concise review of carbon nanotube’s
toxicology, Nano Rev 4 (1) (2013) 21521, https://doi.org/10.3402/
nano.v4i0.21521.
[784] Saeed Khodabakhshi, Pasquale F. Fulvio, Enrico Andreoli, Carbon black
reborn: Structure and chemistry for renewable energy harnessing, Carbon
162 (2020) 604e649, https://doi.org/10.1016/j.carbon.2020.02.058. https://
doi.org/10.1016/j.carbon.2020.02.058.
[785] A. Bianco, Y. Chen, E. Frackowiak, M. Holzinger, N. Koratkar, V. Meunier, et
al., Carbon science perspective in 2020: current research and future chal-
lenges, Carbon 161 (2020) 373e391, https://doi.org/10.1016/
j.carbon.2020.01.055.
[786] Pumera M., Materials Electrochemists’ Never-Ending Quest for Efficient
Electrocatalysts: The Devil Is in the Impurities. ACS Catal. 2020, 10, XXX,
7087e7092. https://doi.org/10.1021/acscatal.0c02020.
[787] F. Pan, B. Li, E. Sarnello, Y. Fei, Y. Gang, X. Xiang, et al., Atomically dispersed
iron-nitrogen sites on hierarchically mesoporous carbon nanotube and
graphene nanoribbon networks for CO2 reduction, ACS Nano (2020), https://
doi.org/10.1021/acsnano.9b09658.
[788] Q. Fu, H. Saltsburg, M. Flytzani-Stephanopoulos, Active nonmetallic Au and
Pt species on ceria-based water-gas shift catalysts, Science 301 (5635) (2003)
935e938, https://doi.org/10.1126/science.1085721.
[789] G.F. Han, F. Li, W. Zou, M. Karamad, J.P. Jeon, S.W. Kim, et al., Building and
identifying highly active oxygenated groups in carbon materials for oxygen
reduction to H2O2, Nat Commun 11 (1) (2020) 2209, https://doi.org/10.1038/
s41467-020-15782-z.
[790] G. Malta, S.A. Kondrat, S.J. Freakley, C.J. Davies, L. Lu, S. Dawson, et al.,
Identification of single-site gold catalysis in acetylene hydrochlorination,
Science 355 (6332) (2017) 1399e1403, https://doi.org/10.1126/
science.aal3439.
[791] M. Holmes, Global carbon fibre market remains on upward trend, Reinforced
Plastics 58 (6) (2014) 38e45, https://doi.org/10.1016/S0034-3617(14)
70251-6.
[792] M.P. Browne, V. Urbanova, J. Plutnar, F. Novotný, M. Pumera, Inherent im-
purities in 3D-printed electrodes are responsible for catalysis towards water
splitting, J Mater Chem A 8 (2020) 1120e1126, https://doi.org/10.1039/
c9ta11949c.
[793] C. Moreno, M. Vilas-Varela, B. Kretz, A. Garcia-Lekue, M.V. Costache,
M. Paradinas, et al., Bottom-up synthesis of multifunctional nanoporous
graphene, Science 360 (6385) (2018) 199e203, https://doi.org/10.1126/
science.aar2009.