Materials

View Article Online

View Journal

Horizons
Accepted Manuscript

This article can be cited before page numbers have been issued, to do this please use: B. Szczesniak, S.
Borysiuk, J. Choma and M. Jaroniec, Mater. Horiz., 2020, DOI: 10.1039/D0MH00081G.
Volume 5
This is an Accepted Manuscript, which has been through the
Materials
Number 3
May 2018
Pages 311-580
Royal Society of Chemistry peer review process and has been
accepted for publication.
Horizons Accepted Manuscripts are published online shortly after acceptance,
rsc.li/materials-horizons

before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.

You can find more information about Accepted Manuscripts in the

Information for Authors.

Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
ISSN 2051-6347 Terms & Conditions and the Ethical guidelines still apply. In no event
COMMUNICATION
Blaise L. Tardy, Orlando J. Rojas et al.
Biofabrication of multifunctional nanocellulosic 3D structures:
shall the Royal Society of Chemistry be held responsible for any errors
a facile and customizable route

or omissions in this Accepted Manuscript or any consequences arising

from the use of any information it contains.

rsc.li/materials-horizons
 Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
Page 1 of 19

TOC Graphics
Materials Horizons

DOI: 10.1039/D0MH00081G
View Article Online

Materials Horizons Accepted Manuscript

 Materials Horizons Page 2 of 19
View Article Online
CREATED USING THE RSC ARTICLE TEMPLATE (VER. 3.1) - SEE WWW.RSC.ORG/ELECTRONICFILES FOR
DOI: DETAILS
10.1039/D0MH00081G

ARTICLE TYPE www.rsc.org/xxxxxx | XXXXXXXX

Mechanochemical synthesis of highly porous materials

Barbara Szczęśniak a, Sylwia Borysiuk a, Jerzy Choma a, Mietek Jaroniec*b

Received (in XXX, XXX) Xth XXXXXXXXX 2020, Accepted Xth XXXXXXXXX 2020
First published on the web Xth XXXXXXXXX 2020
DOI: 10.1039/b000000x
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.

Abstract………………………………………………………….……………………………...1
1 Introduction…………………………………………………………....……………………...1

Materials Horizons Accepted Manuscript

1.1 What is mechanochemistry?..................................................................................................1
1.2 Mechanochemical tools…………………………………………………………………….2
10 1.3 History of mechanochemistry……………………………………………………………...2
1.4 Main group mechanochemistry…………………………………………………………….2
1.5 Solution vs. mechanochemical methods…………………………………………………...3
2 Highly porous materials………………………………………....…………………………...3
2.1 Carbons………………………………………………………………………………….....3
15 2.2 Graphene-based materials…………………………………………………………………7
2.3 Metal-organic frameworks………………….……………………………………………..8
2.4 Other nanomaterials…………....…………………………………………………………11
3 Application.............................................................................................................................12
4 Conclusions............................................................................................................................12
20 5 Outlook and future prospects……………………………………………………………….12
References.................................................................................................................................14

Conventional synthesis methods of functional materials are usually time- and energy consuming and contribute to the accumulation of
waste solvents. An alternative solution is the use of environmentally friendly recipes such as mechanochemical synthesis, which may be
25 employed for a large-scale production of materials. Mechanochemistry has been applied in various areas, such as metallurgy, mineral
processing, construction and synthesis of organic compounds, and currently it experiences a renaissance because of its successful
implementation for the synthesis of diverse organic, inorganic and organic-inorganic hybrid nanomaterials. Here mechanochemical
synthesis of highly porous materials is reviewed with special emphasis on novel sorbents. Mechanochemical-assisted methods are well
suited for the preparation of highly porous carbons (such as lignin- or tannin-derived carbons), metal-organic frameworks (e.g., MOF-5,
30 MIL-101 and U-67) or covalent organic frameworks with specific surface areas up to 3500 m2·g-1. Recently, ball milling was also utilized
for the synthesis of ordered coordination polymers and perfectly ordered mesoporous carbons. Nowadays, mechanochemistry became a
powerful and quite universal method for the preparation of various materials. Hence, there is a need for a review summarizing the current
accomplishments in this field. Most of the mechanochemically obtained porous materials reported so far have been designed for adsorption,
catalysis and energy storage related applications.
35

1 Introduction
1.1 What is mechanochemistry?
Mechanochemical reaction depends on the sample Gibbs free
energy change, and machine function, which represents the ability
to accumulate and target stress energy to initialize the reaction.1
Energy required for the initiation and stimulation of chemical
reactions is provided by mechanical action, i.e., shearing,
* Corresponding author
aInstitute of Chemistry, Military University of Technology, 00-908
Warsaw, Poland. E-mail: barbara.szczesniak@wat.edu.pl,
sylwia.borysiuk@wat.edu.pl, jerzy.choma@wat.edu.pl
bDepartment of Chemistry and Biochemistry & Advanced Materials and
Liquid Crystal Institute, Kent State University, Kent, Ohio 44242, USA.
Fax: (+1)-330-672-3816; Tel: (+1)-330-672- 3790; E-mail:
jaroniec@kent.edu
compression, grinding, etc. (Fig. 1). This process enables rapid and
quantitative solid phase-reactions without applied heat. Moreover,
the mass and energy transport occur under solvent-free conditions
or with low amounts of solvents. This means significant reduction
of solvent consumption and waste liquid, which is undoubtedly an
outstanding advantage and in line with the current focus on
environmentally friendly chemical reactions.
A typical mechanochemical reaction relies on a ball milling
process. When the precursors are trapped and crushed between two
balls, they accumulate an excess of potential energy leading to
bonds breakage, defects and other changes on their surface. Hence
this process not only reduces the particle size, but also enhances
reactivity including the generation of active sites. During a milling
process the reaction can occur only at the interfaces between
phases, not in the bulk of the reactants. Therefore, it is crucial to
generate fresh, active surface for particles to contact and react. For
instance, while using ball milling, one have to consider the
following issues: (i) amount of substrates, (ii) size and material of

This journal is © The Royal Society of Chemistry [2020] Mater. Horiz. | 1

 Page 3 of 19 Materials Horizons
milling bowl, (iii) amount, diameter and density of balls, (v) speed
of rotation and (vi) time of milling.
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
Fig. 1 Schematic illustration of mechanochemical reaction
between two reactants.2
1.2 Mechanochemical tools
Nowadays, a wide range of vessels and equipment are
commercially available to perform mechanochemical reactions,
such as mortar grinders and mills: planetary (ball), mixer (shaker),
cryomill, drum and extruder (Fig. 2). The simplest and least
expensive tool is mortar and pestle, but it is not recommended due
to the great difficulty of preserving reproducible conditions.
Electronically controllable mortar grinders and mills ensure: (i)
uniform fragmentation of reactants, (ii) reliable and accurate
grinding or milling process and (iii) reproducible, contamination-
free synthesis conditions. Nevertheless, one should realize that
depending on the reactor used (especially milling balls) some
impurities can be introduced into products that originate from the
material of mechanochemical reactors.
1.3 History of mechanochemistry
Mechanochemistry has a long history and nowadays its popularity
is growing. Mechanochemical processes considered as chemical
transformations caused by mechanical stress, compression or
Fig. 2 Schematic illustration of (a) mortar and pestle, (b) planetary mill, (c) shaker and (d) extruder. Images of the instruments for
mechanochemical synthesis: (e) mortar grinder, (f) planetary mills with equipment and (g) mixer mill with equipment. Adapted with
permission from ref. 4. Copyright © 2018, American Chemical Society.
Mater. Horiz.
View Article Online
DOI: 10.1039/D0MH00081G
friction have a very long history that can be traced to the prehistoric
period. After all, mechanical friction was used by early humans to
make fire. Nowadays, the same effect is used in mining industry
and military for the utilization of sensitive explosives. The written
history of mechanochemistry starts from 315 B.C. when
Theophrastus in his book entitled: “On Stones” described a method
to obtain quicksilver (mercury) by grinding cinnabar (HgS) using
a pestle and mortar made of copper or bronze. During this process,
elemental Hg was formed via metal displacement reaction of HgS
and Cu.5 After that, only at 19th century next records devoted to
Materials Horizons Accepted Manuscript
mechanical reactions can be found. For instance, “dry way” of
AgCl reduction by grinding it with Zn, Sn, Fe and Cu described by
Faraday in 1820 and Lea experiments published in 1866 devoted
to mechanochemical grinding during which different chemical
changes occurred similar to those taking place during thermal
treatment.6,7
The term mechanochemistry was written for the first time by
Wilhelm Ostwald in the “Textbook of General Chemistry” in 1891
while its definition accepted today, i.e., “that branch of chemistry
concerned with chemical and physical changes of solids induced
by the action of mechanical influence“ was proposed by Gerhard
Heinicke in 1984.8 According to the IUPAC recommendations
from 2003 the term mechanochemical reaction refers to “chemical
reaction that is induced by the direct absorption of mechanical
energy“.9 Readers are referred to some well-written previous
reviews for the detailed history of mechanochemistry.2,10–12
1.4 Main classes of mechanochemically-synthesized materials
History indicates that mechanochemistry is not a new concept.
However, most contributions devoted to the development of
mechanochemical processes, methodology and equipment have
been accomplished in the past two decades. The main stimulus in
this field was mechanochemical synthesis of organic compounds.
Thanks to the recent research efforts, mechanochemical concepts
have been successfully utilized for the preparation of designed,
advanced nanomaterials with a wide range of uses which took
mechanochemistry to the next stage. Nowadays,
This journal is © The Royal Society of Chemistry [2020]
 Materials Horizons
mechanochemistry involves a vast area of inorganic, organic and
hybrid compounds, such as: alloys, nanoparticles, main group
elements, metal complexes, organometallic compounds, polymers,
covalent organic frameworks, metal-organic frameworks, zeolites,
carbonaceous materials, supramolecular complexes and energy
materials. Fig. 3 shows the main classes of mechanochemically
synthesized nanomaterials including composites obtained by in-
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
situ or post-synthetic merging of these materials.
Fig. 3 Pictorial representation of mechanochemically synthesized
nanomaterials: metal oxides, porous organic materials, metal-
organic frameworks, zeolites, graphitic carbon nitrides (C3N4),
graphene-based materials, ordered mesoporous carbons, carbons
and metal nanoparticles.
1.5 Solution vs. mechanochemical methods
Mechanochemical synthesis of advanced materials competes with
more conventional, solution-based approaches, which usually
involve heating, addition of expensive/hazardous reagents and
multi-step processing. Simple and reproducible grinding or milling
conditions could overcome these inherent drawbacks. Moreover,
mechanochemistry gives opportunity for the synthesis of new or
modified compounds/materials because of the enhanced reactivity
of reactants upon grinding/milling. Different types of
mechanosynthesis have been introduced so far, such as neat
grinding (without any solvent), liquid-assisted grinding (LAG) or
kneading (other names are solvent-assisted grinding or solvent
drop grinding) indicating that some advantages of more traditional
solution-based methods are sometimes used in mechanochemistry.
2 Highly porous materials
Due to high specific surface area and large pore volume, highly
porous materials have already shown promising performance in
a variety of applications such as energy storage, adsorption,
catalysis, removal of pollutants, fuel cells and supercapacitors.
Nowadays, great efforts have been made to find fast,
environmentally friendly, energy-efficient, and easy to use and
scale up procedures for the preparation of porous functional
This journal is © The Royal Society of Chemistry [2020]
Page 4 of 19
View Article Online
DOI: 10.1039/D0MH00081G
materials. In this field, mechanochemistry gains popularity,
since it enables a green fabrication of large variety of porous
nanomaterials and become a remarkably powerful and universal
synthetic method.
Porosity pictured as void spaces in a material structure is typically
evaluated by using two the most important structural parameters,
namely, the specific surface area (SSA) and total pore volume (Vt).
Most often the pore size distribution (PSD) and average pore size
are also determined to gain additional information about pores.
SSA is usually calculated based on low-temperature nitrogen
Materials Horizons Accepted Manuscript
adsorption isotherms in the relative pressure range of 0.05 – 0.2
according to the BET (Brunauer-Emmett-Teller) multilayer
adsorption model. The total pore volume (Vt) is calculated using
the volume of the nitrogen adsorbed at relative pressure close to
unity. Pore size has a significant influence on the porosity and
adsorption properties of a material. Smaller pores (micropores)
provide high SSA as well as enhanced affinity toward small
adsorbate molecules, while larger pores (mesopores) contribute
considerably to the pore volume Vt providing low-resistance
transport pathways. According to the IUPACs classification,
micropores are pores below 2 nm and mesopores are pores in the
range of 2 – 50 nm. Two types of micropores can be further
distinguished due to their size: ultramicropores (pores below 0.7
nm) and supermicropores (pores in the range of 0.7 – 2.0 nm).13
High porosity is a relative term and depends on the type of
materials. For instance, plenty of MOFs or carbons presented in
the literature possess SSA above 3000 m2·g-1, while SSA about 300
m2·g-1 is considered as high in the case of metal oxides. The record
BET SSA of ~7000 m2·g-1 still gains a MOF material published in
2012.14
2.1 Carbons
Activated carbons have been widely studied and applied in many
fields such as wastewater treatment, gas separation and purification,
solvent recovery and catalysis. For industry applications, they are
predominantly produced from natural feedstocks: hard coal, wood,
lignite or biomass. Highly porous activated carbons are most often
synthesized from natural or synthetic materials by carbonization in
inert atmosphere (N2, Ar) followed by chemical or physical
activation. The most commonly used activation agents are KOH,
H3PO4, ZnCl2, K2CO3, CO2 or steam. In some cases, porous
carbons can be obtained without conventional carbonization or
activation process. For instance, Casco et al.15 reported fast (5 min)
room temperature mechanochemical reaction for the synthesis of
N-doped porous carbons from calcium carbide and cyanuric
chloride without any carbonization/activation step involved (Fig.
4). The as-produced carbons had high SSA up to 1080 m2·g-1, high
N-content up to 16 wt. % and featured good electrical
conductivities considering that the mechanical action was the only
external source of energy.
Mater. Horiz. | 3
 Page 5 of 19 Materials Horizons
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
Fig. 4 Schematic illustration for the preparation of N-doped porous
carbons via mechanochemical reaction between calcium carbide and
cyanuric chloride conducted at room temperature.15
During milling or grinding process, mechanochemical energy reduces
particles size enlarging the overall surface of a bulk sample.
Additionally, the created defects become reactive sites imparting
specific surface property of the sample. Lin et al.16 demonstrated a
green, activation-free method for the fabrication of highly porous
carbons from agricultural wastes utilizing mechanochemistry. The
synthesis involved smashing coconut shells via high energy ball
milling into tiny microparticles with abundant surface and bulk
defects. After subsequent carbonization at 900 ºC for 9 h, the
obtained carbon possessed high SSA of 1770 m2·g-1 and large pore
volume of 1.88 cm3·g-1. These values of the structural parameters
are much greater than those determined for the analogues sample
obtained in the same way but without mechanochemical step (Fig.
5).
Fig. 5 Schematic illustration of highly porous carbon synthesis
from agricultural wastes. Reproduced with permission from ref. 16.
Copyright © 2017, American Chemical Society.
Recently mechanochemical-assisted method was successfully
implemented for a facile preparation of carbon nanospheres.17 The
nanospheres were synthesized from tannic acid (TA) and urea,
both used as carbon precursors, grinded with a eutectic salt
(NaCl/ZnCl2) – pore-creating agent (Fig. 6). Changing the mass
ratio of carbon precursors to the eutectic salt and the molar ratio of
urea to tannic acid, highly porous carbons with SSA varied from
900 to 1570 m2·g-1 were obtained after activation at 800 °C (1 h
under nitrogen). The highest porosity featured the sample obtained
without TA addition. However, the best electrochemical
performance, with a specific capacitance of 110 F·g-1, showed the
carbon synthesized using a molar ratio of urea to tannic acid of 9 :
Mater. Horiz.
View Article Online
DOI: 10.1039/D0MH00081G
1 thanks to the combined effect of textural properties, high nitrogen
content (8.3 wt. %) and high electrical conductivity.
Materials Horizons Accepted Manuscript
Fig. 6 Schematic illustration of the dry synthesis and SEM image
of carbon nanospheres.17
Mechanochemical routes have been frequently used to effectively
mix a carbon precursor with chemical activating agent in order to
enhance the porosity generation during thermal activation.18–23 The
obtained carbons can possess hierarchical porosity and SSA even
above 3000 m2·g-1.21–23 As an example, Borchardt et al.21 ball
milled carbon precursors, lignin and urea with activating agent
K2CO3 in equal proportion in a zirconia vessel with 20 zirconia
balls (diameter 10 mm) for 30 min and thermally activated the
resulting polymer at 800 ºC (Fig. 7). The as-obtained N-doped
porous carbon (denoted as lignin–urea–K2CO3_1) exhibited a very
high SSA of 3040 m2·g-1, large Vt of 2.13 cm3·g-1 and N2 content
of 6.3 wt. %. This sample showed an excellent performance as
supercapacitor electrode material, reaching specific capacitance of
192 F·g-1 in an ionic liquid electrolyte calculated at a current
density of 0.1 A·g-1, much higher than the commonly used
activated carbons. For comparison, analogous porous carbons
(lignin–urea–K2CO3_2 and lignin–urea–K2CO3_3) were
synthesized by using different molar ratio of the substrates.
Nitrogen and water vapor adsorption-desorption isotherms were
used to characterize porosity and surface chemistry of the obtained
samples (Fig. 8). The PSD functions of all three samples reveal the
presence of micropores with an average size of about 1 nm and
small mesopores with an average diameter of 2–4 nm, which is
characteristic for hierarchical materials. Water vapor adsorption
measurements provided additional information about porous
structure as well as surface chemistry of the samples. Very small
kinetic diameter of water molecule allows it to enter smaller pores
than those detected by nitrogen or carbon dioxide. Later, the
Borchardt’s group demonstrated that this synthetic concept can be
adopted for the preparation of highly porous carbons (SSA in the
range of 1900-3000 m2·g-1) from other green precursors such as:
wood waste, TA and cellulose.22 Nevertheless, the highest SSA of
3200 m2·g-1 showed the lignin-derived carbon whose synthesis
involved ball milling of the carbon source with urea and K2CO3.
The authors pointed out a great performance of the obtained
carbons as cathode materials for Li–S batteries, i.e., initial
discharge capacities up to 1300 mAh·gsulfur-1 (95 % coulombic
efficiency) and capacity retention above 75 % within the first 50
cycles at a low electrolyte volume.
This journal is © The Royal Society of Chemistry [2020]
 Materials Horizons Page 6 of 19
View Article Online
DOI: 10.1039/D0MH00081G
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.

Fig. 7 Schematic illustration of highly porous carbon synthesis Fig. 9 (a) Low-temperature N2 adsorption isotherms, (b) PSD
from sustainable precursors. Reproduced with permission from ref. functions and (c) CO2 adsorption isotherms measured at 25 °C and

Materials Horizons Accepted Manuscript

21. Copyright © 2017, Wiley-VCH Verlag GmbH & Co. KGaA, pressure up to 20 bar for mechanochemically activated lignin-
Weinheim. derived carbon (L2600P) and the analogous sample activated
conventionally (L2600). Adapted with permission from ref. 20.
1600 2000
lignin-urea-K2CO3_1 Copyright © 2015, WILEY-VCH Verlag GmbH & Co. KGaA,
1400 1800 lignin-urea-K2CO3_2

1200
1600 lignin-urea-K2CO3_3 Weinheim.
1400
1000 1200
800 1000
800
In general, the CO2 adsorption capacity of sorbents can be
600
400
600 enhanced by either decreasing pore size, tuning surface chemistry
lignin-urea-K 2CO
lignin-urea-K 2CO33_1
_1 400
200 lignin-urea-K 2CO
lignin-urea-K 2CO 33_2
_2
200 (e.g., heteroatom doping and decoration with nanoparticles) or
lignin-urea-K
lignin-urea-K COCO
2 2 33 _3
_3
0
0.0 0.2 0.4 0.6 0.8 1.0
0
0.0 0.2 0.4 0.6 0.8 1.0
forming composite materials. Narrow micropores
Relative Pressure Relative Pressure
(ultramicropores) in the carbon structure act as CO2-philic sites due
Fig. 8 Nitrogen and water vapour adsorption-desorption isotherms to the overlapping adsorption potential from opposite pore walls.
of N-doped lignin-derived carbons. Reproduced with permission The synergistic effect of highly microporous network and N-rich
from ref. 21. Copyright © 2017, Wiley-VCH Verlag GmbH & Co. surface of carbons assures an efficient and selective CO2
KGaA, Weinheim. adsorption under low pressures (≤ 1 bar). Porous structure and
chemical composition of activated carbons highly depends on the
A mechanochemical activation that involves a compression step, type of precursor and activation method including temperature of
so-called compactivation, is another route for the preparation of activation process. Highly microporous carbons from dopamine
highly porous activated carbons.19,20 For instance, the and melamine were synthesized using mechanochemical reaction
mechanochemically activated carbons derived from biomass, i.e., to obtain dopamine-melamine composite in the first step.
sawdust or lignin, reported by Balahmar et al.20 possessed high Subsequent carbonization and KOH-activation at 550 ºC of the
surface area up to 2220 m2·g-1. This activation relied on (i) composite gave a microporous carbon (microporosity around
grinding a carbon precursor with KOH at weight ratio of 2 in a 74 %) with SSA of 870 m2·g-1 and very high N-content of 21 wt. %
mortar, (ii) compression at a load of 10 tones in a 1.3 cm diameter (including 13 wt. % of pyrrolic N). The abundance of nitrogen
die for 10 min, which is equivalent to compactivation at 740 MPa, species and large volume of small-sized micropores (~0.6 nm) in
and (iii) thermal activation at 600 or 650 °C for 1 h under a nitrogen the structure of this carbon resulted in high uptake up to 4.6 and
flow. The carbon obtained from lignin at 600 °C (LP600P) featured 3.6 mmol·g-1 of CO2 under 1 bar at 0 ºC and 25 ºC, respectively.
the highest porosity among all samples studied (SSA of 2220 m2·g- Moreover, according to the ideal adsorption solution theory
1). The conventionally activated (without compression) analogous
(IAST), this sample showed a very high CO2/N2 selectivity of 108
sample, denoted as LP600 possessed SSA of 1280 m2·g-1, so the at 0 ºC for the mixture containing 10 % CO2 and 90 % N2 (10 v. %
mechanochemical activation enabled to boost the porosity of a CO2) and 115 for the mixture of 15 v. % CO2.24 Higher porosity of
final product by 75 % (Fig. 9a). Interestingly, negligible changes carbons was acquired by using ball milling to merge a natural
in the microporosity and pore size distribution were observed for biomass Arundo donax and chitosan with ZnCl2 (chemical
the both samples indicating that the compression step intensified activator) prior to activation at different temperatures: 500, 600
the KOH-assisted activation process without altering the size of and 700 °C.25 The synthesized biocarbons denoted as NDAB3-500,
generated pores (Fig. 9b). Sample L2600P adsorbed high amount NDAB3-600 and NDAB3-700, respectively, possessed SSA up to
of CO2 at 25 °C, i.e., 4.5 and 12.8 mmol·g-1 under 1 and 20 bar, 1860 m2·g-1 and Vt up to 1.0 cm3·g-1 (Fig. 10). Nevertheless due to
respectively (Fig. 9c). At the same conditions the the wide pore size distribution up to 4 nm they showed lower CO2
mechanochemically activated sawdust-derived sample (SD2600P) adsorption capacities (up to 3.6 and 2.1 mmol·g-1 at 0 °C and 25 °C,
adsorbed 5.8 and 10.5 mmol·g-1 of CO2, respectively. A high CO2 respectively) compared to the carbon obtained from dopamine-
adsorption capacity under low pressure (≤1 bar) SD2600P owes to melamine composite characterized by even twice lower SSA.
its large volume of small pores (~0.6 nm). A similar
compactivation process prior to thermal treatment can be used to
transform waste tires into valuable porous carbons with SSA of
about 1000 m2·g-1 and H2 adsorption capacity up to 1.4 wt. % under
1 bar.19

This journal is © The Royal Society of Chemistry [2020] Mater. Horiz. | 5

 Page 7 of 19 Materials Horizons View Article Online
DOI: 10.1039/D0MH00081G
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.

Materials Horizons Accepted Manuscript

Fig. 10 (a) Low-temperature N2 adsorption isotherms, (b) PSD
functions, (c) CO2 adsorption isotherms at 0 °C, and (d) CO2
adsorption isotherms at 25 °C determined for NDAB3-T samples,
Fig. 11 Schematic illustration of the mechanochemical synthesis
where T is activation temperature: A) 500, B) 600 and C) 700 °C.25
of ordered mesoporous carbons.31

Ordered mesoporous carbons (OMCs) attract special attention

A highly porous OMC with SSA of 1030 m2·g-1 was obtained by
because of their well-defined, ordered mesopores.26–28 Usually
using silica as a template and bipyridine and copper chloride as
hard- or soft-templating methods conducted in solution are used to
precursors. The mechanochemical coordination reaction and
form their uniform mesoporous structure.29,30 Hard templating
subsequent carbonization at 500 ºC allowed to obtain uniform
approaches are most often costly, energy- and time-consuming and
dispersion of heteroatoms and highly ordered mesoporous
involve the use of hazardous chemicals such as formaldehyde, HF,
structure after SiO2 and Cu removal.39 Zhao et al.33 obtained series
NH4HF2 or NaOH. Soft-templating strategy involves the use of
of N-doped mesoporous carbons using tannin as a carbon source,
surfactants or block co-polymers that decompose during heat
zinc acetate as a linker, Pluronic F127 as pore directing agent, and
treatment leaving uniform pores in the structure of the final carbon.
a nitrogen source among: urea, melamine, tyrosine and tryptophan
Many scientific groups synthesized ordered or disordered
(Fig. 12). After solvent-free ball milling of reagents, the obtained
mesoporous carbons as well as OMC-based composites by means
metal-organic coordination polymers were carbonized at high-
of mechanochemistry.31–35 It turned out, that the ball milling
temperature (up to 800 ºC) to remove template F127 (occurred at
process provides sufficient energy to initialize coordination
~450 ºC) and evaporate metallic Zn. N-content of the obtained
reactions and allow to uniformly disperse a polymer into the
carbons was in the range of 1.3 – 9.7 wt. % and was dependent on
template voids. Moreover, the mesostructural ordering is preserved
the type and quantity of the nitrogen source used. The authors
under stressful conditions of milling process.
observed that the increase in the N-content led to the decreased
Plant-derived polyphenols, such as hydrolysable tannins (e.g.,
SSA and Vt of the resulted carbons. For example, while using
gallic, digallic or ellagic acid) and condensed tannins (e.g., mimosa
different amounts of tryptophan as a nitrogen source: 0.1, 0.2 and
tannin) are excellent precursors for the preparation of OMCs,
0.3 g, the obtained carbons (labeled as MC-Tryptophan-0.1, MC-
because they are eco-friendly and cheap.31–33,36–38 Recently,
Tryptophan-0.2 and MC-Tryptophan-0.3, respectively) possessed
Castro-Gutiérrez et al.31 prepared ordered mesoporous carbons by
N-content of 1.8, 2.9 and 4.2 wt. % and SSA of 710, 560 and 410
mechanochemical self-assembly of tannin with Pluronic F127
m2·g-1, respectively. The highest CO2 adsorption capacity (~3.5
(PEO99-PPO65-PEO99) in the presence of small amount of water
mmol·g-1 at 0 ºC and 1 bar) showed the most porous sample (MC-
followed by carbonization at 900 °C for 3 h (Fig. 11). Adjusting
Tryptophan-0.1) indicating that, in the case of these sorbents,
the ratio of components used, i.e., tannin : Pluronic : water to be
proper porosity was more influential than specific surface
2 : 1 : 2, they obtained highly ordered mesoporous carbon with
functionalities (N-rich functional groups). The IAST CO2/N2
SSA of 510 m2·g-1 and the volume of mesopores of 0.24 cm3·g-1.
selectivity calculated for MC-Tryptophan-0.1 sample was about 30
Its two-dimensional hexagonal structure was maintained even after
for the mixture of 15 v. % CO2. Fig. 13 shows N2 adsorption
thermal treatment under inert atmosphere at 1500 °C. The authors
isotherms, (b) PSD functions, and (c) CO2 and N2 adsorption
showed that SSA of OMCs can be successfully enlarged up to
isotherms determined for carbons with tryptophan dosage.
~1900 m2·g-1 upon CO2 activation for 75 min at 900 °C as well as
their CO2 adsorption capacity was boosted up to 5.6 mmol·g-1
through potassium acetate activation at 800 °C for 1 h under
nitrogen flow.

Mater. Horiz. This journal is © The Royal Society of Chemistry [2020]

 Materials Horizons
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
Fig. 12 Schematic illustration of N-doped mesoporous carbon
synthesis from various precursors. Reproduced with permission
from ref. 33. Copyright © 2019, Elsevier B.V.
Fig. 13 (a) Low-temperature N2 adsorption isotherms, (b) PSD
functions, and (c) CO2 and N2 adsorption isotherms determined for
a mesoporous carbon with tryptophan dosage. Adapted with
permission from ref. 33. Copyright © 2019, Elsevier B.V.
2.2 Graphene-based materials
Graphene is one-atom-thick nanosheet consisting of sp2 hybridized
carbon atoms arranged in hexagons, which makes it the thinnest
material. Since its isolation by Novoselov and Geim in 2004
graphene has been widely studied all around the world.40 Thanks
to its two-dimensional crystalline structure with long-range π–π
conjugation of the carbon atoms in the planar layer, graphene is
characterized by remarkable properties such as excellent electron
mobility, high thermal conductivity, good optical transmittance,
mechanical stiffness and flexibility, and high SSA (2630 m2·g-
1).41–44 Therefore, over the last 15 years tremendous research effort
has been devoted to the synthesis of various graphene-based
materials for a wide range of applications including electronic,
energy storage (solar cells, supercapacitors, batteries and fuel),
This journal is © The Royal Society of Chemistry [2020]
Page 8 of 19
View Article Online
DOI: 10.1039/D0MH00081G
drug carriers, detectors, adsorbents, filters and aerospace industry
applications.45–50 However, practical applications using graphene
or graphene-derivatives as bulk materials are suppressed,
specifically due to the tendency of agglomeration or re-stacking of
graphene sheets, which significantly affects its porosity and
properties. To avoid the re-stacking of individual sheets, and
therefore retain the unique properties of the bulk material,
researches have been constructed three-dimensional graphene-
derived architectures (e.g., aerogels, hydrogels, sponges or foams)
or pillared/intercalated structures. Additionally, these structures
Materials Horizons Accepted Manuscript
can feature some new or modified physicochemical properties.51–
54 For instance, a mechanochemical-assisted route has been used to
introduce a controlled amount of tetraethoxysilane into surfactant
pre-expanded graphene oxide layers. After calcination highly
porous carbon/silica composites (SSA up to 1040 m2·g-1) with
ordered intercalation structure were acquired.54
Within the first five years since the isolation of graphene, the
reported SSA of graphene-based materials was well below the
theoretical value i.e., 2630 m2·g-1. Afterwards, by applying
activation methods, analogous to those used for activated carbons,
their SSA exceeded 3000 m2·g-1.45,48,55 Now, SSA of highly
perforated activated graphene can be as high as ~3500 m2·g-1.50,56
Interestingly, SSA of the theoretically modeled structure of
specifically perforated graphene sheets reached 5100 m2·g-1.49
According to the literature, using mechanochemistry it is possible
to obtain various graphene derivatives from nonporous pristine
graphite, such as: graphene oxide (Fig. 14a)57, multilayer and few-
layer graphene (Fig. 14b)58,59, graphene nanoplatelets60–64 or other
functionalized graphene-based materials.65,66 Nevertheless, to the
best of our knowledge, SSA of such materials is smaller than 1000
m2·g-1.
Fig. 14 Schematic representation for the examples of
mechanochemical fabrication of graphene-based materials such as
(a) graphene oxide and (b) mixture containing few-layer and even
mono-layer graphene. Adapted with permission from ref. 57.
Copyright © 2018, American Chemical Society. Adapted with
permission from ref. 58. Copyright © 2017, Elsevier B.V.
Few-layer N-doped graphene nanoplatelets reported by Xue et al.63
were fabricated by ball milling of graphite with melamine. During
this process the size of graphite particles was reduced from 30 to 1
μm, which facilitated its subsequent exfoliation under
Mater. Horiz. | 7
 Page 9 of 19 Materials Horizons
ultrasonication. The as-obtained graphene nanoplatelets exhibited
high nitrogen content (11.4 at. %) and showed good performance
as an electrode material for energy conversion and storage
application. Wang et al.62 obtained edge-nitrogenated graphene
nanoplatelets with SSA of 680 m2·g-1 and Vt of 0.9 cm3·g-1 via ball
milling of graphite flakes in nitrogen atmosphere for 7 h. The
obtained graphene-based material exhibited high specific
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
capacitance of 202.8 F·g−1 in 1 M H2SO4 aqueous electrolyte
applying the current density of 0.3 A·g-1. Iodine-doped graphene
nanoplatelets (HIGnPs) synthesized by Jeon et al.61 via ball milling
of low-quality graphite (L-graphite) with iodine for 48 h reached
SSA of 970 m2·g-1 (Fig. 15).
Fig. 15 (a) Schematic representation of the synthesis of graphene
nanoplatelets from graphite, (b) SEM images of the both samples.
Adapted with permission from ref. 61. Copyright © 2018, Elsevier.
Ball milling process has been successfully utilized for a solvent-
free reduction of graphene oxide (GO). The obtained reduced
graphene oxide (rGO) was in the form of dark black powder with
shiny light reflections implying its high crystallinity (Fig. 16).
Electrical conductivity of rGO reached 120 S·m-1 and could be
further enhanced up to 3400 S·m-1 by applying additional heat
treatment at 900 °C for 2 h in an inert atmosphere.67
Fig. 16 Schematic representation of solvent-free mechanochemical
reduction of GO into rGO (denoted as BMRGO) in the presence of
hydrogen. Some shiny light reflection visible in the digital picture
of rGO are marked by white circles. Reproduced with permission
from ref. 67. Copyright © 2014, Elsevier Ltd.
Mater. Horiz.
View Article Online
DOI: 10.1039/D0MH00081G
It is worth mention that mechanochemistry has been frequently
used to prepare various graphene-containing composites including:
graphene/C3N4,68,69 graphene/MOF,70,71 graphene/polymer,72
graphene/metal oxide,58,73,74 and other carbon-based
composites. 75,76 Moreover, mechanochemical concepts are
applicable to introduce some functionalities into the surface of
carbon nanotubes.77–80
2.3 Metal-organic frameworks
Metal-organic frameworks (MOFs) are coordination polymers
Materials Horizons Accepted Manuscript
consisting of metal ions or clusters and organic ligands connected
by coordination bonds forming three dimensional crystalline
structures. MOFs gain a lot of attention, because of their
extraordinarily high porosity (SSA up to 7000 m2·g-1)14,81 as well
as various, adjustable geometries, pore sizes and surface
functionalities. A series of MOFs was synthesized in 90s of the last
century, firstly MOF-2 [Zn(BDC)(H2O), BDC – 1,4-
benzendicarboxylate], thereafter MOF-3 [Zn3(BDC)3], MOF-4
[Zn(BTC)NO3), BTC – 1,3,5-benzentricarboxylate) and the most
recognizable MOF-5 revealing high diversity of these materials.82–
85 The framework of MOF-5 containing Zn O groups linked by
4
terephthalate [Zn4O(BDC)3] become a modular structure to obtain
several other MOFs just by changing length or functionality of its
ligands.
MOFs have shown remarkable gas adsorption properties toward
small adsorbate molecules such as H2, CO2, CO and CH4 thanks to
their highly porous networks with tunable pore sizes and open
metal active sites.86–89 For instance, microporous MOF denoted as
PCN-13 (with 9,10-anthracene dicarboxylate linkers) possesses
pores with diameter of 0.35 nm and can selectively adsorb O2 and
H2 excluding N2 and CO.90 Zn-containing MOF-177 has SSA of
4600 m2·g-1 and shows very high H2 storage capacity of 19.6 wt. %
at -196 ºC and 100 bar.91 Fig. 17 presents examples of MOFs
designed for high adsorption of different gases: PCN-12 (copper-
containing MOF with MDIP - 5,5′‐methylene‐di‐isophthalate
linkers), MIL-101 (chromium terephthalate-based MOF),
HKUST-1 [Cu3(BTC)2], bio-MOF-11 (contains adenine
biomolecular linkers), MOF-5, MOF-74 [Zn2(DHBDC), DHBDC
– 2,5-dihydroxy-1,4-benzenedicaroxylate], MOF-200 (with BBC -
4,4′,44″-benzene-1,3,5-triyl-tribenzoate linkers) and ZTF-1 (NH2-
functionalized zeolitic tetrazolate framework).81,88,92
This journal is © The Royal Society of Chemistry [2020]
 Materials Horizons Page 10 of 19
View Article Online
DOI: 10.1039/D0MH00081G
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.

Materials Horizons Accepted Manuscript

Fig. 17 Scheme of MOF structures with superior gas storage
Fig. 18 Mechanochemical reaction and the structure of Cu3(BTC)2
properties. Figure reproduced from ref. 87; Licensed under CC-BY.
MOF.96
So far, numerous methods have been introduced for the synthesis
Zinc-containing MOF, denoted as MOF-5 is the most recognized
of MOFs including solvothermal, microwave-assisted,
in the family of MOFs based on [Zn4O]6+ oxo-zinc SBU and
sonochemical, slow evaporation, electrochemical,
carboxylate linkers, known as IRMOFs. The first successful
mechanochemical and self-assembly approaches. These methods
mechanosynthesis of MOF-5 was reported in 2015 in which oxo-
require different source of energy and reaction time to obtain the
zinc clusters consisted of [Zn4O]6+ core surrounded by µ-1,2-
final product. The most popular is solvothermal method in which
amidate ligands were milled with terephthalic acid (H2BDC). The
the synthesis reaction last from hours to days. A comparison of
final product was obtained after activation with THF solution
synthesis strategies of MOFs has been reviewed recently in ref.88,93
followed by desolvation under vacuum. A systematic study of
Since mechanochemical reaction has been successfully employed
acid-base relationship between reagents used resulted in the
for the synthesis of coordination polymers and frameworks, it has
synthesis of highly porous MOF with SSA of 2350 m2·g-1 and H2
a great potential to be implemented in their large-scale
adsorption capacity of 1.3 wt. % at -196 ºC.100 Recently, MOF-5
fabrication.94–97
samples with higher SSA up to 3470 m2·g-1 were obtained by
The first mechanochemical synthesis of MOF was reported in 2006
efficient mechanochemical method based on direct grinding of
by James group.98 They obtained a microporous metal–organic
Zn(OAc)2·2H2O with H2BDC in a high speed vibrating ball mill
framework [Cu(INA)2, INA – isonicotinic acid] with high
(Fig. 19a).101 The porosity of MOF-5 was dependent on various
efficiency by grinding copper acetate with INA for 10 minutes
parameters such as the ratio of the zinc salt to the organic linker
without heat applied. A typical copper-containing Cu3(BTC)2
(Zn/BDC), grinding time and speed as well as the solvent used for
MOF can be obtained via simple grinding of Cu(OAc)·H2O with
activation. The Zn/BDC ratio had a great influence on the
H3BTC (benzene-1,3,5-tricarboxylic acid) without added solvent
crystalline structure of MOF-5, and the optimal ratio was found to
within 5-15 min.96 This MOF is based on the octahedral secondary
be 3 : 1. Adsorption properties of this MOF toward linear alkanes
building unit (SBU) with small 0.9 nm channels99 (Fig. 18).
(C1−nC7) has been investigated. The results showed that the larger
Klimakow et al.97 obtained Cu3(BTC)2 with high SSA of 1710
adsorbate molecules the stronger adsorbate-adsorbent interactions
m2·g-1 by LAG synthesis followed by activation with an
are. Therefore, at low pressure, MOF-5 more efficiently adsorbed
ethanol/water mixture. This activation step was essential to remove
longer alkanes. Nevertheless, the saturated adsorption capacities of
acetic acid molecules that blocked micropores of the framework,
MOF-5 toward: nC4, nC5, nC6 and nC7 decreased with the
hence mechanochemically obtained Cu3(BTC)2 finally reached
increasing chain length (Fig. 19b).
comparable values of the structural parameters to that of
commercially available sample synthesized in solution. It should
be noted that even if mechanochemical syntheses of MOFs are
solvent-free, their purification is usually needed and may require a
solvent, as in the case of more traditional methods. Nevertheless,
this process is still one of the most environmentally-friendly and
cost-effective approaches to produce MOFs.

This journal is © The Royal Society of Chemistry [2020] Mater. Horiz. | 9

 Page 11 of 19 Materials Horizons View Article Online
DOI: 10.1039/D0MH00081G
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.

Materials Horizons Accepted Manuscript

Fig. 19 (a) Low-temperature N2 adsorption-desorption isotherms
and (b) linear alkanes adsorption isotherms at 25 ºC measured on
MOF-5. Adapted with permission from ref. 101. Copyright © 2017,
American Chemical Society. Fig. 20 (a–f) SEM images (scale bar 500 nm) and (g) TEM image
(scale bar 20 nm) illustrating the progress of mechanochemical
Apart from the highly porous MOF-5, ball milling methods can be reaction for the preparation of ZIF-8 using nano-sized ZnO, (h)
extended to prepare other porous Zn-containing MOFs such as proposed mechanism for the reaction.102
ZIF-8 (zeolitic imidazolate framework),102–104 MOF-74105 or even
bimetallic frameworks106. For example, Miyake group102 reported Zirconium-containing MOFs based on cationic [Zr6O4(OH)412+]
dry mechanochemical conversion of zinc oxide and an imidazole clusters gain an increasing attention, because they combine high
ligand into ZIF-8. The porous product with SSA of 1480 m2·g-1 porosity with good resistance to water, pH and high temperature.
was obtained after milling for 96 h. The authors proposed three Friščić and collaborators obtained a variety of UiO-type and NU-
parallel steps to explain the mechanism of ZIF-8 type Zr-containing MOFs via mechanochemically-assisted
mechanosynthesis: (i) breakage of ZnO agglomerates, (ii) methods.107,108 For instance, microporous Zr-containing NU-901
conversion of ZnO to ZIF-8 and (iii) agglomeration between ZIF- and UiO-67 MOFs with surface areas up to 2250 m2·g-1 were
8 nanoparticles (Fig. 20). Mechanochemistry can be also used to obtained by solvent-free mechanochemical reaction using
convert ZnO into bimetallic CoZn-ZIF MOF sample. For instance, dodecanuclear zirconium acetate as cluster (see compound 1 in Fig.
Co species were introduced to the framework by the addition of 21) and H4TBAPY – 1,3,6,8-tetrakis(p-benzoic acid)pyrene or
cobalt acetate to ZIF-8 precursors and subsequent ball milling at a H2BPA – biphenyl-4,40-dicarboxylic acid, respectively, as ligand
rotation speed of 150 rpm for 1 h. Thanks to the milling process sources (Fig. 21).108
Zn and Co elements were homogeneously dispersed keeping the
overall framework intact. The bimetallic MOF with highest
amount of Co element showed large SSA of 1690 m2·g-1 and CO2
uptake of 0.85 mmol·g-1 (25 °C and 1 bar).106
Another representative, highly porous MOF is chromium-
containing MIL-101. Prepared under hydrothermal conditions with
the addition of hydrofluoric acid and/or other solvent it can possess
SSA of ~3500 m2·g-1.95 While grinding chromium salt and
terephthalic acid (with a Cr/BDC molar ratio of 1.5) prior to
thermal treatment at 220 °C for 4 h in an autoclave, the obtained
MIL-101 yields SSA of 2760 m2·g-1.95

Mater. Horiz. This journal is © The Royal Society of Chemistry [2020]

 Materials Horizons Page 12 of 19
View Article Online
DOI: 10.1039/D0MH00081G
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.

Materials Horizons Accepted Manuscript

Fig. 22 (a) SEM image of InOF-1, (b) XRD diffractograms and (b)
N2 isotherms measured for fresh and after H2O treatment samples,
and (d) CO2, CH4, N2 isotherms measured on InOF-1 at 0 ºC.
Adapted with permission from ref. 109. Copyright © 2016 Elsevier
Ltd.

2.4 Other nanomaterials

Fig. 21 (a) Milling of the Zr12-containing acetate oxocluster with
Covalent organic frameworks (COFs) are porous organic materials
tetratopic or ditopic ligands lead to the formation of (b) NU-901
constructed entirely from light elements (H, C, O, N or B) through
and (c) UiO-67 MOFs, respectively; (d) different modes of ligands
covalent bonds, in contrast to MOFs. Mechanochemistry, as eco-
binding with Zr-based cluster in each MOF.108
friendly and fast approach, has been also utilized for the synthesis
of COFs.115–121 Biswal et al.118 reported, that unlike the
Mechanochemistry has been used for the preparation of other
solvothermally synthesized COFs, the mechanochemically
valuable MOFs such as In-, Fe- or Cd-containing frameworks,109–
112 and MOF-based composites113,114. Fast (20 min) room- obtained ones showed unforeseen graphene-like layered
morphology. To obtain COFs with ordered, layered networks and
temperature LAG reaction of In(OAc)3·6H2O with H4BPTC and
large domain size, high synthetic control over interlayer π−π
CH3CN enabled to obtain highly crystalline, water stable In-OF-1
stacking and layer planarity is required. Highly porous crystalline
MOF with SSA of 710 m2·g-1 and CO2 adsorption capacity of 4.03
COFs with SSA as high as 3110 m2·g-1 and water adsorption
mmol·g-1 at 0 °C and 1 bar. According to IAST, its CO2/CH4 and
capacities up to 78 wt. % at 25 °C were synthesized using grinding-
CO2/N2 adsorption selectivity reached values of 7.5 and 45,
assisted method.115 Such high porosity of a COF sample was
respectively. Importantly, InOF-1 showed an excellent water
obtained through stepwise grinding of p-toluene sulphonic acid,
stability, i.e., neither phase transition nor framework collapse
3,3′-dimethoxybenzidine, 1,3,5-triformylphloroglucinol and water,
occurred during soaking in water for 12 h. Fig. 22 presents (a) SEM
followed by heating at 170 °C for 60 s. Another report
image of InOF-1, (b) XRD diffractograms and (b) N2 isotherms
demonstrates a crystalline COF with SSA of 1500 m2·g-1 (COF-5d)
measured for a fresh sample and the sample after H2O treatment,
obtained after crystallization for 5 days of an imine-linked COF
(d) CO2, CH4 and N2 isotherms measured on InOF-1 at 0 °C.109
pre-synthesized via grinding-assisted method. The crystallized
Formation of MOF composites is driven by chemical and physical
COF-5d sample reached the CO2 adsorption capacity of 8.1 wt. %
interactions e.g., coordination and hydrogen bonding, electrostatic
giving almost 4 times higher uptake compared to that of the COF
interactions and π-π stacking. For instance, water-assisted ball
before crystallization.116
milling conducted by 16 h with 200 rpm grinding speed was used
Mechanochemical concepts seem promising for scale-up
to merge N-doped graphene with ZIF-8 MOF. The obtained
production of porous metal oxides and zeolites for catalysis,
graphene/MOF composite (N-G/MOF-200) possessed high SSA of
battery technology and adsorption, even though the SSA values of
1732 m2·g-1 and Vt of 0.6 cm3·g-1. The composite obtained by using
these materials are so far below 700 m2·g-1.122–132 Especially, new
350 rpm grinding speed (N-G/MOF-350) exhibited SSA of 1100
catalysts have been intensively studied for application in organic
m2·g-1 and showed the highest diffusion-limited current density of
syntheses, water splitting, removal of pesticides and dyes from
5.0 mA·cm-2 among samples studied, surpassing also the catalytic
wastewater, and removal of VOCs, CO2, CO and NOx. Using a fast,
activity of 10 wt. % Pt/C catalyst (4.3 mA·cm-2).114
mechanochemical nonhydrolytic sol-gel approach, Zhang et al.132
obtained mesoporous Al2O3 (meso-Al2O3), mesoporous
aluminum-containing binary oxides, such as CuOx-Al2O3 and
MnOx-Al2O3 as well as a mixed metal oxide (CuNiFeCoMg)Ox-
Al2O3 (Fig. 23). For example, to prepare the five metals-aluminum

This journal is © The Royal Society of Chemistry [2020] Mater. Horiz. | 11

 Page 13 of 19 Materials Horizons
oxide hybrid all reactants: aluminum isopropoxide, a soft template
and anhydrous metal chlorides were ball milled for 1 h at
vibrational frequency of 30 Hz in the first place. Next, the as-
obtained product was washed with ethanol, dried, and calcinated at
400 °C. The as-synthesized (CuNiFeCoMg)Ox-Al2O3 possessed
SSA of 200 m2·g-1 and exhibited high catalytic activity for CO
oxidation as well as remarkable SO2 resistivity (1000 ppm SO2 at
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
280 °C). A record SSA of 640 m2·g-1 and the highest Vt of 0.75
cm3·g-1 showed meso-Al2O3 characterized by narrow pore size
distribution with predominant pore size of ~5 nm. The structural
parameters of this oxide and the binary metal oxides were
comparable to those obtained by traditional wet chemistry method.
Fig. 23 Schematic illustration for the mechanochemical synthesis
of (a) meso-Al2O3 and (b) mesoporous mixed metal oxides.
Reproduced with permission from ref. 132. Copyright © 2019,
American Chemical Society.
Since graphitic carbon nitride (C3N4) has been introduced in 2009
for visible-light water splitting,133 it has been widely studied as a
photocatalyst to degrade pollutants, initiate CO2 reduction
reactions and produce hydrogen gas, among others.134 Degradation
of dyes, and antibiotics in wastewater has attracted a lot of
attention, because these pollutants pose a direct threat to human
and animal lives. Moreover, using photocatalysts, waste toxic CO2
can be transferred into valuable hydrocarbon fuels reducing global
warming effects simultaneously, as CO2 is considered as a major
greenhouse gas. For these purposes, C3N4 showed many beneficial
advantages, because it is low-cost metal-free catalyst with a band
gap of ∼2.7 eV and superior visible light response.133,135 C3N4 is
usually synthesized by calcination of N-rich precursors such as
urea, cyanamide or melamine, but it can also be obtained via high
energy ball milling of C3N3Cl3 and Li3N136 or mechanochemical-
assisted method from graphite and NH3.137 Despite high theoretical
SSA of 2500 m2·g-1 calculated for ideally layered C3N4,138 a typical
bulk sample possesses low porosity (SSA usually up to 100 m2·g-
1), which leads directly to its poor adsorption capacity134,139. Some
tricks have been implemented to enhance SSA of C3N4, e.g.,
precursor modifications, post-synthetic sonication, additional heat
treatment or ball milling exfoliation.134,140 During ball milling of a
bulk C3N4, size and thickness of its layers can be efficiently
reduced improving its overall porosity.140 Due to the huge progress
made in the mechanochemical synthesis during recent two decades
Mater. Horiz.
View Article Online
DOI: 10.1039/D0MH00081G
in the area of nanomaterials, it was possible to synthesize various
C3N4-based composites and functionalized C3N4 via grinding or
milling processes. Some of those materials, such as
graphene/C3N4,68,69 MOF/C3N4,141,142 metal oxide/C3N4139,143–145
and modified C3N4146,147 showed enhanced photocatalytic
properties.
3 Applications
The mechanochemically obtained nanomaterials have a great
potential to be applied in catalysis and adsorption related
Materials Horizons Accepted Manuscript
applications including: separation, removal of pollutants, ion-
exchange, energy conversion, usage and storage. A rapid growth
of population and industry is responsible for the increasing
emission of toxic gases into atmosphere. The most hazardous are
greenhouse gases such as CO2 and CH4, which contribute to the
global warming effect. Moreover, depletion of crude oil resources
requires new solutions related to the energy production and storage.
Clean energy carriers such as hydrogen and methane are great
alternatives to conventional fuels, though their storage is still a
huge challenge. The current research in this area is focused on the
development of efficient, reproducible sorbents and catalysts. So
far, the most promising candidates for the abovementioned uses
are activated carbons, metal-organic frameworks, metal oxides,
graphene- or C3N4-based materials. It has been recognized that the
porous structure is one of the most important features of sorbents.
In general, adsorption depends on both the molecular size of
adsorbate and adsorbate-adsorbent interactions. Highly porous
materials with pores below 0.7 nm (ultramicropores) are especially
suitable for small-sized molecules adsorption such as H2, CO2 and
CH4. Among the various materials presented here, the highest CO2
adsorption capacity of 5.8 mmol·g-1 at 25 °C and 1 bar showed
highly microporous sawdust-derived activated carbon obtained by
using mechanochemical activation prior to thermal treatment. This
method allows also to acquire effective sorbent for H2 storage (1.4
wt. %) from waste tires. Eco-friendly ball milling process produced
the highly porous lignin-derived activated carbons (SSA up to
3200 m2·g-1), which are especially suitable for Li–S batteries and
supercapacitors. MOFs are well-known for their exceptional high
porosity and gas adsorption capacities. So far, mechanochemistry
afforded some highly porous MOFs such as MOF-5, MIL-101 and
U-67 with SSA up to 3500 m2·g-1. We believe that this method is
well suited for a large scale fabrication of MOFs with ultrahigh
porosity (SSA >4000 m2·g-1). Similarly, the graphene-based
materials have the potential to break records in the field of highly
porous carbonaceous solids. Many reports demonstrate remarkable
catalytic activities of mechanochemically obtained nanoparticles,
porous metal oxides, graphitic C3N4 and their composites and have
been in-depth reviewed in ref.2,134 Mechanochemistry enables to
obtain porous nanomaterials and organic compounds the
preparation of which is to some extent difficult or even impossible
via conventional synthetic procedures.148-156 For instance, an
economically accessible precursor for the synthesis of corundum
nanoparticles (α-Al2O3), an important ceramic and catalyst
material, is a naturally occurring mineral boehmite (γ-AlOOH).
Recently, direct 3 h ball milling of boehmite afforded phase-pure
nanocrystalline α-Al2O3 with SSA exceeding 120 m2·g-1, while the
This journal is © The Royal Society of Chemistry [2020]
 Materials Horizons Page 14 of 19
View Article Online
DOI: 10.1039/D0MH00081G

currently used conventional fabrication processes involve harsh
synthetic conditions and offer lower-quality products.156 Highly
porous nanomaterials (porosity expressed in terms of SSA)
obtained via mechanochemically-assisted methods and their
adsorption properties (if reported) are summarized in Table 1.
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
exploited in the coming years. Fundamental studies on the
mechanochemical synthesis of nanomaterials such as metal oxides
and composite materials are vital. There are still many open
questions, for instance, how the structure of reagents changes upon
mechanochemical action? We believe that novel sorbents, catalysts
and other nanomaterials and practical technologies utilizing
mechanochemistry will emerge in near future.

4 Conclusions
It was demonstrated that porous nanomaterials can be successfully
synthesized via mechanochemical reaction. During grinding or

Materials Horizons Accepted Manuscript

milling processes, mechanical energy is used to conduct reactions
at room temperature without the addition of a solvent or with small
amounts of solvents, thus these methods meet criteria of green
chemistry. Herein, we summarized the major achievements
accomplished so far in the area of mechanochemical synthesis of
porous nanomaterials, with emphasis on the sorbents designed for
adsorption related applications. Highly porous activated carbons
with SSA around 3000 m2·g-1 were obtained by
mechanochemically-assisted methods from biomass. Metal- or
covalent organic frameworks with SSA up to 3500 m2·g-1 were
prepared via fast direct grinding of the precursors. Among the
presented sorbents, the highest CO2 adsorption capacity of 5.8
mmol·g-1 at 25 °C and 1 bar showed sawdust-derived activated
carbon, the synthesis of which included the so-called
compactivation. Herein it was highlighted that
mechanochemistry offers many synthetic routes for the
preparation of functional porous nanomaterials such as activated
carbons, ordered mesoporous carbons, graphene-derivatives,
MOFs, COFs, zeolites, metal oxides, carbon nitrides and a huge
variety of composite materials.

5 Outlook and prospects

Beyond fundamental research, mechanochemical synthesis has an
immense potential for chemical and pharmaceutical industries. The
future market demands are for highly efficient, selective and low-
cost sorbents and catalysts produced via environmentally friendly
methods. Considering a wide range of applications of the
functional nanoporous materials, mechanochemistry is a well-
suited way for developing and producing such materials by using
inexpensive and nontoxic precursors, eliminating or reducing the
usage of solvents, and reducing the synthesis time. Synthetic
conditions can be precisely controlled when materials are prepared
in lab scale quantities. When the synthesis is scaled up, uneven
mass and heat transfer effects can easily deteriorate structure and
consequently properties of the fabricated products. Amounts of the
so far synthesized functional materials by means of
mechanochemistry are often between several grams to even
kilograms.61,64,157-159 However, even if materials show potential of
scaling-up process, further increase in their production could be
limited by difficulties in manufacturing the adequate high-
speed/high-energy grinders or mills. Thus, there are still challenges
in scaling up the mechanochemical preparations.
Currently mechanochemistry is not ready to fully replace the
solution-based synthesis methods, but it is undoubtedly a powerful
and eco-friendly tool that should be investigated and better

This journal is © The Royal Society of Chemistry [2020] Mater. Horiz. | 13

 Page 15 of 19 Materials Horizons View Article Online
DOI: 10.1039/D0MH00081G

Table 1 Porous nanomaterials obtained via mechanochemically-assisted methods.

Porous material Description SSA m2·g-1 Application Ref.
denoted as in the original paper
MOF-5-B Zn-containing metal-organic 3470 Linear alkanes adsorption 101
framework
LUPC Lignin-derived carbon 3200 Li–S batteries 22
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.

TpBD-Me2 Covalent organic framework 3110 Water adsorption (78 wt. % at 25 °C) 118
MIL-101(Cr)-1.5-4 Cr-containing metal-organic 2760 Catalytic cyclohexene oxidation 95
framework
MOF-52a Zn-containing metal-organic 2350 H2 adsorption (1.3 wt. % at -196 ºC) 100

Materials Horizons Accepted Manuscript

framework
UiO-67 Zr-containing metal-organic 2250 Hydrolytic degradation of the nerve agent 108
framework simulant dimethyl 4-nitrophenyl phosphate
LD2600P Lignin-derived 2220 CO2 adsorption (4.5 mmol·g-1 at 25 °C 20
mechanochemically activated and 1 bar)
carbon
NDAB3-500 ZnCl2-activated biocarbon 1860 CO2 adsorption (2.1 mmol·g-1 at 25 °C 25
and 1 bar)
HSAC-MCS-900-9 Coconut-derived carbon 1770 Li–S batteries and creatinine adsorption 16
N-G/MOF-200 N-doped graphene 1732 Energy conversion systems 114
oxide/zeolitic imidazolate
framework composite
HKUST-1 Cu-containing metal-organic 1710 Not reported 97
framework
SD2600P Sawdust-derived 1700 CO2 adsorption (5.8 mmol·g-1 at 25 °C 20
mechanochemically activated and 1 bar)
carbon
Co0.9Zn0.1-ZIF Bimetallic zeolitic imidazolate 1690 CO2 adsorption (0.85 mmol·g-1 at 25 ºC 106
framework and 1 bar)
NU-901 Zr-containing metal-organic 1610 Not reported 108
framework
TA_0 Urea-derived activated carbon 1570 Supercapacitors 17
ZIF-8 Zn-containing zeolitic 1480 Not reported 102
imidazolate framework
Zn-MOF-74 Zn-containing metal-organic 1150 Not reported 105
framework
HOMC Ordered mesoporous carbon 1030 Not reported 39
HNO3_COMP Tires-derived activated carbon 950 H2 adsorption (1.4 wt. % at -196 ºC) 19
HIGnPs Iodine-doped graphene 970 Electrocatalytic oxygen reduction 61
nanoplatelets reaction
GO Graphite oxide 730 Methylene blue adsorption (278 mg·g-1) 57
MC-Trypotophan-0.1 N-doped mesoporous carbon 710 Adsorption of CO2 (2.5 mmol·g-1 at 33
25 °C and 1 bar) and light hydrocarbons
InOF-1 In-containing metal-organic 710 CO2 adsorption (4.03 mmol·g-1 at 0 ºC 109
framework and 1 bar)
ENGNP7 Edge-nitrogenated graphene 680 Supercapacitors 62
nanoplatelets
meso-Al2O3 Mesoporous Al2O3 640 Catalytic CO oxidation 132
[Ga]-MFI-100 Ga-substituted MFI-type 500 Methane conversion 124
zeolite
CH3CO2K-activated CH3CO2K- activated ordered Not CO2 adsorption (5.6 mmol·g-1 at 0 °C 32
mesoporous carbon reported and 1 bar) and supercapacitors

Mater. Horiz. This journal is © The Royal Society of Chemistry [2020]

 Materials Horizons Page 16 of 19
View Article Online
DOI: 10.1039/D0MH00081G

Conflicts of interest 25 G. Singh, I. Young Kim, K. S. Lakhi, S. Joseph, P. Srivastava,

There are no conflicts to declare.
Acknowledgments
BS and JC acknowledge the National Science Centre (Poland) for
support of this research under grant UMO-2016/23/B/ST5/00532.
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
R. Naidu and A. Vinu, J. Mater. Chem. A, 2017, 5, 21196.
26 Á. Sánchez-Sánchez, T. A. Centeno, F. Suárez-García, A.
Martínez-Alonso and J. M. D. Tascón, Microporous
Mesoporous Mater., 2016, 235, 1.
27 A. Huang, J. Yan, H. Zhang, X. Li and H. Zhang, J. Energy
Chem., 2017, 26, 121.

28 J. Gao, X. Wang, Y. Zhang, J. Liu, Q. Lu and M. Liu,

References Electrochimica Acta, 2016, 207, 266.
29 J. Górka and M. Jaroniec, Carbon, 2011, 49, 154.
1 Q. Zhang and F. Saito, Adv. Powder Technol., 2012, 23, 523.

Materials Horizons Accepted Manuscript

30 V. Malgras, J. Tang, J. Wang, J. Kim, N. L. Torad, S. Dutta, K.
2 C. Xu, S. De, A. M. Balu, M. Ojeda and R. Luque, Chem.
Ariga, M. S. A. Hossain, Y. Yamauchi and K. C. W. Wu, J.
Commun., 2015, 51, 6698.
Nanosci. Nanotechnol., 2019, 19, 3673.
3 M. Leonardi, M. Villacampa and J. Carlos Menéndez, Chem. Sci.,
31 J. Castro-Gutiérrez, A. Sanchez-Sanchez, J. Ghanbaja, N. Díez,
2018, 9, 2042.
M. Sevilla, A. Celzard and V. Fierro, Green Chem., 2018, 20,
4 M. J. Muñoz-Batista, D. Rodriguez-Padron, A. R. Puente-
5123.
Santiago and R. Luque, ACS Sustain. Chem. Eng., 2018, 6,
32 J. Castro-Gutiérrez, N. Díez, M. Sevilla, M. T. Izquierdo, J.
9530.
Ghanbaja, A. Celzard and V. Fierro, ACS Sustain. Chem. Eng.,
5 L. Takacs, Chem. Soc. Rev., 2013, 42, 7649.
2019, 7, 17627.
6 M. Faraday, Q. J. Sci., Lit., Arts, 1820, 8, 374.
33 J. Zhao, W. Shan, P. Zhang and S. Dai, Chem. Eng. J., 2020,
7 M. C. Lea, Am. J. Sci., 1892, 43, 527.
381, 122579.
8 M. Petruschke, Acta Polym., 1985, 36, 400.
34 K. Zhang, S. Tao, X. Xu, H. Meng, Y. Lu and C. Li, Ind. Eng.
9 K. Horie, M. Barón, R. B. Fox, J. He, M. Hess, J. Kahovec, T.
Chem. Res., 2018, 57, 6180.
Kitayama, P. Kubisa, E. Maréchal, W. Mormann, R. F. T.
35 D. Leistenschneider, K. Wegner, C. Eßbach, M. Sander, C.
Stepto, D. Tabak, J. Vohlídal, E. S. Wilks and W. J. Work,
Schneidermann and L. Borchardt, Carbon, 2019, 147, 43.
Pure Appl. Chem., 2004, 76, 889.
36 A. Sanchez-Sanchez, M. T. Izquierdo, J. Ghanbaja, G.
10 D. Tan and F. García, Chem. Soc. Rev., 2019, 48, 2274.
Medjahdi, S. Mathieu, A. Celzard and V. Fierro, J. Power
11 E. Boldyreva, Chem. Soc. Rev., 2013, 42, 7719.
Sources, 2017, 344, 15.
12 L. Takacs, J. Mater. Sci., 2018, 53, 13324.
37 P. Zhang, L. Wang, S. Yang, J. A. Schott, X. Liu, S. M. Mahurin,
13 M. Thommes, K. Kaneko, A. V. Neimark, J. P. Olivier, F.
C. Huang, Y. Zhang, P. F. Fulvio, M. F. Chisholm and S. Dai,
Rodriguez-Reinoso, J. Rouquerol and K. S. W. Sing, Pure Appl.
Nat. Commun., 2017, 8, 15020.
Chem., 2015, 87, 1051.
38 F. L. Braghiroli, V. Fierro, J. Parmentier, A. Pasc and A.
14 O. K. Farha, I. Eryazici, N. C. Jeong, B. G. Hauser, C. E.
Celzard, Green Chem., 2016, 18, 3265.
Wilmer, A. A. Sarjeant, R. Q. Snurr, S. T. Nguyen, A. Ö.
39 E. Zhang, G.-P. Hao, M. Elizabeth Casco, V. Bon, S. Grätz and
Yazaydın and J. T. Hupp, J. Am. Chem. Soc., 2012, 134, 15016.
L. Borchardt, J. Mater. Chem. A, 2018, 6, 859.
15 M. E. Casco, S. Kirchhoff, D. Leistenschneider, M. Rauche, E.
40 K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y.
Brunner and L. Borchardt, Nanoscale, 2019, 11, 4712.
Zhang, S. V. Dubonos, I. V. Grigorieva and A. A. Firsov,
16 X. Lin, Y. Liang, Z. Lu, H. Lou, X. Zhang, S. Liu, B. Zheng, R.
Science, 2004, 306, 666.
Liu, R. Fu and D. Wu, ACS Sustain. Chem. Eng., 2017, 5, 8535.
41 A. K. Geim and K. S. Novoselov, Nat. Mater., 2007, 6, 183.
17 G. Ayalneh Tiruye, D. Muñoz-Torrero, T. Berthold, J. Palma,
42 M. D. Stoller, S. Park, Y. Zhu, J. An and R. S. Ruoff, Nano
M. Antonietti, N. Fechler and R. Marcilla, J. Mater. Chem. A,
Lett., 2008, 8, 3498.
2017, 5, 16263.
43 Y. Zhang, Y.-W. Tan, H. L. Stormer and P. Kim, Nature, 2005,
18 R. Rajendiran, M. Nallal, K. H. Park, O. L. Li, H.-J. Kim and
438, 201.
K. Prabakar, Electrochimica Acta, 2019, 317, 1.
44 C. Lee, X. Wei, J. W. Kysar and J. Hone, Science, 2008, 321,
19 K. M. Rambau, N. M. Musyoka, N. Manyala, J. Ren and H. W.
385.
Langmi, Mater. Today Proc., 2018, 5, 10505.
45 Y. Zhu, S. Murali, M. D. Stoller, K. J. Ganesh, W. Cai, P. J.
20 N. Balahmar, A. C. Mitchell and R. Mokaya, Adv. Energy
Ferreira, A. Pirkle, R. M. Wallace, K. A. Cychosz, M.
Mater., 2015, 5, 1500867.
Thommes, D. Su, E. A. Stach and R. S. Ruoff, Science, 2011,
21 C. Schneidermann, N. Jäckel, S. Oswald, L. Giebeler, V.
332, 1537.
Presser and L. Borchardt, ChemSusChem, 2017, 10, 2416.
46 Y. Xu and J. Liu, Small, 2016, 12, 1400.
22 C. Schneidermann, C. Kensy, P. Otto, S. Oswald, L. Giebeler,
47 G. Eda and M. Chhowalla, Nano Lett., 2009, 9, 814.
D. Leistenschneider, S. Grätz, S. Dörfler, S. Kaskel and L.
48 A. Ganesan and M. M. Shaijumon, Microporous Mesoporous
Borchardt, ChemSusChem, 2019, 12, 310.
Mater., 2016, 220, 21.
23 D. Leistenschneider, N. Jäckel, F. Hippauf, V. Presser and L.
49 I. A. Baburin, A. Klechikov, G. Mercier, A. Talyzin and G.
Borchardt, Beilstein J. Org. Chem., 2017, 13, 1332.
Seifert, Int. J. Hydrog. Energy, 2015, 40, 6594.
24 Y. Wu, J. Wang, Y. Muhammad, S. Subhan, Y. Zhang, Y. Ling,
J. Li, Z. Zhao and Z. Zhao, Chem. Eng. J., 2018, 349, 92.

This journal is © The Royal Society of Chemistry [2020] Mater. Horiz. | 15

 Page 17 of 19 Materials Horizons
50 L. Zhang, F. Zhang, X. Yang, G. Long, Y. Wu, T. Zhang, K.
Leng, Y. Huang, Y. Ma, A. Yu and Y. Chen, Sci. Rep., 2013,
3, 1408.
51 K. Chen, L. Shi, Y. Zhang and Z. Liu, Chem. Soc. Rev., 2018,
47, 3018.
52 Y. Ma, H. Chang, M. Zhang and Y. Chen, Adv. Mater., 2015,
27, 5296.
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
53 Y. Ma and Y. Chen, Natl. Sci. Rev., 2015, 2, 40.
54 Y.-H. Chu, Z.-M. Wang, M. Yamagishi, H. Kanoh, T. Hirotsu
and Y.-X. Zhang, Langmuir, 2005, 21, 2545.
55 B. Szczęśniak, J. Choma and M. Jaroniec, Adsorption, 2019, 25,
521.
56 A. Klechikov, G. Mercier, T. Sharifi, I. A. Baburin, G. Seifert
and A. V. Talyzin, Chem. Commun., 2015, 51, 15280.
57 A. E. D. Mahmoud, A. Stolle and M. Stelter, ACS Sustain.
Chem. Eng., 2018, 6, 6358.
58 S. Mashkouri, N. Arsalani and H. Mostafavi, J. Alloys Compd.,
2017, 715, 486.
59 A. Amiri, M. N. M. Zubir, A. M. Dimiev, K. H. Teng, M.
Shanbedi, S. N. Kazi and S. B. Rozali, Chem. Eng. J., 2017,
326, 1105.
60 I.-Y. Jeon, S.-H. Shin, H.-J. Choi, S.-Y. Yu, S.-M. Jung and
J.-B. Baek, Carbon, 2017, 116, 77.
61 I.-Y. Jeon, H.-J. Noh and J.-B. Baek, FlatChem, 2018, 12, 10.
62 G. Wang, J. Zhang, S. Hou, W. Zhang, J. Zhou and Z. Zhao,
Electrochimica Acta, 2016, 208, 47.
63 Y. Xue, H. Chen, J. Qu and L. Dai, 2D Mater., 2015, 2, 044001.
64 I.-Y. Jeon, H.-J. Choi, S.-M. Jung, J.-M. Seo, M.-J. Kim, L. Dai
and J.-B. Baek, J. Am. Chem. Soc., 2013, 135, 1386.
65 I.-Y. Jeon, Y.-R. Shin, G.-J. Sohn, H.-J. Choi, S.-Y. Bae, J.
Mahmood, S.-M. Jung, J.-M. Seo, M.-J. Kim, D. W. Chang, L.
Dai and J.-B. Baek, Proc. Natl. Acad. Sci., 2012, 109, 5588.
66 J. Xu, J. Shui, J. Wang, M. Wang, H.-K. Liu, S. X. Dou, I.-Y.
Jeon, J.-M. Seo, J.-B. Baek and L. Dai, ACS Nano, 2014, 8,
10920.
67 D. W. Chang, H.-J. Choi, I.-Y. Jeon, J.-M. Seo, L. Dai and J.-
B. Baek, Carbon, 2014, 77, 501.
68 M. Wang, Z. Wu and L. Dai, J. Electroanal. Chem., 2015, 753,
16.
69 G. S. Shanker, R. Bhosale, S. Ogale and A. Nag, Adv. Mater.
Interfaces, 2018, 5, 1801488.
70 R. Zhang, C.-A. Tao, R. Chen, L. Wu, X. Zou and J. Wang,
Nanomaterials, 2018, 8, 1067.
71 S. Zhao, D. Chen, F. Wei, N. Chen, Z. Liang and Y. Luo,
Ultrason. Sonochem., 2017, 39, 845.
72 X. Lu, W. He, H. Dou, S. Yang, L. Hao, F. Zhang, L. Shen and
X. Zhang, Mater. Lett., 2012, 71, 57.
73 F. Ye, B. Zhao, R. Ran and Z. Shao, Chem. – Eur. J., 2014, 20,
4055.
74 D. Shan, S. Deng, T. Zhao, B. Wang, Y. Wang, J. Huang, G.
Yu, J. Winglee and M. R. Wiesner, J. Hazard. Mater., 2016,
305, 156.
75 B. Zhang, H. Wang, C. Liu, D. Li, H.-K. Kim, C. Harris, C.
Lao, A. Abdelkader and K. Xi, J. Alloys Compd., 2019, 801,
658.
Mater. Horiz.
View Article Online
DOI: 10.1039/D0MH00081G
76 B. Zhao, Y. Zheng, F. Ye, X. Deng, X. Xu, M. Liu and Z. Shao,
ACS Appl. Mater. Interfaces, 2015, 7, 14446.
77 B. Gao, C. Bower, J. D. Lorentzen, L. Fleming, A.
Kleinhammes, X. P. Tang, L. E. McNeil, Y. Wu and O. Zhou,
Chem. Phys. Lett., 2000, 327, 69.
78 I. Z. Papp, G. Kozma, R. Puskás, T. Simon, Z. Kónya and Á.
Kukovecz, Adsorption, 2013, 19, 687.
79 O. S. G. P. Soares, R. P. Rocha, A. G. Gonçalves, J. L.
Figueiredo, J. J. M. Órfão and M. F. R. Pereira, Carbon, 2015,
C, 114.
Materials Horizons Accepted Manuscript
80 M. A. Kabbani, C. S. Tiwary, P. A. S. Autreto, G. Brunetto, A.
Som, K. R. Krishnadas, S. Ozden, K. P. Hackenberg, Y. Gong,
D. S. Galvao, R. Vajtai, A. T. Kabbani, T. Pradeep and P. M.
Ajayan, Nat. Commun., 2015, 6, 7291.
81 H. Furukawa, N. Ko, Y. B. Go, N. Aratani, S. B. Choi, E. Choi,
A. Ö. Yazaydin, R. Q. Snurr, M. O’Keeffe, J. Kim and O. M.
Yaghi, Science, 2010, 329, 424.
82 H. Li, M. Eddaoudi, T. L. Groy and O. M. Yaghi, J. Am. Chem.
Soc., 1998, 120, 8571.
83 H. Li, C. E. Davis, T. L. Groy, D. G. Kelley and O. M. Yaghi,
J. Am. Chem. Soc., 1998, 120, 2186.
84 H. Li, M. Eddaoudi, M. O’Keeffe and O. M. Yaghi, Nature,
1999, 402, 276.
85 M. Eddaoudi, H. Li and O. M. Yaghi, J. Am. Chem. Soc., 2000,
122, 1391.
86 I. Ahmed and S. H. Jhung, Mater. Today, 2014, 17, 136.
87 E. N. Augustus, A. Nimibofa, I. A. Kesiye and W. Donbebe,
Am. J. Environ. Prot., 2017, 5, 61.
88 M. Rubio-Martinez, C. Avci-Camur, A. W. Thornton, I. Imaz,
D. Maspoch and M. R. Hill, Chem. Soc. Rev., 2017, 46, 3453.
89 B. Szczęśniak, J. Choma and M. Jaroniec, J. Colloid Interface
Sci., 2018, 514, 801.
90 J. L. C. Rowsell and O. M. Yaghi, J. Am. Chem. Soc., 2006,
128, 1304.
91 E. Poirier and A. Dailly, Nanotechnology, 2009, 20, 204006.
92 X.-S. Wang, S. Ma, P. M. Forster, D. Yuan, J. Eckert, J. J. López,
B. J. Murphy, J. B. Parise and H.-C. Zhou, Angew. Chem. Int.
Ed., 2008, 47, 7263.
93 M. Safaei, M. M. Foroughi, N. Ebrahimpoor, S. Jahani, A.
Omidi and M. Khatami, TrAC Trends Anal. Chem., 2019, 118,
401.
94 D. Chen, J. Zhao, P. Zhang and S. Dai, Polyhedron, 2019, 162,
59.
95 K. Leng, Y. Sun, X. Li, S. Sun and W. Xu, Cryst. Growth Des.,
2016, 16, 1168.
96 W. Yuan, A. Lazuen Garay, A. Pichon, R. Clowes, C. D. Wood,
A. I. Cooper and S. L. James, CrystEngComm, 2010, 12, 4063.
97 M. Klimakow, P. Klobes, A. F. Thünemann, K. Rademann and
F. Emmerling, Chem. Mater., 22, 5216.
98 A. Pichon, A. Lazuen-Garay and S. L. James, CrystEngComm,
2006, 8, 211.
99 S. S.-Y. Chui, S. M.-F. Lo, J. P. H. Charmant, A. G. Orpen and
I. D. Williams, Science, 1999, 283, 1148.
100 D. Prochowicz, K. Sokołowski, I. Justyniak, A. Kornowicz, D.
Fairen-Jimenez, T. Friščić and J. Lewiński, Chem. Commun.,
2015, 51, 4032.
This journal is © The Royal Society of Chemistry [2020]
 Materials Horizons
101 D. Lv, Y. Chen, Y. Li, R. Shi, H. Wu, X. Sun, J. Xiao, H. Xi,
Q. Xia and Z. Li, J. Chem. Eng. Data, 2017, 62, 2030.
102 S. Tanaka, K. Kida, T. Nagaoka, T. Ota and Y. Miyake, Chem.
Commun., 2013, 49, 7884.
103 P. J. Beldon, L. Fábián, R. S. Stein, A. Thirumurugan, A. K.
Cheetham and T. Friščić, Angew. Chem. Int. Ed., 2010, 49,
9640.
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.
104 T. Azizi Vahed, M. R. Naimi-Jamal and L. Panahi, J. Drug
Deliv. Sci. Technol., 2019, 49, 570.
105 P. A. Julien, K. Užarević, A. D. Katsenis, S. A. J. Kimber, T.
Wang, O. K. Farha, Y. Zhang, J. Casaban, L. S. Germann, M.
Etter, R. E. Dinnebier, S. L. James, I. Halasz and T. Friščić, J.
Am. Chem. Soc., 2016, 138, 2929.
106 K. Imawaka, M. Sugita, T. Takewaki and S. Tanaka,
Polyhedron, 2019, 158, 290.
107 K. Užarević, T. C. Wang, S.-Y. Moon, A. M. Fidelli, J. T.
Hupp, O. K. Farha and T. Friščić, Chem. Commun., 2016, 52,
2133.
108 A. M. Fidelli, B. Karadeniz, A. J. Howarth, I. Huskić, L.
S. Germann, I. Halasz, M. Etter, S.-Y. Moon, R. E. Dinnebier,
V. Stilinović, O. K. Farha, T. Friščić and K. Užarević, Chem.
Commun., 2018, 54, 6999.
109 Y. Chen, J. Xiao, D. Lv, T. Huang, F. Xu, X. Sun, H. Xi, Q.
Xia and Z. Li, Chem. Eng. Sci., 2017, 158, 539.
110 M. Yaser Masoomi, A. Morsali and P. C. Junk,
CrystEngComm, 2015, 17, 686.
111 T. Friščić, D. G. Reid, I. Halasz, R. S. Stein, R. E. Dinnebier
and M. J. Duer, Angew. Chem. Int. Ed., 2010, 49, 712.
112 M. Pilloni, F. Padella, G. Ennas, S. Lai, M. Bellusci, E. Rombi,
F. Sini, M. Pentimalli, C. Delitala, A. Scano, V. Cabras and I.
Ferino, Microporous Mesoporous Mater., 2015, 213, 14.
113 Y. Li, J. Miao, X. Sun, J. Xiao, Y. Li, H. Wang, Q. Xia and Z.
Li, Chem. Eng. J., 2016, 298, 191.
114 S. Zhuang, H. Singh, B. B. Nunna, D. Mandal, J. A.
Boscoboinik and E. S. Lee, Carbon, 2018, 139, 933.
115 S. Karak, S. Kandambeth, B. P. Biswal, H. S. Sasmal, S.
Kumar, P. Pachfule and R. Banerjee, J. Am. Chem. Soc., 2017,
139, 1856.
116 Y. Liao, J. Li and A. Thomas, ACS Macro Lett., 2017, 6, 1444.
117 D. Balaji Shinde, H. Barike Aiyappa, M. Bhadra, B. P. Biswal,
P. Wadge, S. Kandambeth, B. Garai, T. Kundu, S. Kurungot
and R. Banerjee, J. Mater. Chem. A, 2016, 4, 2682.
118 B. P. Biswal, S. Chandra, S. Kandambeth, B. Lukose, T. Heine
and R. Banerjee, J. Am. Chem. Soc., 2013, 135, 5328.
119 H. Lv, X. Zhao, H. Niu, S. He, Z. Tang, F. Wu and J. P. Giesy,
J. Hazard. Mater., 2019, 369, 494.
120 E. Troschke, S. Grätz, T. Lübken and L. Borchardt, Angew.
Chem. Int. Ed., 2017, 56, 6859.
121 S. B. Peh, Y. Wang and D. Zhao, ACS Sustain. Chem. Eng.,
2019, 7, 3647.
122 S. Miyagawa, K. Miyake, Y. Hirota, N. Nishiyama, M.
Miyamoto, Y. Oumi and S. Tanaka, Microporous Mesoporous
Mater., 2019, 278, 219.
123 K. Yamamoto, S. E. Borjas García and A. Muramatsu,
Microporous Mesoporous Mater., 2007, 101, 90.
This journal is © The Royal Society of Chemistry [2020]
Page 18 of 19
View Article Online
DOI: 10.1039/D0MH00081G
124 M. Yabushita, M. Yoshida, F. Muto, M. Horie, Y. Kunitake,
T. Nishitoba, S. Maki, K. Kanie, T. Yokoi and A. Muramatsu,
Mol. Catal., 2019, 478, 110579.
125 M. H. Nada, S. C. Larsen and E. G. Gillan, Solid State Sci.,
2019, 94, 15.
126 W. Xiao, S. Yang, P. Zhang, P. Li, P. Wu, M. Li, N. Chen, K.
Jie, C. Huang, N. Zhang and S. Dai, Chem. Mater., 2018, 30,
2924.
127 A. A. Il’in, R. N. Rumyantsev, K. K. Dao, A. A. Chuyasova,
U. S. Uzhevskaya, D. S. Popov and A. P. Il’in, Glass Ceram.,
Materials Horizons Accepted Manuscript
2019, 76, 145.
128 K. Jirátová, A. Spojakina, L. Kaluža, R. Palcheva, J.
Balabánová and G. Tyuliev, Chin. J. Catal., 2016, 37, 258.
129 M. Lu, N. Fatah and A. Y. Khodakov, J. Mater. Sci., 2017, 52,
12031.
130 A. Pineda, M. Ojeda, A. A. Romero, A. M. Balu and R. Luque,
Microporous Mesoporous Mater., 2018, 272, 129.
131 A. Tadjarodi, M. Izadi and M. Imani, Mater. Lett., 2013, 92,
108.
132 Z. Zhang, S. Yang, X. Hu, H. Xu, H. Peng, M. Liu, B. P.
Thapaliya, K. Jie, J. Zhao, J. Liu, H. Chen, Y. Leng, X. Lu, J.
Fu, P. Zhang and S. Dai, Chem. Mater., 2019, 31, 5529.
133 X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. M.
Carlsson, K. Domen and M. Antonietti, Nat. Mater., 2009, 8,
76.
134 S. Cao, J. Low, J. Yu and M. Jaroniec, Adv. Mater., 2015, 27,
2150.
135 S. C. Yan, S. B. Lv, Z. S. Li and Z. G. Zou, Dalton Trans.,
2010, 39, 1488.
136 H. Zhao, X. Chen, C. Jia, T. Zhou, X. Qu, J. Jian, Y. Xu and
T. Zhou, Mater. Sci. Eng. B, 2005, 122, 226.
137 L.-W. Yin, Y. Bando, M.-S. Li, Y.-X. Liu and Y.-X. Qi, Adv.
Mater., 2003, 15, 1840.
138 T. Sano, S. Tsutsui, K. Koike, T. Hirakawa, Y. Teramoto, N.
Negishi and K. Takeuchi, J. Mater. Chem. A, 2013, 1, 6489.
139 K. Cerdan, W. Ouyang, J. C. Colmenares, M. J. Muñoz-Batista,
R. Luque and A. M. Balu, Chem. Eng. Sci., 2019, 194, 78.
140 Q. Han, F. Zhao, C. Hu, L. Lv, Z. Zhang, N. Chen and L. Qu,
Nano Res., 2015, 8, 1718.
141 X. Du, X. Yi, P. Wang, J. Deng and C. Wang, Chin. J. Catal.,
2019, 40, 70.
142 C.-C. Wang, X.-H. Yi and P. Wang, Appl. Catal. B Environ.,
2019, 247, 24.
143 K. Zhu, Y. Lv, J. Liu, W. Wang, C. Wang, S. Li, P. Wang, M.
Zhang, A. Meng and Z. Li, J. Alloys Compd., 2019, 802, 13.
144 Y. Xin, G. Qiang, H. Xiaoyan, Y. Congxiang, A. Tao, W.
Zhenjun, S. Guodong, S. Xinghua and Z. Peng, Rare Met.
Mater. Eng., 2018, 47, 3015.
145 Q. Chen, H. Hou, D. Zhang, S. Hu, T. Min, B. Liu, C. Yang,
W. Pu, J. Hu and J. Yang, J. Photochem. Photobiol. Chem.,
2018, 350, 1.
146 O. Y. Posudievsky, A. S. Kondratyuk, O. A. Kozarenko, V. V.
Cherepanov, V. G. Koshechko and V. D. Pokhodenko, Int. J.
Hydrog. Energy, 2019, 44, 17922.
147 Z. Sun, G. Yao, X. Zhang, S. Zheng and R. L. Frost, Appl.
Clay Sci., 2016, 129, 7.
Mater. Horiz. | 17
 Page 19 of 19 Materials Horizons View Article Online
DOI: 10.1039/D0MH00081G

148 N. R. Rightmire and T. P. Hanusa, Dalt. Trans., 2016, 45, 158 L.-Y. Zhao, X.-L. Dong, J.-Y. Chen and A.-H. Lu, Chem. Eur.
2352. J., 2020, 26, 2041.
149 A. A. Gečiauskaitė and F. García, Beilstein J. Org. Chem., 159 P. Zhang and S. Dai, J. Mater. Chem. A, 2017, 5, 16118.
2017, 13, 2068.
150 J. Andersen and J. Mack, Green Chem., 2018, 20, 1435.
151 A. Moores, Curr. Opin. Green Sustain. Chem., 2018, 12, 33.
152 J. L. Howard, Q. Cao and D. L. Browne, Chem. Sci., 2018, 9,
Published on 04 March 2020. Downloaded by Linkopings universitetsbibliotek on 3/4/2020 10:41:42 PM.

3080.
153 J.-L. Do and T. Friščić, ACS Cent. Sci., 2017, 3, 13.
154 D. Tan and T. Friščić, European J. Org. Chem., 2018, 1,18.

Materials Horizons Accepted Manuscript

155 T. Friščić, C. Mottillo and H. M. Titi, Angew. Chemie Int. Ed.,
2020, 59, 1018.
156 A. P. Amrute, Z. Łodziana, H. Schreyer, C. Weidenthaler and
F. Schüth, Science, 2019, 366, 485.
157 X. He, Y. Deng, Y. Zhang, Q. He, D. Xiao, M. Peng, Y. Zhao,
H. Zhang, R. Luo, T. Gan, H. Ji and D. Ma, Cell Reports Phys.
Sci., 2020, 1, 100004.

Mater. Horiz. This journal is © The Royal Society of Chemistry [2020]