Chapter 6 - Water treatment and

environmental remediation applications

of carbon-based nanomaterials Xiaoli
Tan & Xin Wang
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 C H A P T E R

6
Water treatment and environmental
remediation applications of carbon-based
nanomaterials
Xiaoli Tan, Xin Wang
MOE Key Laboratory of Resources and Environmental Systems Optimization, College of Environmental
Science and Engineering, North China Electric Power University, Beijing, P.R. China

1. Introduction distinguished new energy source, nuclear po-

Pollution is termed as the presence of undesir-
able chemical matters preventing the natural
process or causing adverse effects to living or-
ganisms and the environment [1e4]. Identifica-
tion and treatment of environmental pollutants
and their prevention measurements are key
steps in the protection of the environment.
Material science plays a vital role in cleaning
environmental pollutants, and materials science
technology has progressed exponentially in the
last decade especially nanomaterials [5,6]. The
pure and clean water is getting scarce due to
industrialization, and the world is facing a
shortage of clean water especially in the devel-
oping world. Water contaminants can be or-
ganics, bacteria, viruses, dyes, heavy metal ions
and radionuclides [7,8], the heavy metal such
as lead (Pb), cadmium (Cd), zinc (Zn), nickel
(Ni), arsenic (As), chromium (Cr), and mercury
(Hg) with nonbiodegradable nature posing a
great risk to human health [9,10]. As a
wer, frequently referred to in “solving the energy
crisis,” has recently received attention for its abil-
ity to satisfy basic energy requirements and
relieve energy pressures. Nevertheless, the
extensive operation and utilization of nuclear en-
ergy will undisputedly produce radioactive
pollution, thereby resulting in different levels
of environmental pollution and potential toxico-
logical effects [8]. Therefore, it is of great urgency
to develop highly efficient and environmentally
friendly methods for the removal or the elimina-
tion of radionuclides from aqueous solutions.
Radioactive elements such as uranium (U), euro-
pium (Eu), strontium (Sr), technetium (Tc),
and americium (Am) have raised concerns about
potential hazards to human health and environ-
mental stability due to their severe pernicious-
ness and durability [11,12].
Because of these severe adverse effects,
removal of heavy metal ions and radionuclides
from water is of prime importance for saving
the human lives from such problematic health

Nanomaterials for Recovery of Radioactive Metal Ions

https://doi.org/10.1016/B978-0-323-85484-9.00006-6 229 © 2022 Elsevier Inc. All rights reserved.
230 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
issues. Toxic metal ions could be removed by
numerous methods, like ion exchange, reverse
osmosis, precipitation filtration, biosorption,
coagulation, and extraction [13e15]. Adsorption
is considered the best method as it is cost-
effective, highly efficient, and easy to operate
for removing trace levels of heavy metal ions
or radionuclides. A variety of materials have
been tested as adsorbents for water contamina-
tion remediation. Commonly used nanomateri-
als for adsorption of pollutants are metal
oxides (Fe3O4, CuO, TiO2, etc.) [16,17], transition
metal chalcogenides (NiS/Ni3S4, MoS2, ZnS,
ZnSe, etc.) [18e21], transition metal carbides
and carbonitrides (MXenes) [22], layered double
hydroxides (LDHs) [23], magnetic nanomaterials
[24], polymer nanocomposites [25] and carbon
nanomaterials, etc. [26]. However, in the scienti-
fic community, carbon-based nanomaterials are
gaining popularity as nano sorbents for water
treatment due to their size and shape dependent
properties, environmentally benign nature, abun-
dance, and ease of handling [17,27]. In this chap-
ter, we will try to review the latest advancement
in the application of carbon nanomaterials,
namely activated carbons (ACs), carbon nano-
tubes (CNTs), graphene, and its derivatives
including graphene oxide (GO) and carbon nano-
fibers (CNFs) in the purification of heavy metal
and radionuclides in ion-contaminated water.
2. Properties of carbon-based
nanomaterials
2.1 Activated carbon
AC is recognized as one of the most popular
and widely used adsorbent in water and waste-
water treatment throughout the world [1,28].
AC is a common term used to describe carbon-
based materials which contains well-developed
internal pore structure. AC is produced from a
variety of carbonaceous rich materials such as
wood, coal, lignite and coconut shell [29]. The
credit to develop commercial AC goes to a Swed-
ish chemist von Ostreijko who obtained two
patents, in 1900 and 1901, on covering the basic
concepts of chemical and thermal (or physical)
activation of carbon, with metal chlorides and
with carbon dioxide and steam, respectively
[30]. The process of chemical activation of
sawdust with zinc chloride was carried out for
the first time in an Austrian plant at Aussing in
1914 on an industrial scale, and in the dye plant
of Bayer in 1915 [31]. In this type of activation,
pyrolytic heating of the carbonaceous material
was performed in the presence of dehydrating
chemicals such as, zinc chloride or phosphoric
acid [32,33]. Despite the efficiency of commercial
AC is high, there have been some drawbacks on
its usage owing to its expensive nature [34].
Current research concentrates on producing
ACs using readily available and cheap materials
with high carbon content and easy preparation,
like plant wastes, agricultural wastes and by-
products from industries [35e37]. Production
of adsorbents using such waste products for wa-
ter/wastewater treatment will help in reducing
the expenses that may be incurred on disposing
of such wastes, and the generating of ACs.
As a carbonaceous material, AC is often pro-
duced by pyrolysis of cellulose-based substances
or bituminous coal at high temperature in the
absence of air. High surface area, porous struc-
ture, and surface reactivity are some of the
important characteristics of ACs [29]. The
adsorption capacity of AC is dependent greatly
on the activation process. The purpose of the
activation step is to improve porosity and the
combustion of the tars present during carboniza-
tion [38]. The processes of activation are based
on the reaction of various components that
make up the carbon structure and can be catego-
rized into physical, chemical, and physical/
chemical activation. The first step of the process
involves removal of the tars which cause pore
blockage. This helps to ease the contact between
the surface of the carbon and the activation
agent. This is followed by the second step in
which small crystals of carbon are combusted.
In the third phase, the oxidation of the carbon
particles takes place [39].
 2. Properties of carbon-based nanomaterials
Physical type of activation is also called ther-
mal activation and is done by oxidizing precur-
sor with the help of activating agent usually
within the temperature ranges of 800e1100
C
to obtain particular composition of AC [40].
The physical activation process consists of two
phases [40]; the first phase entails the burning
of the precursors, while at the second phase, acti-
vation is carried out using activating agents such
as steam, or carbon dioxide [41,42]. The volatile
matters in the char are excluded which brings
about the observation of the porous texture of
the ACs. The paramount aim of gasification is
to increase the pores. Nevertheless, the tempera-
ture must be set with caution. At a decreased
temperature, reactions take place inside the car-
bon surface during the initial state. While at
increased temperature, the reactions become
controlled by diffusion outside the carbon parti-
cles [39]. The ACs yield produced during phys-
ical activation is a bit low, which limits its usage.
Chemical type of activation, the materials are
subjected to activation as well as carbonization.
The precursors are injected with a certain quan-
tity of activating agents. The activating agents
usually used are potassium carbonate, zinc
FIGURE 6.1 Synthesize methods and activator classification for the preparation.
231
chloride, potassium hydroxide, calcium carbon-
ate, sodium hydroxide, and phosphoric acid,
etc. [32,33,43], as shown in Fig. 6.1. The chemical
activation process is normally carried out at a
lower temperature, unlike the physical activa-
tion process. The carbon content obtained from
chemical activation is relatively higher than the
quantity obtained during the physical activation
process. But it requires further washing to
remove the chemical which limits its application
[44,45]. Several kinds of research carried out by
previous authors focused on the physical or
chemical type of activation process. ACs ob-
tained from either of these two methods possess
micropores or are of a low surface area [46,47].
Hence, a combination of both physical as well
as chemical types of activation is necessary. Kha-
lili et al. opined that with physical and chemical
activation processes, there is a likelihood of get-
ting AC with distinct surface characteristics. ACs
with high surface area are deemed important in
solving environmental issues. For physical or
chemical activation process to take place,
burning of the biomass is done and followed
by activation with physical and chemical acti-
vating agents [48]. In addition, there are many
232 6. Water treatment and environmental remediation applications of carbon-based nanomaterials

researchers to load metal oxide or functional
compounds on the surface of the ACs [49,50].
The structure of ACs is highly complex and
depends on the raw material used to produce
it, the method of production, and pretreatment
procedure. AC is sometimes described as hav-
ing a “crumpled” layered surface, in which
flat sheets are broken and curved back upon
themselves. It generally consists of small
graphite crystallites with highly disordered,
irregular, rough, and heterogeneous surfaces
[51]. The surface area of ACs can range from
500 to 1400 m2 g1, with values as high as
2636 m2 g1 [29,52]. The porosity of AC can be
increased by pretreatment with acids or bases
that causes reorganization of their surface and
pores [29]. The porous structural characteristics
of AC are clearly shown by SEM images of coco-
nut shell ACs obtained at different H3PO4
impregnation ratios (Fig. 6.2). The AC prepared
at high impregnation ratio displayed pores with
large pore size. This was understandable. As
the impregnation ratio increased, more H3PO4
could be embedded into the carbon matrix
and participate in the carbon gasification reac-
tions [53]. To get an insight into the effect of
temperature on the porosity, AC honeycomb
monolith (ACH) was prepared from bitumi-
nous coal. A higher carbonization temperature
resulting in chars more resistant to steam acti-
vation, and yielding ACH with less total-pore
volume, higher percentage of micropore vol-
ume, and higher mechanical strength. A longer
steam activation time resulted in the conversion
of a higher proportion of micropores to meso-
pores [54].
The chemical characteristics of ACs are
largely determined by a certain degree of surface
chemical heterogeneity, which is related to the
presence of heteroatoms, i.e., atoms present in

FIGURE 6.2 SEM images of (A) AC-S-1-CO2, (B) AC-S-2-CO2, (C) AC-S-3-CO2, and (D) AC-S-4-CO2 (the as-obtained AC
was named AC-S-X-CO2, where X (¼1, 2, 3, or 4) referred to the H3PO4/precursor impregnation ratio used to prepare the
sample) [53].
 2. Properties of carbon-based nanomaterials
the carbon structure that are not only carbon,
such as oxygen, nitrogen, hydrogen, sulfur, and
phosphorus, which are derived either from the
nature of starting material or introduced during
the activation process [55]. Surface functional
groups (which are formed from these hetero-
atoms) and the delocalized electrons of the car-
bon structure determine the acidic or basic
character of the AC surface [56].
The acidic/basic character of AC surfaces is
closely related to the oxygen-containing surface
groups [57,58]. These groups which are mainly
present on the outer surface or edge of the basal
plane contribute toward the chemical nature of
the carbon. As these outer sites constitute the ma-
jorities of the adsorption surface, the concentra-
tion of oxygen on the surface has a great impact
on the adsorption capabilities of AC [59]. Some
examples of oxygen-containing functionalities
detected on the carbon surface include the
following: carboxylic, lactone, phenol, carbonyl,
pyrone, chromene, quinone, and ether groups
(Fig. 6.3A). Functional groups such as carboxylic
acid, lactone, and phenolic hydroxyl have been
postulated as the sources of surface acidity [62].
Oxygen-containing functional groups are created
when the carbon surface is oxidized [43,63,64].
The activation methods commonly used to intro-
duce oxygen-containing acidic groups are oxida-
tion by gases and wet oxidants. Carbon dioxide
and steam can be used in the gas phase treatment.
ACs shown a high degree of aromaticity with the
presence of oxygen functional groups (carboxyl-
ates, lactones and phenols) on its surface [64].
Wet oxidations can introduce a higher amount
of oxygen into the carbon surface at much lower
temperatures compared with the gas phase
treatment. HNO3 modification generates a signif-
icantly large number of surface functional groups
such as carbonyl, carboxyl, and nitrate groups.
NaOH causes an increase in the content of
hydroxyl groups. The HCl treatment results in
an increase in the volume of single-bonded oxy-
gen functional groups such as phenols, ethers,
and lactones [43]. It has been demonstrated that
oxidation of AC in the gas phase increases mainly
the concentration of hydroxyl and carbonyl
233
surface groups, while oxidation in the liquid
phase can incorporate a higher amount of oxygen
in the form of carboxylic and phenolic hydroxyl
groups onto the carbon surface at much lower
temperatures compared with the gas phase
oxidation [65].
Basicity of ACs can be associated with:
(I) resonating p-electrons of carbon aromatic
rings that attract protons, and (II) basic surface
functionalities (e.g., nitrogen-containing groups)
capable of binding with protons [60,66]. It
was proposed that certain oxygen-containing
surface functionalities such as chromene, ketone,
and pyrone can contribute to the carbon basicity
(Fig. 6.3A). However, the basic character of ACs
arises primarily from delocalized p-electrons of
graphene layers. It was pointed out that the
p-electrons of these layers could act as Lewis ba-
ses. Some researchers studied the contribution of
basal planes to the carbon basicity [67,68]. The
surface basicity of two series carbons was stud-
ied, where oxygen-free carbon sites can adsorb
protons from solution. These sites are located
in p-electron rich regions on the basal plane of
carbon crystallites. Therefore, basic sites are
Lewis-type associated with the carbon structure
itself [65]. It has been shown that introduction
of nitrogen functional groups into the carbon
surface can increase the capacity of ACs to
adsorb UO2þ 2 [69]. Nitrogen-containing function-
alities can be introduced through either reaction
with nitrogen-containing reagents (such as NH3,
nitric acid, and amines) or activation with
nitrogen-containing precursors (Fig. 6.3B)
[70,71]. Possible structures of the nitrogen func-
tionalities include the following: amide group,
imide group, lactam group, pyrrolic group,
and pyridinic group. Nitrogen functionalities
generally provide basic property, which can
enhance the interaction between carbon surface
and acid molecules such as, dipole-dipole, H-
bonding, covalent bonding, and so on [61].
2.2 Graphene
Graphene, an allotrope of carbon, has trig-
gered a new “gold rush” since its discovery by
 234
6. Water treatment and environmental remediation applications of carbon-based nanomaterials
FIGURE 6.3 Proposed acidic and basic oxygen functionalities on carbon surfaces (left) [60]; Types of nitrogen surface functional groups (right):
(A) pyrrole, (B) primary amine, (C) secondary amine, (D) pyridine, (E) imine, (F) tertiary amine, (G) nitro, (H) nitroso, (I) amide, (J) pyridone,
(K) pyridine-N-oxide, (L) quaternary nitrogen [61].
 2. Properties of carbon-based nanomaterials
Novoselov and Geim [72,73]. As the first two-
dimensional (2D) atomic crystal has attracted
great attention in the scientific community [74].
Ideal graphene is a single layer of sp2-hybridized
carbon atoms joined by covalent bonds. Because
of the difficulty in isolating single layers of gra-
phene, “few-layer” graphene (2e5 layers), multi-
layer graphene (2e10 layers) and graphite
nanoplates (2D graphite material with a thick-
ness and/or lateral dimension less than
100 nm) are all considered graphene-family
nanomaterials [75]. Now, graphene has been in
the limelight for some time and many re-
searchers have been working on graphene syn-
thesis; thus, several methods have been
reported for the exfoliation of graphite into gra-
phene [76,77]. They can be divided into two
main categories: top-down approach (mechani-
cal exfoliation (scotch tape); graphite intercala-
tion; nanotube slicing; pyrolysis method;
reduction of graphite oxide; electrochemical
exfoliation; sonication; ball milling; radiation
based methods) and bottom-up approach
FIGURE 6.4 Graphene oxide and Reduced graphene oxide [78].
235
(growth from metal-carbon melts; epitaxial
growth on silicon carbide (SiC); dry ice method;
deposition) [76,77]. At present, the dominant
type of graphene used in adsorption application
is prepared via the GO route (Fig. 6.4) not only
because of its potential for large-scale produc-
tion, but also because it produces a functional
form of graphene that is attractive for adsorption
applications [79]. GO is an intermediate product
during synthesis of reduced graphene oxide
(RGO) and prepared by oxidative exfoliation of
graphite [78]. GO is considered the oxidized
form of graphene, functionalized by a range of
reactive oxygenous functional groups, resulting
in extended graphene sheets decorated with
epoxy and hydroxyl functional groups in the
basal planes and carboxylic acid groups at the
edges, and the oxygenous functional groups on
GO make a significant contribution to its hydro-
philicity and high negative charge density,
which is important for the heavy metal adsorp-
tion [80]. Therefore, we mainly introduce the
properties of GO and RGO.
236 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
GO is conventionally prepared by chemical
oxidation and subsequent exfoliation of pristine
graphite with either the Brodie, Staudenmaier,
Hofmann, or Hummers’ methods, or some varia-
tions of these methods. In 1859, Brodie first found
that only graphitizable carbons containing re-
gions of graphitic structure could be oxidized to
generate graphite oxide by potassium perchlorate
and concentration nitric acid mixture [81]. Then,
Staudenmaier heated the mixture of graphite, sul-
furic acid, nitric acid and potassium perchlorate,
and prepared graphite oxide in 1898 [82]. In
1937, Hofmann et al. [83] used concentrated sul-
furic acid in combination with concentrated nitric
acid and KClO3 for the oxidation of graphite for
the preparation of graphite oxide. In 1958, a
convenient method was introduced to prepared
graphite oxide with concentration sulfuric acid,
sodium nitrate and potassium permanganate by
Hummers and Offeman [84]. At present, there
also had improved or modified Hummers
method [85,86]. All these methods chemically
oxidized graphite to various levels, and the inter-
layer distance of graphite oxide increased from
0.34 nm to 0.8e1.0 nm due to the intercalation
of oxygenous functional groups [87,88]. The in-
crease in interlayer distance could weaken the
van der Waals forces between the adjacent
graphitic layers and is beneficial to the exfoliation
of graphite oxide to obtain GO via ultrasonic
method or mechanical stirring [89]. The concen-
tration of exfoliated GO in organic solvents could
be up to 1 mg mL1, while that in water could
reach to 7 mg mL1 due to the hydrophilic oxy-
genous functional groups on the surface [85].
The reduction of GO to graphene has been
approached by a variety of methods [90]. The
FIGURE 6.5 Synthesis process of GO and RGO from the pristine graphite.
simplest way is thermal annealing, which causes
disproportionation of GO into CO2 and graphene.
Although this method is attractive due to its
simplicity, perfect graphene is not obtained,
even at temperatures up to 1100
C [91]. Instead,
a ruptured carbon framework is obtained that
contains hole defects functionalized with oxygen
functionalities, such as carbonyl groups or ethers.
Temperatures higher than 1500
C are required
for the complete deoxygenation of GO, which
causes reorganization of the carbon framework
[92]. Such conditions are not favorable due to
the high energy cost or the incompatibility with
temperature-sensitive substrates. Chemical
reduction of graphite oxide is one of the excellent
procedures to synthesized RGO/graphene in
large quantities. The GO is reduced by a suitable
chemical process; the reduced GO formed resem-
bles graphene but contains residual oxygen and
other hetero atoms, as well as structural defects
[86]. Various inorganic and organic reducing
agents such as phenyl hydrazine [93], hydrazine
hydrate [94], sodium borohydride [95], ascorbic
acid [96], hydroxylamine [97], hydroquinone
[98], etc. [86] have been explored for the chemical
reduction of GO. During the reduction processes,
most oxygen-containing functional groups of GO
are eliminated and the p-electron conjugation
within the aromatic system of graphite is partially
restored. Finally, the RGO gets precipitated from
the reaction medium because of the recovered
graphite domains of chemically converted gra-
phene sheets with increased hydrophobicity and
p-stacking interaction [86]. The most widely
applied technique used for preparing chemically
converted reduced GO is the chemical reduction
of GO as shown in Fig. 6.5.
 2. Properties of carbon-based nanomaterials
GO is a monolayer graphite oxide, the 2D GO
exhibits a typically wrinkled and sheet-like struc-
ture, as shown in Fig. 6.6A. The typical thickness
of the prepared monolayer GO sheets (Fig. 6.6B)
is about 0.7e1.2 nm, which is much larger than
that of the ideal graphene (0.335 nm) due to the
existence of epoxy, carboxyl and hydroxyl groups
on both sides of the GO sheet [102,103]. Compar-
ison with the X-ray diffraction of GO and RGO
(Fig. 6.6C), a typical broad peak near 10.21
degrees (d-spacing ~8.67 A) can be observed for
237
the GO powder. The peak of RGO shows
an obvious shift to higher 2q angles (25.04 de-
grees; d-spacing ~3.56 A), suggesting that RGO
was well ordered with 2D sheets with more thor-
ough removal of surface functional groups [101].
X-ray photoemission spectroscopy (XPS) in
Fig. 6.6D shows the C1 spectra of graphite, GO
and RGO powder samples. In general, the RGO
exhibits the similar XPS spectrum to that of the
natural graphite, C]C bonds dominate, as
shown by one single peak with small tails at the

FIGURE 6.6 (A) TEM image of GO [99]; (B) hydrazine-reduced graphene oxide sheets [100]; (C) X-ray diffraction (XRD)
patterns of graphite, GO and RGO powder; (D) XPS spectra of graphite, GO and RGO; (E) TGA thermograms for GO and
RGO; (F) Raman spectra of GO, RGONH2 NH2 and RGONaNH3 powder [101].
238 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
higher-binding energy region, confirming the
good restoration of C]C bonds in the RGO. In
contrast, the original GO signal shows two sepa-
rated peaks because of the high percentage of ox-
ygen functionalities, which contained the CeC/
C]C in the aromatic rings, the CeO of epoxy
and alkoxy groups and C]O/OeC]O groups
[101,104]. Thermogravimetric analysis (TGA)
was used to further assess the level of reduction
in GO platelets (Fig. 6.6E). The GO sample
showed significant weight loss with an onset tem-
perature at slightly >10
C, which is attributed to
the elimination of interlamellar water, followed
by loss of oxygen from the GO platelets them-
selves at slightly higher temperatures. RGO
showed much higher thermal stability because
of the more complete de-oxygenation and better
graphitization with enhanced van der Waals
forces between layers [93]. Raman spectroscopy
provides a nondestructive method for character-
izing graphene. Graphene typically exhibits three
main Raman features, G-band, D-band and
two-dimensional modes, each having different
physical origins. Raman spectra of GO and
RGO powder are shown in Fig. 6.6F. The Raman
spectrum of GO and RGO exhibited two intense
peaks at 1328 and 1595 cm1, which correspond
to the D and G bands, respectively. The ratio of
FIGURE 6.7 structure representation of (A) SWCNTs and (B) MWCNTs [108].
I(D)/I(G) of the RGO increased when compared
with GO, indicating that numerous small sp2 do-
mains were formed during the reduction [93,101].
2.3 Carbon nanotubes
After the discovery of buckyball (a ball-like
molecule made of pure carbon atoms) in 1985
by Kroto et al. [105], a tubular form of carbon
was reported by Iijima in 1991 and named car-
bon nanotubes (CNTs) [106]. CNTs have hollow,
one-dimensional (1-D) tubelike structures, with
thin carbon walls, which bring fascinating me-
chanical, electrical, and thermal properties
[107]. CNTs have nano-sized diameters with
high aspect ratios. They can be thought of as gra-
phene nanosheets rolled into cylindrical tubes,
and can be categorized as single-walled CNTs
(SWCNTs) and multi-walled CNTs (MWCNTs)
(Fig. 6.7) [109]. The unique structure of CNTs of-
fers excellent intrinsic properties, including a
large active surface area, high chemical and me-
chanical stabilities, and high electrical conductiv-
ity, which provides immense potential for use as
sensors and electronics for biomedical applica-
tions, as composites, and for adsorption [110].
The high surface area and porosity, the hollow,
layered architecture, small diameter, and high
 2. Properties of carbon-based nanomaterials
aspect ratio of CNTs make them effective for
pollutant adsorption, and they are widely
employed to adsorb water contaminants [10].
There are mainly about three methods to pro-
duce carbon nanotube.
Arc-discharge is the easiest and most common
method of producing CNTs. In this method,
CNTs are formed by creating a hot plasma
discharge between two graphite electrodes
which are connected to the power supply (100
A; 20 V) in the presence of helium (He) gas
(Fig. 6.8A). According to the Ebbesen and
Ajayan [113], as the pressure of He in the cham-
ber increased up to a certain value, the yield of
nanotubes also increases, but after that value,
further increase in He pressure leads to the fall
in CNT yields. Better quality of the nanotubes
depends upon the lowering of the current
[114]. Various gases like, N2, CF4 were used in
place of He gas [115,116]. Shimotani et al. [117]
reported the increased yield of nanotubes with
the use of organic vapors.
Laser-ablation, at first Smalley and his col-
leagues reported the synthesis of single-walled
nanotubes with this method in 1995 [118].
FIGURE 6.8 (A) arc-discharge [111]; (B) Laser-ablation [112]; (C) Chemical vapor deposition.
239
In this method, the carbon source (graphite) is
doped with small amounts of metallic catalyst
(Co and Ni) which is then vaporized with the
help of pulsed laser beam in the presence of inert
gas (typically argon) at very high temperatures
(approximately 1200
C) and at a constant pres-
sure of 500 Torr. As the Nd:YAG laser beam im-
pregnates the target material, it starts vaporizing
and condenses on the other end which is at
comparatively lower temperature (Fig. 6.8B).
Some researchers used double pulsed laser to in-
crease the vaporization which also increased the
yield of single-walled nanotubes up to 1 g day1
[107,119]. Due to the requirement of high-power
usage and employability of expensive lasers, this
synthesis route is a very costly affair.
The chemical vapor deposition (CVD) method
is used for bulk production and controlled
growth of nanotubes [120]. In this method, as
shown in Fig. 6.8C, synthesis of CNTs take place
due to decomposition of a mixture of hydrocar-
bon gases (methane, ethylene, etc.) or volatile
carbon compounds present in the chamber
onto a metallic substrate, where metallic nano-
particles behave as catalyst and nucleation sites
240 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
in the growth process of carbon nanotubes at
temperatures of 500e1000
C and under atmo-
spheric pressure. The selection of catalyst and
preparation of substrate decides the type and
quality of the nanotubes produced. Usually, Fe,
Co, Ni nanoparticles are used as catalyst [121].
Porous silicon is considered an ideal substrate
for controlled growth of carbon nanotubes. In
2002, Govindaraj and Rao [122] used organome-
tallic compounds in place of hydrocarbon gas for
the synthesis of CNTs. The main advantage of
using organometallic compounds is that there
is no requirement of the removal of the catalyst
support after the reaction due to the presence
of same phase of carbon source and catalyst
simultaneously. Further modifications were
done in this technique later. Plasma-enhanced
CVD (PECVD) is the widely used method for
CNT synthesis. This technique was first used
by Ren et al. [123] in 1998. In this process also,
a direct current plasma is used which is respon-
sible for the alignment of the carbon nanotubes.
This technique is basically used in the fabrication
of CNT-based flat panel displays, solar cells etc.
Similarly, a number of studies have been done to
synthesize CNTs by various other types of CVD
methods [124,125].
In general, CNTs are categorized into three
types based on the two-dimensional form of
their sheets: zigzag, armchair and chiral nano-
tubes (Fig. 6.9). The zigzag typically has a hexag-
onal pattern moving around the body of the
tubule. The armchair form contains one or two
cyclohexane conformers, with the carbon atom
also describing a hexagonal pattern as it moves
around the body of the tubule body. The third
form of CNTs is the chiral form. The term chiral
denotes ‘handedness,’ and indicates that the
tube can be twisted in any direction. The chiral
shape of SWCNTs is similar to the zigzag and
armchair forms. All these types usually occur
within SWCNTs [126].
SWCNTs consist of sheets of sp2-hybridized
carbon (graphene sheets) rolled into cylinders
with diameters ranging from 6 to ~20 Å
(Fig. 6.10A), depending on the particular method
and conditions during their synthesis. Lengths
typically range in the hundreds of nanometers
or micrometers [128]. The contact surface of
SWCNTs with pollutants is more than MWCNTs
because SWCNTs consist of a single cylindrical
layer. However, SWCNTs as a sorbent are used
less than MWCNTs for removing contaminants
because its synthesis is more difficult and more
expensive than MWCNTs [126].
MWCNTs contain a group of a graphene cyl-
inders nested together (Fig. 6.10B). A TEM exam-
ination reveals an intershell spacing of between
0.335 and 0.34 nm, supplementing a diminishing
tube diameter. The smallest diameter and largest
spacing are found in the high cover, subsequent
in an unwelcome force, and associated to the
decreasing diameter in the CNTs shell. The
bulk graphite crystal spacing value of 0.34 nm
is nearly as large as that of the CNTs themselves
[126]. Ru [129] established that the interlayer
spacing mean value is 0.3444  0.001 nm, and
that CNTs are larger by a few percent than
bulk graphite crystal. There is a spacing between
the layers, denoted by d ¼ 3.39 Å, which is based
on theoretical computation and is greater than
that observed for graphite. Using a TEM image
experimentally, MWCNTs were found to have
a spacing of d ¼ 3.4 Å [113]. This magical CNT
structure results in awesome chemical and phys-
ical properties. Because of the bond between the
carbon atoms in the sp2 direction, CNTs are one
of the strongest materials in the world [130].
Concluded that CNTs have a strength and
Young’s modulus 10e100 times greater than
that of steel [126]. CNT associate with each other
due to attractive dispersive forces to form bun-
dles, typically comprising tens or hundreds of in-
dividual nanotubes. Adsorption of molecules
takes place on these bundles [128]. Thus, to
gain insight into adsorption on carbon nanotube,
one must consider the structure of the bundle
and the adsorption sites available to the adsor-
bate molecules. Four types of adsorption sites
can be identified: the nanotube interior sites,
the sites on the exterior surface, the groove sites,
and the interstitial sites, as shown in Fig. 6.10C.
 2. Properties of carbon-based nanomaterials 241

FIGURE 6.9 Molecular models of exhibited by SWNTs based on the chirality: armchair, zigzag, and chiral based confor-
mation [107].

FIGURE 6.10 Electronic microscope images of different CNTs: (A) TEM image of SWCNT bundle; (B) SEM image of
entangled MWCNT agglomerates [127]; (C) Four types of adsorption sites of carbon nanotubes [128].
242 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
Internal sites: these sites are found within the
hollow structure of tubes and available only
when ends of the tube are open. Interstitial chan-
nels: these sites are easily accessible for the
adsorbate species and found in the interior space
of the bundle between individual nanotubes.
External grooves: the grooves present on the pe-
riphery of a nanotube bundle and the exterior
surface of the outer most nanotubes, where two
adjacent parallel tubes meet. Exposed surface
site or outside surface: outside surface site is
highly accessible for the adsorbate (external sur-
face adsorption) and found on the curved sur-
face of individual nanotubes on the outside the
nanotube bundles [131,132].
2.4 Carbon nanofiber
Carbon nanofiber (CNF) was first reported in a
patent filed more than 120 years ago; carbon fila-
ments are grown from carbon-containing gases
using a metallic crucible. In 1991, Iijima [106]
found carbon nanotubes and other fullerenes dur-
ing arc discharge, which triggered an outburst of
interest in carbon nanotube and nanofiber. Nano-
meter scale carbon fibers (carbon nanofibers)
show high surface area-to-volume ratio, nano-
scale diameter and mechanical properties, all of
which are of great potential application in mate-
rials science, composite production, energy stor-
age and the chemical industry. The hydrocarbon
FIGURE 6.11 growth mechanism of vapor-growth carbon nanofiber using ultrafine catalytic metal particle.
gases and polymers are widely employed as car-
bon precursors for the production of carbon nano-
fibers [133e135]. Synthesis routes of carbon
nanofiber are mainly CVD, electrospinning, and
templating. The carbon nanofibers derived from
different routes embody different carbon struc-
tures and morphologies [136].
The CVD method is not prepared from a
fibrous precursor, but rather from hydrocarbon
gas, using a catalytic growth process, involving
a complicated chemical and physical process; ul-
trafine transition metal particles, such as iron or
nickel particles with diameter less than 10 nm,
are dispersed on a ceramic substrate, and a hydro-
carbon, such as, benzene diluted with hydrogen
gas, is introduced at a temperature of about
1100
C. Hydrocarbon decomposition takes place
on the catalytic particle, leading to continuous
carbon uptake by the catalytic particle and
continuous output by the particles of well-
organized tubular filaments of hexagonal sp2-
carbon. Thus, the associated costs are inevitably
high. The CVD method is only capable of pro-
ducing relatively short fibers that are difficult
to align, assemble, and process into applica-
tions. CNFs from vapor-growth carbon nano-
fibers have a very special structure like
annular-rings; the nanofiber growth and struc-
ture are shown in Fig. 6.11. The advantage of
vapor-growth carbon nanofiber structure is
sp2 graphite. The thickness of the fibers can be
 2. Properties of carbon-based nanomaterials
adjusted by the metal particle size and the
orientation of the graphite plane can be steered
by the growth temperature and/or the nature
of the metal, such as, iron, which tends to give
to parallel fiber, while nickel often leads to
fishbone-type fibers. However, it required the
carbon precursors to be gas or low boiling point
organic molecules, high temperature, and the
presence of nanometal particles, or else, the
yield of nanofiber is lower [136].
Electrospinning is an effective technique to
produce polymeric nanofibers. The rapidly devel-
oping technique of electrospinning provides a
straightforward and cost-effective approach to
produce fibers with diameters ranging from sub-
microns to nanometers with diameters of approx-
imately 300 nm. It offers many opportunities to
tailor the fiber morphology, chemical composi-
tion, fibrous architecture, and functionality. Dur-
ing electrospinning, a polymer solution is
stretched under a high electrical voltage into
fine filaments, which deposit randomly on an
electrode collector forming a randomly oriented
nanofiber web. A typical electrospinning setup
consists of a metallic spinneret, a syringe pump,
a high-voltage power supply, and a grounded
collector in a humidity-controlled chamber
(Fig. 6.12). A polymer solution, polymer melt, or
FIGURE 6.12 scheme of fundamental setup for electrospinning [137].
243
a sol-gel solution is continuously pumped through
the spinneret at a constant rate, while a high-
voltage gradient is applied between the spinneret
tip and the collector substrate. The solvent contin-
uously and rapidly evaporates, while the jet
stream is whipped and stretched by electrostatic
repulsion forming solidified continuous nanofib-
ers (diameters 50e500 nm) on the grounded col-
lector. Improved electrospinning techniques
have been able to produce aligned nanofiber
arrays, nanofibers with porous surfaces, and
bicomponent cross-sectional configurations (e.g.,
core sheath and side-by-side nanofibers), and to
generate nanofibers on a large scale [137].
In addition to electrospinning and CVD syn-
thesis, templated synthesis with porous sub-
strates and nanowires provides alternative
ways for the production of CNFs. For instance,
Xing et al. [138] demonstrated the templated
synthesis of CNFs by using anodic aluminum
oxide (AAO) membranes and commercially
available colloidal silica nanoparticles (Si NPs)
as cotemplates and phenol resin as a carbon
source. As indicated in Fig. 6.13, Si NPs were
firstly incorporated into the inner wall of AAO
membrane to form Si@AAO, and then phenol
resin was added into the dual templated for
carbonization at 973 K under N2 gas flow to
244 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
FIGURE 6.13 Schematic diagram for the synthesis of MCNFs (AAO, anodic aluminum oxide; NPs, nanoparticles) [138].
form SieC@AAO substrate. Finally, free-
standing CNFs with mesoporous structure
were produced by etching the AAO and Si NPs
in the alkaline solution. In a similar study,
CNFs with uniform structure have been pro-
duced by using tubular porous Al2O3 substrates
and CVD growth of carbon [139]. Carbon
nanofibers containing linear mesocage arrays
were prepared via evaporation-induced self-
assembly method within AAO template with
an average channel diameter of about 25 nm.
The mesocages have an elongated shape in the
transversal direction and possess a large pore
size of about 18 nm. Spark plasma sintering
and hot extrusion processes have been employed
for fabricating carbon nanofiber-aluminum ma-
trix bulk materials. The aluminum powder and
the carbon nanofibers were mixed in a mixing
medium of natural rubber. The carbon nano-
fibers were well dispersed onto the aluminum
particles. The carbon nanofibers were found
to be located on every grain boundary and
aligned with the extrusion direction of the
aluminum-carbon nanofiber bulk materials.
The carbon nanofibers and the formation of
Al4C3 play an important role in the enhancement
of the mechanical properties of the aluminum-
carbon nanofiber bulk material [136].
Carbon nanofibers are described as a noncon-
tinuous 1D carbon nano-allotrope of cylindrical
or conical shape (Fig. 6.14AeC), consisting of
stacked and curved graphene sheets arranged
in various ways. Carbon nanofibers can show
different shapes, as depicted in Fig. 6.14DeF,
based on the criterion of the angle of the gra-
phene layers that compose the filament. Besides
platelets (Fig. 6.14D), tubular or ribbon carbon
nanofibers (i.e., carbon nanotubes, Fig. 6.14E,
so-called fishbone carbon nanofibers) exist in
which the graphene layers are oriented under
an angle between principal and perpendicular
axis [141]. The distinctive arrangements of the
graphene layers depend on the geometric as-
pects of the metallic nanoparticle catalyst and
the feedstock of the gaseous carbon (CO or hy-
drocarbon gas) which is introduced during the
 3. Removal of heavy metal ions by carbon-based nanomaterials 245

FIGURE 6.14 SEM (A, B) and TEM (C) images of carbonized nanofibers [140]; Schematic representations of the three types of
CNFs with different basal-to-edge surface area ratios: (D) platelet-type CNF, (E) tubular-type CNF, and (F) fishbone-type CNF [141].

synthesis processing [142]. It was found that the
different graphene contact areas (edge planes
and basal) play distinct roles within the physical
and chemical behavior of CNFs. They are
frequently described as sp2-based linear fila-
ments with a diameter ranging from 50 to
200 nm and a high aspect ratio exceeding 100.
In general, the carbon nanofiber derived from
CVD or carbonization of electrospinning nano-
fiber shows undeveloped or nonpore structure
and poor functional groups by these methods,
which inhibits its effective application in adsorp-
tion/separation, catalyst supports, and elec-
tronic materials fields. In adsorption filed,
chemical activation, enhancing pore structure
and graft with polymer and metal oxides are
useful way to improve their potential [143e145].
3. Removal of heavy metal ions by
carbon-based nanomaterials
For decades, carbon nanomaterials have
attracted intense attention from scientists and
been employed in a prodigious number of appli-
cations [26,146]. Carbon nanomaterials are the
most common nanoadsorbents, due to their abun-
dant availability, excellent adsorption capacities,
cost-effectiveness, high chemical and thermal sta-
bilities, high active surface areas, and environ-
mentally friendly natures and thus contribute to
wastewater management [147]. Being highly
porous with a large surface area, AC [34] has
been the most commonly used adsorbent for
years. And different forms of carbon or function-
alized carbon such as graphene [77,148], CNT
246 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
[149], CNF [145] also have been implemented for
adsorption. Research on the adsorption of water
contaminants using carbon-based nanomaterials
is proliferating [26,150]. In this chapter, it is vital
to review the current state of the article, for the
use of carbon-based nanomaterials for adsorption
of heavy metal and radionuclides, and to explore
new dimensions and emerging trends which
could help to provide new directions in this active
research area.
3.1 Activated carbon-based
nanomaterials
AC is considered universal adsorbent because
of its inherent physical properties such as large
surface area, porous structure, high adsorption
capacity and large reactive surface. Extensive
research on heavy metal adsorption from indus-
trial wastewater using AC from agricultural or
industrial products wastes have been carried
out. For instance, Shrestha et al. [151] purchased
the lignite and coconut shell-based ACs for
Zn(II) adsorption. The maximum adsorption ca-
pacity for Zn(II) ions was found to be
9.43 mg$g1. Park et al. [152] prepared the
porous biochar from rice straw at 600
C to
remove the Cu(II) and Zn(II). The adsorption ca-
pacities of rice straw biochar calculated by Lang-
muir model for Cu(II) and Zn(II) were 56.5 and
38.6 mg$g1 in single-metal system and 40.2
and 7.9 mg$g1 in binary-metal system, respec-
tively. The results demonstrate that the Cu(II)
and Zn(II) adsorption by rice straw biochar
was the exchangeable cation and complexation,
as shown in Fig. 6.15A. Xu et al. [37] used the
dairy manure to produced two kinds of chars
(DM200 and DM350) at 200 and 350
C. AC pyro-
lyzed at the high temperature show better affin-
ity for Cu(II), Zn(II) and Cd(II), which is
attributed to its higher content of CO2 3 . The
maximum sorption capacities of Cu, Zn, and
Cd by DM350 were 54.4, 32.8, and 51.4 mg$g1,
respectively. Park et al. [153] also collected
sesame straw from a local agricultural field and
used to produce biocarbon by pyrolyzing at
700
C for 4 h. They had tested the competitive
sorption of metals by the adsorbents. The
maximum adsorption capacities (mg$g1) of
metals by AC determined from the Langmuir
isotherms were in the order of Pb (102) > Cd
(86) > Cr (65) > Cu (55) > Zn (34) in the mono-
metal adsorption isotherm and Pb (88) > Cu
(40) > Cr (21) > Zn (7) > Cd (5) in the multime-
tal adsorption isotherm, as shown in Fig. 6.15B.
AC shows the potential for the remediation of
heavy metal. However, the adsorption capacity
needs to be further improved.
Improving the adsorption property of AC, it is
a key parameter to improve the porosity struc-
ture. The activated agent such as acid, alkali
and ZnCl2 and so on can enhance the porosity
structure. Xu et al. [33] produced ACs from
reedy grass leaves by chemical activation with
H3PO4 in N2 atmosphere, the surface area
of the ACs produced at 500
C for 2 h were
1474 m2 g; Anisuzzaman et al. [154] produced
the best AC using physical and chemical activa-
tion phosphoric acid (H3PO4), which was found
to be around 1238 m2 g1 of the SBET. Moham-
madi et al. [155] prepared high-surface-area AC
by chemical activation of glycyrrhiza glabra
residue with ZnCl2 as active agent. ZnCl2 modi-
fied AC had higher SBET ¼ 1836.46 m2 g1 are
larger than that of HCl (3.56 m2 g1) and KOH
(20.98 m2 g1) modified activated carbon at the
pyrolysis temperature of 700
C, and its adsorp-
tion capacity can achieve 398.4 mg g1 for
Cr(VI). And the maximum adsorption capacity
of Pb(II) and Ni(II) ions were found to be 200
and 166.7 mg g1.
Improving the adsorption property of AC can
be expected to enhance the adsorption sites or
surface functional groups. Lian et al. [156] pre-
pared AC by chemical modification using
HNO3 and H3PO4 to enhance Pb(II) adsorption.
Batch adsorption experiments revealed the
improvement of adsorption capacity by 39 times
over the unmodified AC. The maximum
 3. Removal of heavy metal ions by carbon-based nanomaterials 247

FIGURE 6.15 (A) Adsorption mechanism of rice straw biochar and single- and binary-metal adsorption isotherms for Cu and
Zn by rice straw biochar [152]; (B) Monometal and multimetal adsorption isotherms for the five metals (Cd, Cr, Cu, Pb and Zn) by
sesame straw in the batch experiment. (C) Monometal adsorption isotherm, (B) Multimetal adsorption isotherm. Square box:
Comparison of the maximum adsorption capacity of the heavy metals in monometal and multimetal adsorption isotherms [153].
248 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
adsorption capacities calculated from Langmuir
models were 120.6, 123.9, and 131.6 mg g1,
respectively, at 298, 308, 318 K. Pb(II) was
mainly combined with the carboxyl, hydroxyl,
and phosphate functional groups via electro-
static interactions and hydrogen bonding. Yunus
et al. [157] prepared two types of honeydew peel
activated carbon with 10%, 20% and 30% of
H2SO4 (HDP-ACS) and H3PO4 (HDP-ACP).
SBET is ranged from 706.35 to 950.09 m2$g1.
The maximum adsorption capacity (Qmax) was
834.94 mg for Cr3þ and 326.19 mg for Zn2þ per
gram of HDP-ACS. On the contrary, HDP-ACP
had 888.85 mg for Cr3þ and 336.51 mg for Zn2þ
g1. Kasnejad et al. [158] introduced nitrogen
functional groups such as amine, pyridinic, and
pyrrolic onto the surface of adsorbents to replace
oxygen groups for producing strong adsorbents
toward heavy metals like Cu(II) ion. Heat treat-
ment of the preoxidized adsorbents under the at-
mosphere of ammonia at 800
C for 3 h. The
nitrogen functional groups fixed on the surface
of adsorbent, gave a basic characteristic to it.
This basic nature could strengthen the reaction
of AC surface with Cu2þ ions according to the
acidebase Lewis theory. The Cu2þ adsorption
tests showed that the aminated carbon could
adsorb Cu(II) with a higher initial rate and
greater capacity than the virgin adsorbent
and the aminated one without preoxidation.
The nitrogen functional groups of the peroxide-
aminated sample were found as the responsible
sites for the enhanced metal ion adsorption ca-
pacity and rate.
AC also combine with other chemical com-
pound to improve its performance. A novel engi-
neered biochar prepared through modification
with chitosan and pyromellitic dianhydride
(PMDA) was investigated as an adsorbent for
the removal of heavy metal ions from single-
metal and mixed-metal solutions (Cd, Cu and
Pb). The Langmuir model fit better than the
Freundlich model, implying that the monolayer
adsorption played a significant role in the metal
removal mechanism (Fig. 6.16AeC). The
chitosan-PMDA modified biochar had strong se-
lective adsorption of Cu(II). The types of effec-
tive functional group for these heavy metal
removals were different. The NeC]O group
played a dominant role in the process of Pb(II)
removal, while several N-containing functional
groups and C]C groups participated in the
adsorption of Cd(II). The novel engineered bio-
char had selective adsorption capacity for copper
due to the N-containing functional groups,
meanwhile abundant carbonyl groups also
participated in the removal of copper, and may
reduce Cu(II) to Cu(I) [159]. Poly (acrylic acid)
modified activated carbon nanocomposite
(PAA-AC) was synthesized for Cd(II) removal.
The maximum capacity and equilibrium time
for adsorption of Cd(II) by PAA-AC were
473.2 mg$g1 and 15 min (Fig. 6.16D and E).
Moreover, the removal of Cd(II) for real electro-
plating wastewater by PAA-AC could reach
98.5%. These meant that the removal of Cd(II)
by PAA-AC was highly efficient and fast. The
adsorption mainly was a chemical process by
chelation [160]. AC modified by linear polyethy-
leneimine (PEI) was to prepare polyethylenei-
mine modified AC (PEI/AC) adsorbent, which
was applied in the Cd(II) ions adsorption in
wastewater. The adsorption of Cd(II) by PEI/
AC was a pH-dependent process with a
maximum adsorption capacity of 45 mg g1 at
an initial solution pH of 6e7 [163]. A two-in-
one attempt for the removal of metal ions on
AC has been developed. The method was based
on the modification of AC with tartrazine then
its application for the removal of Pb(II), Cd(II),
and Cr(III) ions at different pH values. The
Qmax were 121.3, 67 and 56.7 mg$g1 at initial
pH values of 1.0, 6.0 and 10, respectively. The
adsorption capacity for Pb(II), Cd(II), and Cr(III)
ions has been improved with respect to nonmo-
dified carbon reaching a maximum of 140%
[164]. For easy separation of AC from solution,
magnetic activated carbon/chitosan composite
(MAC/CS) from spent coffee grounds and
shrimp shells were synthesized using green tea
 3. Removal of heavy metal ions by carbon-based nanomaterials 249

FIGURE 6.16 Adsorption isotherms of lead (A), cadmium (B) and copper (C) onto chitosan and pyromellitic dianhydride
(PMDA) modified biochar (CPMB) [159]; (D) Adsorption kinetics of Cd(II) on poly (acrylic acid) modified activated carbon
nanocomposite (PAA-AC); (E) Adsorption isotherms and removal of Cd(II) on PAA-AC [160]; (F) Schematic illustration of
the possible mechanism for the adsorption of Ni(II) ions onto MACCS beads [161]; (G) adsorption mechanism of Cd2þ onto
Fe2þ/Fe3þ and NaOH modified biochar [162].

extract as a cross-linker [161]. A possible adsorp-
tion mechanisms of Ni(II) ions onto the MAC/
CS beads is proposed, where the adsorption pro-
cess mainly took place through ion exchange,
complexation and electrostatic attraction
(Fig. 6.16F). The biochar was modified by
Fe2þ/Fe3þ and NaOH, and a further analysis of
the adsorption of Cd(II) on the new biochar
was conducted. The adsorption capacity for
cadmium of the modified biochar was
406.46 mg g1, which was 16 times that of the
original biochar; the CeOeFe structure that
formed on its surface was the main reason for
the sharp increase in adsorption. Among the
iron components, iron oxides (Fe3O4, g-Fe2O3
and FeeOeFe), iron-containing functional
groups (-Fe-R-COOH and Fe-R-OH, etc.) and
the mineral crystal reacted with the Cd(II) ion
in aqueous solution to exchange, form com-
plexes and precipitate, achieving the purpose
250 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
of fixing the heavy metal. In addition, the aro-
matic structure C¼Cp can also adsorb Cd2þ to
generate C¼Cp-Cd, as shown in Fig. 6.16G [162].
Nowadays, nano mineral modified AC show
a promising adsorption capacity for pollutants
removals by combining the advantages of
porous structure of char and unique property
of nano minerals. The zinc oxide loading to
granular-ACs was used for Pb(II) adsorption.
The zinc oxide loading to AC was found to be
effectively used for the Pb(II) adsorption.
From the experimental results, the surface
functional groups responsible for the Pb(II)
adsorption on the zinc oxide loaded AC were
considered hydroxyl groups that formed on
the oxide, while those on the oxidized AC
were considered carboxylic groups [49]. In
addition, nano ZnO/ZnS modified biochar
was synthesized from slow pyrolysis of the
zinc contaminated corn stover obtained from
a biosorption process. The characterization
results indicated that the zinc mineral modified
biochar had a better porous structure
(BET ¼ 397.4 m2$g1) than the common biochar
(BET ¼ 102.9 m2$g1), and zinc minerals were
evenly anchored on the biochar surface as
nano ZnO/ZnS. The enhancement of the metals
removal by the nano ZnO/ZnS modified bio-
char were mainly attributed to the hydroxyl
groups on the surface of nano ZnO/ZnS parti-
cles and well-developed porous structure cata-
lyzed by zinc salt during pyrolysis process
[50]. In addition, other new technique was
developed to functionate AC. Highly concen-
trated amino group-modified biochars derived
from 12 biomass residuals are achieved using
a two-step radio-frequency Ar/NH3 plasma.
The uptake capacities of Pb(II) (123.1 mg$g1),
Cu(II) (98.5 mg$g1), and Cd(II) (61.2 mg$g1)
on aminated biochars are 5.42, 5.38 and 7.56
times higher than those on raw biochars.
This study shows attractive prospects for
the fundamental research in powder modifica-
tion as well as potentials in environmental
management [165].
3.2 Graphene-based nanomaterials
Graphene has tremendous potential in
adsorption. Its main derivations have GO and
RGO, which contain hydroxyl, carboxylic, and
epoxide functional groups on the surfaces.
Considering the high surface area and abundant
functional groups on the GO surfaces, the mate-
rial showed high adsorption capacity in the
removal of heavy metal ions from aqueous solu-
tions. Zhao et al. [166] prepared few-layered GO
(FGO) by modified Hummers’ method. The c-
axis spacing of graphite increased from 0.34 to
0.87 nm during the oxidation process, which
was attributed to the formation of the oxygen-
containing functional groups (e.g., CeO and
C]O) on the surfaces of FGO. The maximum
removal capacity of Pb(II) on FGO at 293 K
was 842 mg$g1. Wang et al. [167] prepared
RGO by reducing GO with ethylenediamine.
The adsorption behavior of RGO for Pb(II),
Cd(II), Cu(II), and Mn(II) was studied. The
adsorption capacities of RGO were found to
be 413.22, 162.33, 55.34 and 42.46 mg g1 for
Pb(II), Cd(II), Cu(II), and Mn(II), respectively,
and adsorption reaches equilibrium within
60 min.
Graphene has shown excellent properties in
wastewater treatment, but still many drawbacks
exist which limits the practical applications of
the graphene-based materials. For instance, gra-
phene/RGO sheets with a hydrophobic graphitic
lattice tend to undergo layer to-layer aggregation
in water due to hydrophobic forces, whereas GO
sheets with carboxyl, hydroxyl, and epoxy groups
on the surface can form relatively stable suspen-
sions [168,169]. In order to enhance its dispersibil-
ity and to reduce the aggregation of graphene/
GO, all kinds of surface-modified graphene/GO
were synthesized via chemical modification or
attaching a stabilizer such as a soluble polymer
or a surfactant to graft different functional groups
on the surfaces. Various organic molecules func-
tionalized GO materials have already fabricated
and applied in adsorption areas [170e176].
 3. Removal of heavy metal ions by carbon-based nanomaterials
Sitko et al. [170] prepared the aminosilanized
graphene oxide (GO-NH2) was prepared for
selective adsorption of Pb(II) ions, as shown in
Fig. 6.17A. The adsorption is controlled by a
chemical process involving the surface complexa-
tion of Pb(II) ions with the nitrogen-containing
groups on the surface of GO-NH2. Such features
of GO-NH2 nanosheets as wrinkled structure,
softness, flexibility, and excellent dispersibility
in water allow achieving very good contact
with analyzed solution, and adsorption of Pb(II)
ions is very fast. Tan et al. [171] enhanced sorp-
tion capacities of GO for copper(II) and lead(II)
under weakly acidic conditions by L-trypto-
phan-functionalization (GO/l-Trp). The number
of -COONa increases after GO reacted with
1-Trp and -COONa on GO/1-Trp plays a sub-
stantial role in enhancing sorption capacities.
The eOH, eNH2, and eCOOH groups on GO/
1-Trp are negatively charged with the pH
increase, as shown in Fig. 6.17B, and its sorption
capacity toward Cu(II) and Pb(II) is strengthened.
Carpio et al. [172] produced graphene oxide func-
tionalized with ethylenediamine triacetic acid
(GOeEDTA) for heavy metal adsorption. The
maximum adsorption capacity of the GOeEDTA
was determined to be 454.6 and 108.7 mg$g1 for
Pb2þ and Cu2þ. Li et al. [173] synthesized the
diethylenetriaminepentaacetic acid (DTPA)-
modified magnetic graphene oxide (MGO) for
removal of Cu(II), Pb(II), and Cd(II) ions from
acidic aqueous solutions. DTPA/MGO compos-
ites exhibited excellent adsorption property in
acidic aqueous solutions. The maximum adsorp-
tion capacities at pH 3.0 for Cu(II), Pb(II), and
Cd(II) ions were 131.4, 387.6, and 286.5 mg g1,
respectively (Fig. 6.17C). Yap et al. [174] designed
cysteamine functionalized RGO (Cyst-prGO)
by thiol-ene click reaction and applied to the
removal of Hg(II). The high elimination capacity
(169  19 mg$g1), high selectivity and high
regeneration ability were achieved (Fig. 6.17D).
No doubt that chemical modification of
GO with different functional groups have shown
high adsorption capacity, fast adsorption
251
kinetics, and superior selectivity in the preconcen-
tration of heavy metal ions from wastewater.
GO/polymer composites have excellent adsorp-
tion properties for heavy metal ions [177e182].
The active functional groups from GO and poly-
mer can interact with heavy metal ions through
ion exchange, surface complexation, and chela-
tion, the high specific surface area can also pro-
vide enough adsorption sites and thereby
enhances the adsorption capacity of GO/polymer
composites for the binding of heavy metals. Luo
et al. [177] fabricated an efficient adsorbent by a
simple cross-linking reaction between GO and
oligomeric poly3-aminopropyltriethoxysilane
(PAS) oligomer, as shown in Fig. 6.18A. PAS-
GO has a priority tendency to adsorb Pb and
Cu from a mixed solution of metal ions, especially
from practical industrial effluent. Liu et al. [178]
studied the graphene oxides cross-linked with
hyperbranched polyethylenimine (GO-HPEI) on
the Pb(II) ions, as shown in Fig. 6.18B. The GO-
HPEI gel exhibited an adsorption capacity as
high as 438.6 mg$g1 for Pb(II) ions, and its insol-
ubility in water makes the separation from waste-
water easy. Musico et al. [179] used poly(N-
vinylcarbazole) (PVK) to blend with GO to form
a PVKeGO polymer nanocomposite for removal
of Pb(II) from water. The highest adsorption ca-
pacity of the PVKeGO nanocomposite for Pb2þ
was 887.98 mg$g1 and fits well the Langmuir
model. Li et al. [180] successfully synthesized chi-
tosan/sulfydryl-functionalized GO composite
(CS/GO-SH) via covalent modification and elec-
trostatic self-assembly. In the ternary metal ion
system, the results demonstrated that CS/GO-
SH is an effective adsorbent when various ions
exist simultaneously. The order of adsorption
competitive capacity is Cd(II) > Cu(II) > Pb(II),
as shown in Fig. 6.18C. Yakout et al. [181] have
studied the extraction of Cu(II) and Pb(II) ions
from different types of aqueous solution by novel
cross-linked GO sheets by modified extracted
cellulose. The cross-linked GO sheets showed
maximum adsorption capacity 46.39 and
186.48 mg$g1 for Cu(II) and Pb(II), respectively.
 252
6. Water treatment and environmental remediation applications of carbon-based nanomaterials
FIGURE 6.17 (A) Adsorption mechanism of aminosilanized graphene oxide nanosheets (GO-NH2) for lead [170]; (B) Adsorption mechanism of L-
tryptophan-functionalized graphene oxide for copper(II) and lead(II) [171]; (C) Adsorption isotherms of Cu(II), Pb(II), and Cd(II) ions on DTPA/MGO
(pH ¼ 3.0, m V1 ¼ 0.4 mg mL1, T ¼ 293 K, t ¼ 24 h) [173]; (D) Influence of co-ions on Hg(II) adsorption by Cyst-prGO (*[Hg(II)] ¼ 30 mg$L1, [M
(II)] ¼ 1000 mg$L1; **[Hg(II) ¼ [M(II)] ¼ 1000 mg L1) [174].
 3. Removal of heavy metal ions by carbon-based nanomaterials 253

FIGURE 6.18 (A) Synthesize process and adsorption mechanism of PAS-GO for Pb(II) [177]; (B) Adsorption mechanism of
GO-HPEI for Pb(II) [178]; (C) Adsorption isotherms of Cd (II), Pb (II), and Cu (II) adsorbed by CS/GO-SH in ternary metal ion
systems (dosage of CS/GO-SH 1.0 mg$mL1 at 293 K, initial solution pH of 5, contact time 90 min) [180]; (D) Cr(VI) removal
efficiency of G-PDAP at different pH levels with 500 mg$L1 initial Cr(VI) concentration [182].

Dinda et al. [182] synthesized sulfuric acid doped
diamino pyridine polymers in situ on GO surface
(G-PDAP) via mutual oxidation-reduction tech-
nique. It shows very high adsorption capacity
(609.76 mg$g1) during removal process. The
composite takes only 100 min to remove the
high concentration of 500 mg$L1 Cr(VI) from
water. Interesting features for this material are
the enhancement of removal efficiency at lower
acidic condition due to the formation of acid
doped emeraldine salt during polymerization,
as shown in Fig. 6.18D. The preparation of the
GO-organic compound nanocomposites was not
complicated, and the surface grafted organic com-
pound could provide more active sites and
oxygen-containing functional groups, which
were favorable for the formation of surface com-
plexes with metal ions and thereby enhanced
the sorption capacity of the composites. Another
advantage of such composites is that the surface
254 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
grafted organic compounds could prevent the ag-
gregation of the GO in aqueous solutions, which
is also favorable to provide more functional
groups and active sites for the binding of metal
ions to the composites.
However, a great challenge is that the high-
water solubility and small size of these function-
alized GO materials make them extremely diffi-
cult to be separated from wastewater after
heavy metal ions adsorption. To overcome this
deficiency, Fe3O4 was compounded with GO to
form magnetic graphene/iron oxide composites
(Fe3O4/GO) which showed the advantages of
both Fe3O4 and GO nanomaterials with high
sorption capacity and separation efficiency.
Harijan et al. [183] synthesized magnetite gra-
phene composite (MGC) for Cr (VI) removal.
The maximum sorption capacity for Cr (VI) on
MGC was much higher than that of Fe3O4 nano-
particles. The graphene sheets could not only
prevent the agglomeration of Fe3O4 nanopar-
ticles and enable a good dispersion of this oxide
but also substantially enhance the specific sur-
face area of the composite. Kumar et al. [184]
synthesized graphene oxide-MnFe2O4 magnetic
nanohybrids (GONH) for efficient removal of
Pb and As from water. This exceptional adsorp-
tion property is due to the combination of the
unique layered nature (allowing maximum sur-
face area) of the hybrid system and the good
adsorption capabilities of both the GO and NP.
Bhunia et al. [185] reported that the maximum
adsorption capacity of RGO-Fe(0)-Fe3O4 for
As(III) is as high as 44 mg$g1, followed by
RGO-Fe(0) (37 mg$g1), this material can also
adsorb other heavy metal ions like Cr(VI),
Cd(II), Pb(II), and Hg(II) ions from wastewater.
Researchers also tried to synthesized multifunc-
tional MGO [186e190]. Sun et al. [186] prepared
magnetic triethylene tetramine-graphene oxide
ternary nanocomposite (CoFe2O4-TETA-GO)
and application for Cr(VI) removal. The satu-
rated adsorption capacity of Cr (VI) was about
180.12 mg g1 on the CoFe2O4-TETA-GO at
pH ¼ 2. Li et al. [187] synthesized magnetic
chitosan and graphene oxide-ionic liquid
(MCGO-IL) composites as biodegradable bio-
sorbents by impregnating MCGO with ionic
liquid. The stronger intermolecular hydrogen
bond between MCGO-IL and Cr(VI) and the hy-
droxyl and amine groups were believed to be
the metal ion binding sites. Cui et al. [188] used
EDTA functionalized MGO (EDTA-mGO), a
good adsorbent for Pb(II), Hg(II) and Cu(II), was
synthesized in the present work. The maximum
adsorption capacity was 508.4 mg g1 for Pb(II),
268.4 mg$g1 for Hg(II) and 301.2 mg$g1 for
Cu(II) from Langmuir isotherm. In addition, there
are researcher further functionated the magnetic
graphene/GO.
In addition, GO can also interact with other
commonly used metal oxides such as MnO2
SiO2, ZnO, and ZrO2 and thereby can form
composites for the application in wastewater
treatment. Wang et al. [191] fabricated novel gra-
phene oxide-ordered mesoporous silica mate-
rials with 2D mesoporous structure and large
surface area through sol-gel and self-assembly
methods. The results showed that the materials
exhibited superior adsorption capacity, the
removal efficiencies for As, Cd, Cr, Hg, and Pb
reached 97.7%, 96.9%, 96.0%, 98.5%, and 78.7%,
respectively. Lingamdinne et al. [192] synthe-
sized a hybrid graphene oxide based inverse
spinel nickel ferrite (GONF) nanocomposite ma-
terial and subsequent utilization in heavy metal
removal from aqueous solution. Santhosh et al.
[193] synthesized cobalt ferrites decorated 2D
porous graphene nanocomposites (PG-C) for
the cationic and anionic metal ions removal.
The adsorption capacity of PG-C for Pb(II) ions
was found to be 131.40 and 68.85 mg$g1 for
Cr(VI). Luo et al. [194] prepared GO-ZrO(OH)2
by hydrothermal coprecipitation and the adsorp-
tion capacities for As(V) and As(III) were 84.89
and 95.15 mg g1, respectively, which were
4.64 and 3.54 times higher than that of ZrO(OH)2
nanoparticles. According to the results reported
by Ren et al. [195], graphene/d-MnO2, which
was synthesized by oxidation-reduction
 3. Removal of heavy metal ions by carbon-based nanomaterials
processes, had the adsorption capacity of
46.6 mg$g1 for Ni(II). Under optimal condi-
tions, the maximum adsorption of Ni(II) over
the graphene/d-MnO2 composites were 1.5 and
15 times higher than those of d-MnO2 and
graphite nanosheet, respectively. However,
compared with other nanomaterials, it is still a
challenging task of improving the removal effi-
ciency of GO/metal oxide composites.
3D graphene-based materials (3D GMs) also
have been proved as an effective means in
providing the self-supporting architecture to
avoid the aggregation of graphene nanosheets
[196e203]. Which then improves recyclability
and regeneration. The microporous, mesopo-
rous, and macroporous morphologies of 3D
graphene-based aerogels (3D BAs) make them
convenient and easily recyclable catalysts using
just simple physical separation. 3D GBMs can
also enhance the practical application of the com-
posite material such as porous structure and the
high surface area of 3D GBMs. Furthermore,
the mesoporous and macroporous structure of
the 3D GBMs can increase the specific surface
area, which then enhance the adsorption pro-
perties of the material toward reactants. The
adsorption capacity of 3D GBMs is greater than
or comparable to other adsorbents [169]. For
example, the 3D graphene/d-MnO2 showed
excellent adsorption capacity for Pb2þ
(643.62 mg g1), Cd2þ (250.31 mg g1), Cu2þ
(228.46 mg g1), which was due to the large sur-
face area, porosity, and interlayer trapping effect
[196]. 3D GO/biopolymers (BSA, CS, and DNA)
hydrogels, and these hydrogels exhibited excel-
lent adsorption behavior to heavy metal ions
due to synergistic effects of the electrostatic
attraction along with the complexation between
surface hydroxyl or amino groups and heavy
metal ions [197]. The adsorption amounts of 3D
GO/BSA, 3D GO/DNA, and 3D GO/CS into
Pb(II) were 110, 129, and 147 mg g1, respec-
tively. The adsorption capability for Cu(II)
were 391, 370, and 480 mg g1, respectively. To
further boost the adsorption selectivity of 3D
255
GBMs, many functional elements were intro-
duced to 3D GBMs, including SiO2 and MoS2
[198,199]. Lei et al. [200] developed a 3D gra-
phene oxide foam/Fe3O4 nanocomposite
(GOF/Fe3O4) and evaluated its adsorption per-
formance for Cr(IV) removal. Chen et al. [201]
developed a novel 3D self-supporting material
using an aerosol capillary approach. Due to their
unique structural characteristics, the 3D balls
exhibited a rapid adsorption rate and superior
adsorption capacity toward the copper ion
(Cu2þ). Graphene/a-FeOOH hydrogel showed
the strong adsorption capability in heavy metal
ion removal partially originating from synergis-
tic impacts of the electrostatic attraction, ion ex-
change and surface complexation [202]. Surface
complexion occurred between metal oxyhydrox-
ides which come from additional Fe ions as well
as the targeted heavy ion pollutants. Generally,
the accession of cross-linking into 3D GBMs en-
hances heavy metal adsorption. In some cases,
the outcome is not always according to the
expectation, such as raising the amount of chito-
san triggered a massive decrease in adsorption
capacity because of the excessive folding of
GO sheets, which results in blockage of more
adsorption sites. Thus, the quantity of additives
changing the behavior of 3D GBMs, need to be
controlled, although the 3D GBM composition
has lower influence on adsorption capacity to-
ward metal ions compared with dyes [203].
3.3 Carbon nanotube-based
nanomaterials
Due to their extraordinary chemical, physical
and electrical properties, CNTs are used in
many applications including medical science,
electrical engineering, material science and envi-
ronmental engineering. However, there are
some significant limitations to CNTs because of
the interactive forces that arise between the
carbonic nanostructures, which can lead to aggre-
gation, difficulty in manipulation and poor
256 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
dispersibility. The main chemically active sites in
carbon nanotubes are located around defective
segments such as pentagons, oriented against a
tube body which generally consists of only hexa-
gons; and it may be this that gives CNTs their
great ability to interact with other compounds.
Salam et al. [204] used the multi-walled carbon
nanotubes (MWCNTs) to remove heavy metal
ions from aqueous solution. The removal of
Cd(II), Pb(II), Cu(II), and Zn(II) from aqueous so-
lution were characterized with low adsorption ca-
pacities; 0.084, 0.386, 0.398, and 0.325 mg g1 at
298 K, respectively. Functionalizing CNTs is the
key step to enhance their efficiency.
Purify or oxidize the surface of CNTs is an
essential step to improving CNTs and enhancing
their special characteristics. Lu et al. [205] purified
the single-walled carbon nanotubes (SWCNTs)
and MWCNTs with sodium hypochlorite solu-
tions. The equilibrium capacities of Zn2þ at 5, 15,
25, 35, and 45
C are 31.2, 35.6, 36.8, 39.6, and
41.4 mg g1 for the SWCNTs and 25.5, 27.5, 27.8,
28.5, and 29.5 mg g1 for the MWCNTs. At the
same conditions, the Zn2þ sorption capacity of
CNTs was much greater than that of commercially
available powdered AC, reflecting that SWCNTs
and MWCNTs are effective sorbents. Rosenzweig
et al. [206] studied Cu(II) adsorption on alcohol
functionalized (OH-CNT), acid functionalized
(COOH-CNT) and pristine CNTs. They found
the adsorptive capacity of MWCNTs for Cu(II)
species in water depends on the type of functional
group present on their surface. The amount of
Cu(II) adsorbed per gram of CNTs are 7.0 mg$g1
on OH-CNT, 5.5 mg$g1 on COOH-CNT, and
0.7 mg$g1 on pristine CNT. Sankararamak-
rishnan et al. [207] used CNTs and washed with
acid to produce nanofloral clusters. It was found
that maximum adsorption of Cr(VI) took place
at pH 2 and for Cd(II) in the pH range of 7e9. It
had the saturation capacity of 264.5 and
229.9 mg$g1 for both Cr(VI) and Cd(II), respec-
tively (Fig. 6.19). Tofighy et al. [208] used nitric
acid-oxidized CNT sheets to remove some diva-
lent heavy metal ions (Cu2þ, Zn2þ, Pb2þ, Cd2þ,
Co2þ) from aqueous solutions. Preference of
adsorption onto the oxidized CNT sheets can be
ordered as Pb2þ > Cd2þ > Co2þ > Zn2þ > Cu2þ.
The adsorption capacity of Pb2þ attained 101.05
mg g1 at initial concentration of 1200 mg L1,
while the adsorption capacity of Cd2þ, Co2þ,
Zn2þ and Cu2þ were 75.84, 69.63, 58.00 and
50.37 mg g1.
Loading metal oxide on the surface of CNT
also can improve the adsorption capacity. Zhao
et al. [209] synthesized titanium dioxide/multi-
walled carbon nanotubes (TiO2/MWCNTs)
nanocomposites and used for the adsorption of
Pb(II) from aqueous solution. The time depen-
dence of Pb(II) adsorption onto TiO2/MWCNTs
and MWCNTs nanocomposites can be described
by a pseudo-second-order kinetic model. The
Langmuir isotherm model agrees well with the
equilibrium experimental data. The maximum
adsorption capacity of TiO2/MWCNTs and
MWCNTs nanocomposites has been found to
be 137.0 and 33.0 mg$g1, respectively. Wang
et al. [210] prepared manganese oxide-coated
carbon nanotubes (MnO2/CNTs) and used to
remove Pb(II) from aqueous solution. From the
Langmuir isotherms, the Qmax was determined
to 78.74 mg g1. Comparing with CNTs, signifi-
cant improvement of Pb(II) adsorption shows
MnO2/CNTs can be good Pb(II) absorbers. Di
et al. [211] loaded ceria nanoparticles on aligned
carbon nanotubes (CeO2/ACNTs) by chemical
reaction of CeCl3 with NaOH in aligned CNT so-
lution and subsequent heat treatment. The best
Cr(VI) adsorption effect of CeO2/ACNTs occurs
at a pH range of 3.0e7.4. The largest adsorption
capacity of CeO2/ACNTs reaches 30.2 mg$g1
at pH 7.0. The experiment results suggest that
CeO2/ACNTs have great potential applications
in environmental protection.
In order to easily separate small size CNT from
aqueous solutions. Peng et al. [212] firstly pre-
pared CNTs-iron oxides magnetic composites to
remove Cu2þ and Pb2þ. The adsorption is pH
dependent. The adsorption capacities for Pb(II)
and Cu(II) in the concentration range studied at
 3. Removal of heavy metal ions by carbon-based nanomaterials
FIGURE 6.19 Synthesize process and adsorption isotherm of Cr(VI) and Cd(II) on nanoclusters [207].
pH 5.0 reach 0.51 and 0.71 mmol g1, respec-
tively. Chen et al. [213] prepared MWCNT/iron
oxide magnetic composites for the adsorptions
of Ni(II) and Sr(II). The adsorption capacity of
the magnetic composites is much higher than
that of MWCNTs and iron oxides. The solid
magnetic composites can be separated from the
solution by a magnetic process. Ji et al. [214]
developed a one-step thermal decomposition
strategy to make superparamagnetic nearly
cubic monodisperse Fe3O4 nanoparticles load
on MWCNTs (MWCNTs/Fe3O4); then, the as-
prepared MWCNTs/Fe3O4 nanocomposites
were modified with 3-aminopropyltriethoxysilane
(APTS) (MWCNTs/Fe3O4eNH2). The maximum
adsorption capacities are 41.77 and 75.02 mg$g1
for Pb(II) on MWCNTs/Fe3O4 and on MWCNTs/
Fe3O4eNH2 nanocomposites at pH 5.3, res-
pectively. The results reveal that the adsorption
properties of the MWCNTs/Fe3O4eNH2
257
nanocomposites are better than the MWCNTs/
Fe3O4 nanocomposites. The MWCNTs/Fe3O4
and MWCNTs/Fe3O4eNH2 magnetic nanocom-
posites can be reused by regeneration in 0.1 M
NaOH. Zhang et al. [215] synthesized thiol-
functionalized MWCNT/magnetite nanocom-
posites (MPTS-CNTs/Fe3O4). The removal
efficiency of CNTs/Fe3O4 nanocomposites and
MPTS-CNTs/Fe3O4 nanocomposites was highly
pH dependent and the optimal pH value for
adsorption was 6.5. The adsorption isotherms
of Hg2þ and Pb2þ by MPTS-CNTs/Fe3O4 nano-
composites matched well with the Langmuir
model with the Qmax of 65.52 and 65.40 mg g1,
respectively. Vilardi et al. [216] produced the
CNTs-nano zero-valent iron (CNTs-nZVI) com-
posite for the adsorption of Cr(VI). In the case
of competitive adsorption, Cr(VI) exhibited the
highest affinity for the adsorbent. The preferable
Cr(VI) removal was also observed using binary
258 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
systems of the tested metals by means of the
CNTs-nZVI nanocomposite.
Grafting organic compound on the surface
also is an important route to improve the adsorp-
tion performance of carbon nanotube. Ren et al.
[217] grafted 2-vinylpyridine (VP) on the surface
of MWCNTs (MWCNT-g-VP) by using N2
plasma technique, as shown in Fig. 6.20A. Ac-
cording to the results simulated by Langmuir
model, the Qmax of Pb(II) are 15.9 mg$g1 on
MWCNTs and 37.0 mg g1 on MWCNT-g-VP
at pH ¼ 6.0. The variation in separation factors
indicates that the sorption of Pb(II) on MWCNTs
and MWCNT-g-VP is favorable. Kumar et al.
[218] used the dodecyl-benzene-sulfonic-acid to
doped polyaniline/MWCNTs (DP/MWCNTs)
nanocomposite by in situ oxidative polymeriza-
tion, as shown in Fig. 6.20B. DP/MWCNTs
was found to be ideal adsorbent for the removal
of Cr(VI) compared with pristine and oxidized
MWCNTs. The adsorption isotherm of Cr(VI)
onto DP/MWCNTs fitted the Freundlich isotherm
model and maximum monolayer adsorption
capacity was found to be 55.55 mg g1. Kumar
et al. [219] reported an interesting interaction be-
tween oxidized MWCNTs (oxi-MWCNTs), tetra
n-heptylammonium bromide (ionic liquid) and
total chromium (Cr(VI)/Cr(III)). The maximum
adsorption capacity was found to be 85.83
mg g1 from a nonlinear Langmuir isotherm
model. The adsorption efficiency of Cr(VI) was
not influenced by Cu2þ, Cd2þ, Co2þ, Zn2þ,
Ni2þ, or Pb2þ, while Fe2þ and Mn2þ did interfere
by reducing the Cr(VI) to Cr(III) state. In the case
of anionic species, i.e., at 100 mg L1 levels of
nitrite, chloride, sulfite, and phosphate, the
adsorption of Cr(VI) was inhibited by the
competition for the HCrO4 ion at the active
sites of the oxi-MWCNT adsorbent (Fig. 6.20C
and D). Under the given experimental condi-
tions, these ions did not form stable ion-pairs
with the quaternary ammonium cation and
thus did not compete with the bichromate for
the active sites in the adsorbent. Dichiara et al.
[220] examined the removal of Cu(II) from
aqueous solutions through adsorption on free-
standing hybrid papers comprising a mixture
of graphene and different types of carbon nano-
tubes (CNTs). As shown in Fig. 6.20E and F, it
can be observed that in each case the uptake of
Cu(II) per unit mass of adsorbent is always
higher when the SWCNTs are combined with
graphene promoting an improvement in adsorp-
tion capacities on the order of 50% better than
that of the SWCNTs alone.
3.4 Carbon nanofiber-based
nanomaterials
CNFs exhibit remarkable physicochemical
characteristics, including high tensile strength,
excellent thermal and chemical stabilities, low
density, and high conductivity, which have led
to their application in a variety of fields, e.g., as
sensors, batteries, for catalysis, and in aerospace
technology. The high surface area, porosity, and
selective active surface sites of CNFs suggest ap-
plications in adsorption. However, CNFs have
not been as extensively studied as other carbon
nanomaterials for the adsorption of water
contaminants.
For the unmodified carbon nanofiber, the
adsorption is relatively low. Garcia-Diaz et al.
[221] used the helical ribbon CNF to remove
Cu2þ from solution. The characterization of
CNF by zeta potential showed an isoelectronic
pH of 1.9. CNF has a great influence on Cu2þ
adsorption, the experimental data fit well to
pseudo-second-order kinetic and Langmuir
isotherm models (Qmax ¼ 8.80 mg$g1) at
T ¼ 298 K and pH ¼ 4. The Cu2þ adsorption
could be explained by the particle diffusion
model. Pan et al. [222] synthesized the carbon
nanofiber web (CNW) by electrospinning of
polyacrylonitrile (PAN) and polyvinylpyrroli-
done (PVP) copolymer precursor solution and
a following rather low-temperature (450
C)
 3. Removal of heavy metal ions by carbon-based nanomaterials 259

FIGURE 6.20 (A) Schematic diagram of plasma grafting processes [217]; (B) Schematic representation of DP/MWCNTs prep-
aration and adsorption of Cr(VI) onto DP/MWCNTs [218]. Effect of cations (C) and anions (D) on the adsorption of chromium(VI)/
Cr(III) by oxi-MWCNTs [219]; (E) Time-dependent adsorption of Cu(II) on different carbonaceous materials for a 3 h time period
(temperature: 20
C; initial concentration: 25 mg$mL1; solution pH 6.8). (F) Uptakes of Cu(II) on pristine and COOH- and OH-
functionalized SWCNTs and their hybrid counterparts. The straight and the dashed lines correspond to the uptake of Cu(II) on
graphene and granular AC, respectively (temperature: 20
C; initial concentration: 20 mg$mL1; solution pH 6.8) [220].

thermal treatment. The CNW has an efficient
adsorption capacity of 56.9 mg g1 for Cr(VI)
ions and the adsorption capacity remained up
to 55% after five cycles, indicating that the
CNW has a promising in practice for application
in Cr(VI) ions adsorption.
In parallel to other carbon derivatives, chemi-
cal activation treatment of CNFs is done to
enhance the specific surface area, pore sizes, and
pore volume, which regulates its surface applica-
tion characteristics. Yuan et al. [223] prepared an
electrospun CNF mat via electrospinning polyac-
rylonitrile (PAN), followed by thermal
preoxidation and carbonization. The point of
zero charge pH (pHpzc) of CNF was around
7.93. CNF demonstrated high adsorption capacity
and fast adsorption kinetics for Cr(VI) at pH < 3.
The maximum adsorption capacity of Cr(VI) on
CNF was 118.8 mg g1 at pH 2. XPS analysis
revealed that the removal of Cr(VI) might be the
result of a combination of redox reaction and elec-
trostatic adsorption, as shown in Fig. 6.21A. Kam-
palanonwat et al. [225] prepared polyacrylonitrile
(PAN) nanofiber mats by electrospinning and
they were further modified to contain amidino
diethylenediamine chelating groups on their
260 6. Water treatment and environmental remediation applications of carbon-based nanomaterials

FIGURE 6.21 (A) Schematic diagram of Cr(VI) adsorption on CNF from aqueous solution [223]; (B) Langmuir and Freund-
lich adsorption isotherm models for the adsorption of Cr(VI) onto PAN-NH2 nanofibers. The solid lines represent Langmuir and
Freundlich fittings to the experimental data. T ¼ 23  1
C, V ¼ 40 mL, pH ¼ 2 and PAN-NH2 nanofibers ¼ 20 mg [224].

surface via heterogenous reaction with diethyle-
netriamine. The obtained aminated PAN
(APAN) nanofiber mats have the Qmax of 150.6,
155.5, 116.5 and 60.6 mg$g1 for Cu(II), Ag(I),
Fe(II), and Pb(II) ions, respectively. Deng et al.
[226] used electrospun nanofiber as a sorbent in
packed fiber solid-phase extraction for selective
separation and preconcentration of lead(II). And
the metal ion could be desorbed from it by three
times of elution with a small volume of
0.1 mol L1 HNO3 aqueous solution. Verma
et al. [227] synthesized novel triethanol amine-
grafted hollow CNFs, supported on carbon beads
via templating method for the removal of Cr(VI)
ions from water. CNFs were grown on carbon
beads by CVD using the in situ incorporated Cr
nanoparticles in the beads, as the catalyst. The
adsorption capacity of Cr(VI) was determined to
be ~51 mg g1 and negligible interference for
coexisting metal ions in water with the Cr(VI)
adsorption. Avila et al. [224] prepared polyacrylo-
nitrile (PAN) nanofibers functionalized with
amine groups (PAN-NH2) using a simple one-
step reaction route. The adsorption process
showed pH dependence and the maximum
Cr(VI) adsorption of 156 mg g1 at pH ¼ 2
(Fig. 6.21B). XPS and FT-IR revealed that the
adsorption of Cr(VI) species on PAN-NH2 was
facilitated through both electrostatic attraction
and surface complexation. High desorption effi-
ciency (>90%) of Cr(VI) was achieved using
diluted base solutions that may allow the reuse
of PAN-NH2 nanofibers.
There are some researchers had loaded the
metal oxide on the surface of carbon nanofiber.
Haddad et al. [228] loaded ZnO nanoparticles
on electrospun polyacrylonitrile (PAN) nano-
fiber mats. Adsorption results indicated that
the fabricated PAN/ZnO (2.0 wt%) composite
nanofiber mats showed the best adsorption per-
formance with 261% and 167% increase in
adsorption capacities for Pb(II) and Cd(II) from
aqueous solutions, respectively, compared with
pristine PAN nanofibers. Khosravi et al. [144]
prepared TiO2 and TiO2/ZnO nanofibers by
electrospinning technique, and the nanofiber
were coated on the sewage sludge carbon sur-
face for adsorption of Ni(II) and Cu(II) from
aqueous solutions and industrial wastewaters
of Iran. The maximum monolayer sorption ca-
pacities of Ni(II) and Cu(II) were found to be
282.3 and 298.1 mg$g1. Almasian et al. [229]
synthesized mesoporous MgO/poly(propylene
glycol) (MgO/PPG) hybrid nanofibers for the
removal of heavy metal ions from solutions.
The regeneration experiment of nanofibers
showed that the adsorption capacity for Cd, Cu
and Pb was as high as 1900.05, 1919.28 and
 3. Removal of heavy metal ions by carbon-based nanomaterials
1922.79 mg$g1 after seven cycles, respectively.
Similar to other CNMs used in adsorption,
the introduction of magnetic groups into
CNFs facilitates the separation process after
adsorption is complete. Bassyouni et al. [230]
synthesized Fe3O4/o-MWCNTs/PA6 hybrid
nanofiber membrane composite. The adsorption
efficiency of the composite is strongly depending
on various factors, such as; pH, in batch mode.
The novel Fe3O4/o-MWCNTs/PA6 hybrid
composite not only exhibited the effective sepa-
ration capability of Pb(II) ions from an aqueous
solution but also can be separated more easily
from the solution system. The hybrid nanofiber
membranes also exhibited easily regeneration
and recycling at least for four adsorption-
desorption recycles. The unique properties
render the hybrid composite highly promising
as an advanced adsorbent with tremendous po-
tential in wastewater treatment for heavy metal
removal at industrial scale.
Grafting various organic molecule and poly-
mers is popular way to synthesize functional car-
bon nanofiber [231e239]. There are many articles
about this functional routine. Shariful et al. [231]
fabricated chitosan/poly ethylene oxide (chito-
san/PEO) nanofibers at different chitosan:PEO
weight ratio by electrospinning process. The
maximum adsorption capacity of the beadless fi-
bers for Cu(II), Zn(II), and Pb(II) ions were found
to be 120, 117, and 108 mg$g1, respectively.
Habiba et al. [232] synthesized chitosan/polyvi-
nyl alcohol (PVA)/zeolite nanofibrous composite
membrane via electrospinning. The resulting
membrane was stable in distilled water, acidic,
and basic media in 20 days. The adsorption abil-
ity of nanofibrous membrane was studied over
Cr(VI), Fe(III), and Ni(II) ions using Langmuir
isotherm. Li et al. [233] reported a novel and
high efficient lead ion-imprinted adsorbent of
chitosan nanofiber mats by electrospinning of
chitosan solution with Pb(II) as template and
glutaraldehyde as cross-linker, as shown in
Fig. 6.22A. The equilibrium adsorption capacity
for Pb(II) ions of such chitosan nanofiber
261
adsorbents can arrive at 577 mg g1, which is
two or five times higher than that of the common
chitosan-based adsorbents. The equilibrium
adsorption capacity in the order of Pb(II) >
Cu(II) > Cd(II) > Ni(II) > Zn(II). The nanofiber
adsorbents can be regenerated and still has equi-
librium adsorption capacity of 359 mg g1 for the
second Pb(II) ion adsorption. Yarandpour et al.
[234] prepared mesoporous PAA/dextran-
polyaniline core-shell nanofibers with combina-
tion of electrospinning (Fig. 6.22B) and in situ
polymerization methods and their heavy metal
adsorption ability was investigated. The synthe-
sized nanofibers showed high maximum adsorp-
tion capacity of 1111.11 and 833.33 mg g1 for
Pb2þ and Cu2þ, respectively obtained from Lang-
muir isotherm model. Wang et al. [236] prepared
polyacrylonitrile/polypyrrole (PAN/PPy) core-
shell structure nanofibers via electrospinning fol-
lowed by in situ polymerization of pyrrole
monomer for the removal of Cr(VI) from
aqueous solution. Adsorption results indicated
that the adsorption capacity increased with the
initial solution pH decreased. The adsorption
equilibrium reached within 30 and 90 min
(Fig. 6.22C), and the process can be described
using the pseudo-second-order model. The
maximum adsorption capacity calculated from
the Langmuir model increases from 61.80 to
74.91 mg g1 as the temperature increased from
25 to 45
C. Guan et al. [237] prepared hordein
and hordein/N,N0 -methylene bisacrylamide
(MBA) nanofiber membranes by electrospinning
technique. Then the fabricated membranes were
modified with b-cyclodextrin (b-CD) to remove
heavy metal ions from aqueous solution. It was
found that additions of MBA and b-CD at proper
concentrations could significantly improve the
adsorption capacities and the maximum adsorp-
tion of hordein, hordein/MBA, and hordein/
MBA/b-CD nanofiber membranes were 64.94,
81.97, and 88.50 mg g1, respectively. And the
adsorption rates of Cu(II) by the three nanofiber
membranes could still be maintained at 68%,
71%, and 74%, respectively (Fig. 6.22D).
262 6. Water treatment and environmental remediation applications of carbon-based nanomaterials

FIGURE 6.22 (A) Preparation of the lead ion-imprinted cross-linked electrospun chitosan nanofiber mats [233]; (B) The pro-
posed interaction between different components in synthesize process [234]; (C) Effect of contact time and initial concentration
on the adsorption of Cr(VI) of the PAN/PPy nanofiber mat. T ¼ 25
C and initial solution pH 2.0 [236]. (D) Adsorption capacity
and reactive cycles of the hordein, hordein/MBA, hordein/MBA/b-CD nanofiber membranes [237].

Sun et al. [238] spun different proportions of treatment at different temperatures and the rela-
CNTs and polyacrylonitrile into filaments, tionships among CNTs and pores in carbon
discussed the structure of CNTs exposed on the nanofibers. Different pH, dosage, initial concen-
surfaces of nanofibers after carbonization tration of pollutants and adsorption time on the
 4. Removal of radionuclides by carbon-based nanomaterials
adsorption of Cr(VI) was studied on carbon
nanofiber porous materials with carbon nano-
tubes. Parlaylci et al. [239] developed nylon-
6,6(N6,6)/GO nanofibers. The batch adsorption
model for Cr (VI) adsorption was applied as a
function of time, initial Cr(VI) concentration,
adsorbent dosage, and pH to examine nanofiber
activity. The maximum adsorption capacity for
Cr (VI) ion was found to be 47.17 mg g1 of
N6,6/using the related isotherm curves and
equations.
4. Removal of radionuclides by
carbon-based nanomaterials
In recent years, increasing attention has been
paid to the contamination caused by radioactive
waste [240]. It is in urgent need for the treatment
of radionuclide contaminated water and land,
especially after the Fukushima nuclear accident.
Leaking of radionuclides such as 90Sr, 137Cs,
235
U, 129I, etc. has aroused serious public concern
because the fission products can get into the food
chain from freshwater systems. Such radionu-
clides in contaminated water with high mobility
would move into soils and enter into plants, ul-
timately becoming a part of animals and human
beings [241]. For work safety in the nuclear in-
dustry and for human health, the investigations
on fast and efficient removal of long-lived radio-
nuclides from nuclear wastewater have great sci-
entific and application value.
A variety of technologies have been investi-
gated as potential means of attenuating radio-
nuclide concentration, such as precipitation,
membrane filtration, sorption, and ion ex-
change etc. [242e244]. Among these methods,
sorption technique has been widely used
because it is easily operated, economical and
can be applied on a large scale for practical ap-
plications. Carbon materials with high specific
surface area, have been one of the most effective
materials for environmental treatment, and
have obtained great attentions recently. In order
263
to review the radioactive ion adsorption
on carbon-based nanomaterials, the carbon
nanomaterials and their derivatives were
divided into four categories: (1) AC (2) gra-
phene (GO in particular) (3) carbon nanotube
(CNT) and (4) carbon nanofiber (CNF). These
carbon nanomaterials can be utilized in the
removal of radioactive metal-contaminated wa-
ter due to their fascinating properties like high
surface area, ease of recycling, and easiness to
desorb the adsorbed radioactive ions; using
only mineral acid solution and regenerated ma-
terial, it can be reused with retention of adsorp-
tion capability. In addition to these properties,
the carbon nanomaterials can easily be fabri-
cated with other nanomaterials and are easy
to be functionalized resulting in multifunctional
nano-adsorbent. Carbon-based materials are
highly biocompatible with living organisms
and environment. An overview of the pub-
lished articles indicates that the frequency of
application of GO and its derivatives as radio-
nuclides sorbent is higher than the other
carbon-based nanomaterials (Fig. 6.23). The
application of GO and its derivatives has
widely expanded in recent several years. This
expansion may be due to the presence of
various functional groups at the surface of GO
that can be easily modified with the chemical
methods, while extensive use of AC may be
for the low cost of the raw materials and the
easy preparation. CNT as sorbent ranks third,
FIGURE 6.23 The frequency of application of carbon-
based nanomaterials for radionuclide sorption.
264 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
and there are several studies of CNF for this
purpose. Of course, AC, CNT and CNF can be
typically oxidized by multiple procedures to
provide suitable functional groups of carboxyl
on their surface. These carboxyl groups can be
then modified with other appropriate func-
tional groups to selective adsorb radioactive
ion. In recent years, new nanocomposites based
on a modification of the sorbent with a natural
compound as green sorbents have been very
much considered due to their proper properties
such as low cost, high efficiency, renewable,
and so on.
There is also an immense effect of different pa-
rameters such as pH, contact time, and type of
adsorbents on the process of radionuclides
adsorption. We believed that carbon nanomate-
rials have fascinating physicochemical proper-
ties and have great potential to be exploited in
the environmental remediation and water purifi-
cation. This chapter summarizes the application
of carbon-based materials in the removal of ra-
dionuclides (such as U(VI), Eu(III), Sr(II), etc.)
from aqueous system. The main sorption mecha-
nisms are investigated by using kinetics analysis,
thermodynamic analysis, surface complexation
models, spectroscopic techniques and theoretical
calculation. It is evident to conclude that carbon-
based materials have good potential for the
removal of radionuclides from aqueous system.
However, it is necessary to carry out more
research works focusing on the development of
lower cost, higher efficient and environmentally
friendly carbon-based materials either for scien-
tific interests or practical applications.
4.1 Activated carbon-based
nanomaterials
ACs are regarded as good adsorbents for the
removal of radionuclides from liquid phases.
ACs possess a large surface area, as mentioned
in Section 2, and different surface functional
groups; including carboxyl, carbonyl, phenol,
quinone, lactone and other groups bound to
the edges of the graphite-like layers. They are
therefore the most promising material for the
adsorption of radioactive ions and can be pre-
pared at a large scale from a variety of carbon
sources especially form agricultural waste.
Due to its selective adsorption, this material is
already used for the separation of metal ions
from solutions in the nuclear industry. Adsorp-
tion of U(VI) from aqueous solution has also
been successfully performed [245e247]. Yi
et al. [245] investigated the adsorption of
U(VI) on coconut husk ACs (Fig. 6.24). They re-
ported a maximum sorption capacity of
6.67 mg g1 for U(VI) ions. Belgacem et al.
[246] reported the removal of uranium from
solution by AC developed from ground used
tire with a maximum sorption capacity of
158.73 mg g1. Yakout et al. [247] working
with AC from rice straw, found that this AC
had a maximum removal capacity of
100 mg g1. U(VI) showed a decreased adsorb-
ability when it coexisted with humic acid
(HA) from the start (41.5 mg g1 in simulta-
neous) compared with the case when U(VI)
was added after equilibrium adsorption of HA
on ACs (11.9 mg g1 in sequential) at pH 5.5.
They discussed the mechanism and suggested
that humic substance is strong inhibitor of ura-
nium binding and should be removed before
from wastewater treatment for uranium.
AC also be used to remove Cs, Sr, Eu, and Th
from aqueous media [248e251]. Potassium iron
hexacyanoferrate K/FeeFe(CN)6, ammonium
molybdophosphate or potassium nickel hexa-
cyanoferrate loaded AC was prepared for the
uptake of Cs; while magnetic composite for the
easy separation of AC from radioactive waste-
water [248e250]. In a comprehensive study con-
ducted by Strelko et al. [251], three ACs were
tested for their removal of radioactive137Cs,
239
Pu, 241Am, and 90Sr. Other investigations
also observed enhanced sorption of different
radioactive isotopes on specially prepared gran-
ular ACs: 137Cs and 90Sr, Th(IV), U(VI), and
 4. Removal of radionuclides by carbon-based nanomaterials 265

FIGURE 6.24 Effect of initial U(VI) concentration on U(VI) adsorption by AC (left) [245]; Effect of humic acid on the
adsorption of uranium on RSK carbon (right) [247].

(152þ154) TABLE 6.1 Kd values of the adsorbed ions on

Eu and 65Zn on acid-oxidized granular MACCS at agitating rate of 400 rpm,
AC [252,253]. Abu-Dalo et al. [254]. have opti- temperature of 25  1
C, initial metal
mized benzotriazole-granular active carbon concentration of 50 mg L1, and pH 5.6
(GAC) for the purpose of sequestering trans- [256].
uranic elements from industrial wastewaters us-
Exchanging pH of the metal Ionic
ing stable isotopes accepted as models for ions solutions Kd (mL gL1) radii (Å)
radioactive metals U(VI), Eu(III), Sr(II), and
Ce(III). In order to research the sorption of thor- Eu3þ 5.62 6270.00 0.95
ium(IV) and uranium(VI) ions from aqueous so- Ce 3þ
975.30 1.07
lutions, the granular-ACs was modified with Sr 2þ
63.08 1.18
€
nitric acid by Oter et al. [255]. Adsorption of þ
Cs 59.74 1.67
Th(IV) and U(VI) onto modified carbon has
been evaluated in terms of equilibrium, kinetics
and thermodynamics studies. Moloukhia et al. research of active carbon, which contribute
[256] prepared a kind of high-quality modified greatly to the removal of U(VI) by AC. The
ACs by oxidation using H2O2 and HNO3. The numbers and kinds of these groups can be
modified ACs coconut shells (MACCS) have increased or changed by activating agents for
high removal efficiency, distribution coefficient the removal of U(IV) from solution. Expect for
(Table 6.1), and capacity especially for Eu3þ easier preparation, AC can also be functionalized
ions compared with some other synthetic and easily. Chelating agents, including trimercapto-
natural sorbents. The affinity sequence of the triazine, thiocarbonates, and dimethyldithiocar-
investigated ions on MACCS in the same condi- bamates have been employed to enhance metal
tions has the sequence: Eu3þ>Ce3þ>Sr2þ>Csþ. radionuclide separation performance. Numerous
The ions with smaller ionic radius are easily functional groups such as amidoxime [257], ben-
adsorbed and move faster than that the ions zoylthiourea [258], and polyethyleneimine [259]
with greater ionic radius. were selected to modify ACs by different tech-
In fact, surface groups in activated carbon have nique for improving the adsorption performance
an important place in the surface chemistry of U(VI). Liu et al.’s [257] experiments indicated
266 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
that amidoxime-based ACs had a high removal
amount toward U(VI) (14.16 mg g1), which
was much higher than that of ACs. N/O/P con-
taining functionalities was introduced through
either reaction with N/O/P containing reagents
or activation with their containing precursors.
Biochar is charcoal created by pyrolysis of
biomass, which might be an interesting alterna-
tive to replace the industrial ACs for water clean-
ing. Several studies have reported that biochar
exhibits a strong affinity to adsorb U(VI)
[260e264]. These studies only present bulk
U(VI) ion adsorption data, which do not provide
molecular-scale insights into the coordination of
aqueous uranyl species adsorbed to the biochar
surface. Alam et al. [265] reported the mecha-
nisms of aqueous U(VI) species adsorption to
biochar, they used the flexible surface complexa-
tion modeling approach to simulated the adsorp-
tion behavior of U(VI) on biochar spectroscopic
data suggest that U(VI) is coordinated to the sur-
face of the biochar primarily through eCOOH
and eOH functional groups. In the EXAFS
spectra (Fig. 6.25), they found FT feature at a dis-
tance ~1.9 Å corresponds to equatorial U-Oeq
shells, revealing the possibility of an O]U]O
transdioxo structure. And the splitting of the
U-Oeq shell itself can be attributed to the pres-
ence of inner-sphere surface complexes. The FT
feature at approximately 3.0 Å in the samples
was fitted with a UeC shell, indicative of
inner-sphere surface complexation [265]. In
fact, the unmodified biochar is not adsorptive
enough in practical purifying process, though
biochar is one of the economic and environment
friendly adsorbents. Comparing with functional
nanomaterials, the adsorption capacity of bio-
char is relatively low (8e35 mg g1 for U(VI))
due to the limited active functional groups
[265]. Therefore, the production and study of
specific groups-containing biochar was the
objective of a recent issue. The grafting of
carboxyl groups can enhance the adsorption ca-
pacity for U(VI) to dozen times higher than the
untreated one [260].
With the increasing critical environmental
standards, it is noticed that raw biochar mate-
rials may fail to remove contaminants at high
concentrations and is not satisfied with the
need of selective removal of pollutants in the
complicate actual wastewater. In this point,
biochar-based hybrid composites generally
received great attention in the wastewater treat-
ment [266]. The hybrid materials usually have
better performance in the wastewater treatment
due to the combination of the advantages of
foreign materials with BCs. For example, Peng
et al. [267] used polyethyleneimine to modify
the surface of BCs, which brought more surface
functional groups and strong selective adsorp-
tion toward U(VI) ions. Wang et al. [69] investi-
gated the modification of moso bamboo
biochar with polyethyleneimine (PEI) for the effi-
cient enrichment of U(VI) in aqueous solution
(Fig. 6.26). The alkali/acid-treated biochars
with amine groups (PEI-alkali-biochar or PEI-
acid-biochar) gives the maximum adsorption ca-
pacities of 212.7 mg g1 for PEI-alkali- biochar
and 185.6 mg g1 for PEI-acid-biochar, which
are almost 9e10 times higher than that of pris-
tine biochar (20.1 mg g1). The U(VI) adsorption
on PEI-alkali/acid-biochar is mainly controlled
by the complexation between U(VI) and amine
groups [69].
4.2 Graphene-based nanomaterials
GO tends to be more hydrophilic than gra-
phene due to GO has oxygen-containing func-
tional groups that may form stable complexes
with many contaminants. The transformation
of graphene into GO can allow efficient applica-
tion in environmental treatment. GO has many
oxygen-containing functional groups on its basal
plane and on the edges in the form of epoxy, hy-
droxyl and carboxyl groups. GO has great poten-
tial in environmental remediation and energy
applications. For uranium, Zhao and coworkers
[268] explored the adsorption of uranium on
 4. Removal of radionuclides by carbon-based nanomaterials 267

FIGURE 6.25 XANES and EXAFS spectra of U(VI) adsorbed onto WS. (A) XANES spectra of U(VI) adsorbed samples and
uranyl reference. (B) EXAFS signals weighted by k3 spectra. (C) R space curve fitting results. Solid lines are experimental data,
and dotted lines are fitted data.

FIGURE 6.26 Adsorption kinetics of U(VI) adsorption on pristine biochar, PEI-alkali-biochar and PEI-acid-biochar (left).
Schematic illustration for the synthesis of PEI-alkali/acid-biochar and adsorption mechanism (right) [69].

graphene by carrying out series of batch exper-
iments, and a maximum adsorption of
97.5 mg g1 had been obtained toward U(VI)
(Fig. 6.27). In addition, Li et al. [269] prepared
single-layered GO material to adsorb U(VI)
and achieved a considerable adsorption capac-
ity of about 299 mg g1. EXAFS spectroscopy
study on U(VI) adsorbed GO suggested that
functional groups on GO formed stable inner-
sphere complexes with UO2þ 2 at pH ¼ 3.9 and
the coordination number of UO2þ
2 in the equato-
rial plane was approximately 5. Wu et al. [270]
concluded the uranyl was more likely to
combine with carboxyl and hydroxyl groups
at high pH value compared with those in
neutral environment by analyzing the vibration
frequencies and binding energies of various
GO/uranyl complexes.
The high surface area and rich functional
groups offer GOs excellent performance for
268 6. Water treatment and environmental remediation applications of carbon-based nanomaterials

FIGURE 6.27 Sorption isotherms of U(VI) on the graphene oxide nanosheets at different temperatures (left).
pH ¼ 5.0  0.1, m V1 ¼ 0.06 g L1, I ¼ 0.01 M NaClO4. The solid lines represent the Langmuir model simulation, and the
dash lines represent the Freundlich model simulation [268]. (A) Raw U LIII-edge k3-weighted c(k) EXAFS spectra and
(B) their corresponding Fourier transforms of U(VI) adsorbed on GO sheets at pH 3.9, 6.1 and 7.6, respectively. C0(U) ¼
0.5 mM, CGO ¼ 0.4 g L1, and contact time ¼ 24 h. The bottom-most spectrum is from uranyl hydroxide precipitate prepared
as a solubility-limiting phase [269].

removing radionuclides such as Cs(I), Sr(II),
Eu(III) and Th(IV), Pu(IV), etc. [240,271,272]
from aqueous solutions. The high specific sur-
face area and large number of oxygen-
containing functional groups, the c-axis spacing
of GOs (0.87 nm) is enough for most of radionu-
clides (e.g., r* 0.42 nm for Co(II), 0.41 nm for
Sr(II), and 0.33 nm for Cs(I)) to enter the inter-
layer space of GOs, thereby can form strong
complexes which are very difficult to be des-
orbed from GOs. The delocalized p electron sys-
tems of graphene layer as Lewis base can form
electron donor-acceptor complexes with radio-
nuclides as Lewis acid through Lewis acidebase
interaction, which also contributes to the high
sorption capacity of radionuclide on GOs [273].
Wang et al. synthesized GOs using Hummers’
method and applied them as adsorbents to
remove radionuclides (U(VI), 152þ154Eu(III),
85þ89
Sr(II) and 134Cs(I) ions) at low level concen-
trations, and compared the single and competi-
tive sorption properties of the radionuclides on
GOs (Fig. 6.28). They found the sorption of ra-
dionuclides on GOs was mainly attributed to
surface complexation via the coordination of
radionuclides with the oxygen-containing func-
tional groups on GO surfaces. The competitive
sorption results indicated that the selectivity
sorption capacities were U(VI)>Eu(III)>Sr(II)>
Cs(I) [274].
Xie et al. [275] characterized the carboxylic
functional group and an unexpected sulfonate
functional group on GO as the reactive surface
sites and quantified via diffuse layer modeling
of the GO acid/base titrations. Data from vari-
able pH and variable concentration batch exper-
iments was simultaneously modeled using the
DLM-SCM assuming Eu(III) and U(VI) sorption
to both carboxylate ([ ¼ COO]) and sulfonate
sites ([ ¼ SO3 ]) (Fig. 6.29). The SCM model
demonstrates U(VI) sorption to GO occurs
mostly through complexation with carboxylate
sites except at very low pH (1e2) where sorp-
tion is dominated by U(VI) binding to sulfonate
groups. On the contrary, Eu(III) sorption to
GO via sulfonate group dominates from pH
1e4 [275].
Ai et al. [276] investigated the binding
configurations and adsorption energies of
different GO/uranyl complexes with various
 4. Removal of radionuclides by carbon-based nanomaterials 269

FIGURE 6.28 Single sorption (A) and competitive sorption (B) of U(VI), 152þ154Eu(III), 85þ89Sr(II) and 134Cs(I) on GOs.
m V1 ¼ 0.2 g L1, the initial concentration of each radionuclide was 1.010-5 mol L1, pH 5.5  0.1, T ¼ 20  1
C,
I ¼ 0.01 mol L1 NaClO4 [274].

FIGURE 6.29 Experimental data (dots) and SCM fit (lines) of (A) Eu(III) sorption to GO as a function of pH and (B) U(VI)
sorption to GO as a function of pH. Sorption isotherms and SCM fit for (C) Eu(III) and (D) U(VI) at a constant pH of 5. All
experiments were performed using 0.1 g L1 GO in a 10 mM NaCl electrolyte solution [275].
270 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
oxygen-containing groups (epoxy group
(eOe), carboxyl (eCOOH), monohydroxyl
(eOH) and bihydroxyl (eOHeOH)) by DFT
method. The optimized geometries for uranyl
ion interacts with epoxy group functionalized
graphene in neutral ([GO-O- / UO2]2þ) and
acidic environment ([GO-O-H / UO2]3þ) were
depicted in Fig. 6.30. The bond length between
the axial oxygen (UeOax) and U atom in bare
[UO2(H2O)5]2þ was about 1.732/1.733 Å, and
it became longer in [GO-O- / UO2]2þ (1.733/
1.735 Å), [GO-O-H / UO2]3þ (1.757/1.759 Å).
For the [GO-O-H / UO2]3þ structure, with the
protonation on the exposed epoxy O atom,
the eOH group was dropped away the surface
because of its strong complications with the
UO2þ2 . High pH level was more favorable for
the adsorption process of uranyl species on
the GO due to the stronger electrostatic interac-
tion between negatively charged O atom and
uranyl ion. The GO containing bihydroxyl
groups had the highest adsorption capacity
toward the uranyl species. In addition, Shi
and coworkers [270,277,278] have investigated
the coordination modes and thermodynamic
behaviors between GOs and Th(IV), U(VI),
Np(V) and Pu(VI, IV) using the quasi-relativistic
DFT method. The structural and electronic
FIGURE 6.30 The optimized structures of GO(-O-)/uranyl and GO(-COOH)/uranyl at different pH levels. Bond lengths
are in Å [276].
properties as well as thermodynamic behaviors
of the GO complexes with Np(V), Pu(VI) and
Pu(IV) had been explored theoretically
[277,278]. They found that Pu(VI) and Np(V)
complexes with GOs were five-coordination at
the equatorial plane, while Pu(IV) complexes pre-
fer to form eight-coordination. The analysis of
NBO and quantum theory of atoms in molecules
showed that the Pu(IV)eO bonds of Pu(IV)/GO
complexes possessed more covalency, while the
electrostatic interactions dominated the Np(V)-
OG and Pu(VI)-OG bonds.
GOs can incur irreversible aggregation and/or
polydisperse in its thickness, lateral size and
shape, which may hinder the effective
sorption behaviors and thereby reduces the
sorption capacity. Therefore, many researchers
grafted polymers including polyaniline [279],
polyacrylamide [280], thiacalixarene [281], O-
phosphorylethanolamine [282] onto GOs to
introduce various functional groups and to
enhance their dispersibility in solutions and
thereby improves the removal ability of some
radionuclides. The maximum sorption capacities
of Cs(I), Sr(II), Eu(III) and U(VI) on the
GO-supported polyaniline (PANI@GO) nano-
composites were enhanced to 1.39, 1.68, 1.65
and 1.03 mmol g1, respectively. The PANI has
 4. Removal of radionuclides by carbon-based nanomaterials
a strong affinity for radionuclides and heavy
metal ions due to the large number of amine
and imine functional groups, these functional
groups can form very strong complexes with ra-
dionuclides on the nanocomposite surfaces
[283]. The chemical binding of radionuclides
with the nitrogen-containing functional groups
is much stronger than that of radionuclides with
the oxygen-containing functional. the high sorp-
tion of radionuclides on GOs and GO-based ma-
terials is mainly attributed to the surface
functional groups.
Apart from these, there is much correlative
research on the removing of U(VI) by GO/
LDH or GO/metal oxide complexes. The prepa-
ration of GO-based materials and their applica-
tion in the sorption of radionuclides (such as
U(VI), Eu(III), Sr(II), etc.) from aqueous system
are investigated by using kinetics analysis, ther-
modynamic analysis, surface complexation
models, spectroscopic techniques and theoretical
calculation. Wang’s group [284e286] has done
much useful work to develop GO-based mate-
rials. They successfully synthesized many
kinds of GO-based materials (functionalized
GO and GO-based composites) and used them
for environmental remediation. Shi’s group
[270,277,278] studied the interaction mecha-
nisms of radionuclides and GO-based materials
by spectroscopy technology combined with
theoretical calculations. There are also some pat-
ents about the application of GO-based materials
in environmental renovation. The magnetic
nanoparticles in GO composites could serve as
a good stabilizer against the aggregation of GO
nanosheets because of the strong van der Waals
interactions between the layers of graphene
nanosheets [287,288]. The magnetic composites
can be easily separated from solution using mag-
netic separation, and thereby can be used in
large scale in possible real applications. Nano-
scale zero-valent iron (NZVI) can be deposited
on GOs to prepare NZVI/GO composites, which
not only increase the stability and dispersion of
271
bare NZVI but also improve electron transfer
and increase the preconcentration of metal ions
by the coupling of the advantages of NZVI
reduction and GO high adsorption capacity
[289]. The combination of selective ion transport,
fast water permeability, good mechanical prop-
erties, and regular intersheet spacing of GO
membranes or foam makes them a highly
appealing prospect for water purification appli-
cations, either as a separation membrane, foam
or as an adsorbent [241]. Williams and Carbone
[290] demonstrate that GO membranes may
remove 99Tc, present in the form of pertechnetate
(TcOe 4 ), from water with a high degree of selec-
tivity, suggesting they provide a cost-effective
and efficient means of achieving 99Tc decontam-
ination. Cai et al. [241] synthesized the fully
phosphorylated graphene oxide foam (phos-
GOF) and the as-prepared 3D phos-GOF was
served as an adsorbent to capture U(VI) from
aqueous solution. A 3D GOF decorated by hy-
drophilic phosphate-rich functional groups to
enhance the adsorption performance toward
U(VI) with easy collection and recycling of GO.
It is evident to conclude that GO-based materials
have good potential for the removal of radionu-
clides from aqueous system. However, it is
necessary to carry out more research works
focusing on the development of lower cost,
higher efficient and environmentally friendly
GO-based materials either for scientific interests
or practical applications.
4.3 Carbon nanotube-based
nanomaterials
The CNTs have been the focus of the nanotech-
nology research since their discovery due to their
unique physicochemical properties. These cylin-
drical nanostructure allotropes of carbon are be-
ing applied in catalysis and water filters, etc.
Their diameter can be of 1 nm to several nanome-
ters with a large specific surface area (150e1500
m2 g1), and they possess mesopores which
272 6. Water treatment and environmental remediation applications of carbon-based nanomaterials
make them the ideal candidate for the removal of
radionuclides via adsorption. The contact surface
of SWCNTs with pollutants is more than
MWCNTs because SWCNTs consist of a single
cylindrical layer. However, SWCNTs as a sorbent
are used less than MWCNTs for removing con-
taminants because its synthesis is more difficult
and more expensive than MWCNTs.
The application of CNTs as adsorbents to
remove radionuclides from aqueous solutions
have been studied extensively, and the radionu-
clides can be preconcentrated efficiently by
CNTs [291e293]. The experimental conditions of
solutions, including pH and radioactive ion con-
centrations, can affect the adsorption characteris-
tics of MWCNTs, and the adsorption models
were used to fitted their experimental data. For
example, Wang’s group [293] examined the use
of uncapped MWCNTs as adsorbents for radio-
nuclide 243Am(III). About 85% 243Am(III) was
sorbed by MWCNTs after 4 days of contact time
in batch experiments, and over 95% 243Am(III)
was sorbed to MWCNTs after 1 month of contact
time. As shown in Fig. 6.31 for the kinetic desorp-
tion measurements, more than 99% of 243Am(III)
forms strong complexation with the chelating
resin. In the presence of MWCNTs, the initial
243
Am(III) concentration first drops rapidly
to ~96% of the initial concentration and then
decreases very slowly (Fig. 6.31). They suggested
that the slow desorption kinetics of 243Am(III)
bound to MWCNTs could be an indication that
the metal ions might as well be captured inside
the nanotube. They also found that Eu(III) and
Am(III) adsorption isotherms on oxidized
MWCNTs were linear when initial concentration
ranges of Eu(III) and Am(III) were from 5  107
to 5  106 mol$L1, showing that the sorption
was still unsaturated [294], Chen et al. [291]
used the surface complexation modeling to model
Sr(II) and Eu(III) adsorption onto oxidized
MWCNTs with the aid of FITEQL 3.2.
Most published papers reported the removal
of radionuclides by batch experimental study,
several works were focused on the comparison
of Eu(III) and 243Am(III) on CNTs from experi-
mental and theoretical calculations. Wang et al.
[295] studied the sorption of Eu(III) and
243
Am(III) on CNTs and found that the sorption
of Eu(III) on CNTs was stronger than that of
243
Am(III) on CNTs, which is due to the different
binding energies (Ebd) of Eu(III)/Am(III) with
different oxygen-containing functional groups
(Fig. 6.32). They found that Ebd values of Eu(III)
on CNT are much high than those of 243Am(III)
on CNT, suggested that Eu(III) can form stronger
complexes with the oxygen-containing groups of
CNTs than 243Am(III).
CNTs can easily be functionalized with
various organic molecules which can make
them specific for the selection of adsorbates
and their adsorption capability could be
improved [296e299]. The carbon nanotubes
alone as well as in their oxidized and in their
composite forms have tremendous ability to
adsorb the radioactive ions, and much research
is underway for their application in purifying
polluted water [296,297]. Some studies have
revealed that plasma-oxidized MWCNTs have
the better adsorption properties than chemically
oxidized ones; this can be ascribed to higher
number oxygenated functional groups present
on the surface of the carbon nanotubes
[298e300]. Furthermore, it has been reported
that plasma-oxidized MWCNTs can be easily
recycled and reused. The application of carboxy-
methyl cellulose (CMC) grafted MWCNTs
(MWCNT-g-CMC) in the removal of UO2þ 2
from aqueous solution was also investigated
[300]. The maximum adsorption capacity of
UO2þ 2 adsorption calculated from the Langmuir
model is 6.0  105 mol$g1 for as-produced
MWCNTs, 1.1  104 mol$g1 for N2 plasma
treated MWCNTs, and 4.7  104 mol$g1 for
MWCNT-g-CMC composites under the same
experimental conditions. The results indicate
that MWCNT-g-CMC composites have much
higher adsorption ability in the removal of
UO2þ 2 than the as-produced MWCNTs. Other
schemes of application envisage chemical
 4. Removal of radionuclides by carbon-based nanomaterials 273

FIGURE 6.31 Fractions of 243Am(III) species in MWCNTs suspension as a function of the contact time with a chelating resin
in 0.1 M NaClO4. The concentration of 243Am(III) is 7.4  107 mol L1 and that of MWCNTs is 0.5 g L1. (A) Free 243Am(III)
solution, pH 5.0  0.2; (B) presence of MWCNTs, pH 7.0  0.1 [293].

impregnation of the ACs to increase sorption
selectivity and removal efficiency, especially
from acidic media. Grafting with phosphate or
trioctylamine, which are selective for the uranyl,
are possibilities to improve the adsorption effi-
ciency of U by ACs from aqueous media
[301,302]. The composite material of MWCNTs
has also been utilized for the adsorption of heavy
metal ions from water. The MWCNTs-Fe3O4,
MWCNT/hydroxyapatite, magnetic Fe/Zn
layered double oxide CNTs, nanocomposites
have been successfully applied for the removal
of the heavy ions of U(VI), Co(II), Eu(III) and
Th(IV) ions etc. from water [303e306]. The
adsorption efficiency of functionalized or modi-
fied MWCNTs are several times more effective
in radionuclides adsorption than unmodified
MWCNTs. Chen et al. [303] reported the
maximum capacity of U(VI) adsorption achieved
to be 380.8 mg$g1 on magnetic Fe/Zn layered
double oxide@carbon nanotube composites (M-
Fe/Zn-LDO@CNTs) at the experimental condi-
tion of pH ¼ 6.0 and T ¼ 298.15 K, which was
triple than that of CNTs (140.8 mg$g1). high
removal efficiency for actinides (such as U(VI)
and 241Am(III)) through the strong electrostatic
interaction and surface complexation. They also
investigated the competitive adsorption of
U(VI) in the presence of coexisting anions
  
CO2 2
3 , Cl , Br , SO4 , NO3 and cations Mg ,
2þ
2þ þ þ
Ca , Na and K (Fig. 6.33). And the influences
have been discussed in detail according the for-
mation of dissolved uranyl complex or the occu-
pied adsorption site on adsorbents. The
synthesis of iron oxides/MMWCNTs compos-
ites with a high separation property has been
become a new research issue in the past years.
Fortunately, the sorption capacity of radionu-
clides onto magnetic composites through graft-
ing of natural and synthetic polymers can be
distinctly improved. Chen et al. [306] studied
the interaction between Eu(III) and an
MWCNT/iron oxide magnetic composite in the
absence and presence of poly(acrylic acid)
(PAA). as a function of pH, initial Eu(III) concen-
tration, and found that PAA resulted in strong
enhancement of Eu(III) adsorption at low pH.
Belloni [307] reviewed CNTs in treating and
sequestering nuclear waste stems from recent
research results that specifically investigate the
interaction between CNTs and actinides or lan-
thanides. He discussed the potential applications
Another random document with
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The Project Gutenberg eBook of Survival factor
This ebook is for the use of anyone anywhere in the United States
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Title: Survival factor

Author: Charles V. De Vet

Illustrator: Paul Orban

Release date: September 7, 2023 [eBook #71592]

Language: English

Original publication: New York, NY: Royal Publications, Inc, 1957

Credits: Greg Weeks, Mary Meehan and the Online Distributed

Proofreading Team at http://www.pgdp.net

*** START OF THE PROJECT GUTENBERG EBOOK SURVIVAL

FACTOR ***
 SURVIVAL FACTOR

By CHARLES V. DE VET

Illustrated by ORBAN

They were trapped on a viciously

primitive planet, by an electronic
bloodhound that was viciously unpredictable!

[Transcriber's Note: This etext was produced from

Infinity September 1957.
Extensive research did not uncover any evidence that
the U.S. copyright on this publication was renewed.]
The survey team was seven parsecs beyond the Rim when the
bloodhound picked up their trail.
Three years earlier the inevitable had happened. The humans of the
Ten Thousand Worlds had met another race with the faster-than-light
space drive—and an expanding population. The contacts had been
brief—and violent. Each race had set up defenses against the other,
and maneuvered for position and control of the habitable worlds
separating them. The aliens' bloodhounds formed the outer circle of
their defense perimeter.
The s-tracer continued its bleak chirping as Wallace read the figures
on its dial and made a swift calculation. "We have time for one dip
into spacebridge," he informed Saxton, the other member of the
team. "If we don't find a planet fast when we come out, we've had it."
Saxton nodded. "We'd better backtrack. Set the bridge for that star
group we recorded yesterday. Hurry. We haven't any time to spare."
Four minutes later Wallace brought the two handles of the bridge
control together—and the ship winked into hyperspace. Wallace's
body jerked upright, and he sat stiff and straight, fighting the impulse
to retch that rode his stomach muscles. The room around him took on
the visual consistency of thin milk. The low hum of the ship's
instruments increased in intensity through the hands that he pressed
tightly to his head. Mingled with the sound of the small motors was
Saxton's high-strained muttering: "I can't take any more of it! I can't
take any more of it!"
Then all was normal again. They were out of hyperspace.
Wallace reached for a knob on the board in front of him and began
turning it slowly. Both men watched the vision panel on the front wall.
After a minute a blue globe floated in from one side. "We'll have to try
that one," Wallace said. "It at least has atmosphere."
"We don't have any choice," Saxton answered. With his head he
indicated the s-tracer. Its stark chirping had begun again.
"The hound's closer than I thought," Wallace complained. "We'll have
to risk a faster passage to the surface than would ordinarily be safe."
Drops of perspiration that had gathered on his forehead joined
together and ran down the side of his nose. He shook his head to
clear them away.
By the time they entered the blue planet's atmosphere the intervals
between the chirps of the s-tracer had shortened until now they were
almost continuous. Gradually, as they plunged toward the planet's
surface, the room's temperature rose. They stripped to their shorts
and kept the pace steady. When it seemed that they could stand the
heat no longer the ship paused, and settled slowly to the ground.
Quickly Wallace shut off the drive motors. The only sound within the
ship was the purring of the cooling apparatus.
"Any chance that it can detect our cooling motor?" Saxton asked.
"I don't believe it can follow anything smaller than our main drive,"
Wallace answered. He pointed to the s-tracer. "It's already lost us. Of
course we know it won't go away. It'll circle the planet until we come
out and try again."
During the next hour, as the temperature within the ship returned
slowly to normal, Wallace and Saxton kept busy checking the gauges
that measured and recorded the elements in the planet's atmosphere.
At last Saxton sighed heavily. "Livable," he said.
"Closer to Earth norm than we could have hoped," Wallace agreed.
"What do we do now?"
"We could stay here for two years—until the bloodhound runs out of
fuel. That's the estimated time it's supplied for."
"That doesn't sound like a very encouraging prospect." Saxton's dark
tan features were lined with worry. "We don't have food enough, for
one thing. Maybe the aliens will get discouraged and go away."
"Hardly. You've forgotten that the bloodhounds are fully automatic,
and unmanned. A machine doesn't discourage very easily."
"We sure as heck ought to be able to outwit a machine," Saxton said.
He thought for a moment. "If we waited until it was across the planet
from us, we might have time to get out, and take another jump toward
home. One more and we'd be far enough in so our own cruisers could
take care of the bloodhound."
Wallace shook his head. "Its speed is too great. Our best chance is
that it doesn't hold to a straight path around the planet. The aliens—
not knowing the size of any body we might land on—wouldn't set it for
a dead-line trajectory. I hope."
There was nothing for them to do until the s-tracer had followed the
movements of their stalker long enough to make an adequate graph.
They decided to go outside while they waited.

Wallace and Saxton took only a few steps—and stopped in

amazement. They had a visitor!
The native rose from his kneeling position on the ground and stood
erect. Wallace studied the face of the naked, stick-thin savage, trying
to penetrate beneath the dirt and grime, beneath the mask of
impassive features, to find the quality that held him in questioning
immobility. For a moment he succeeded.
It was not high intelligence that he found, but rather an innate
conviction of power. A conviction and self-assurance so deep that it
needed no demonstration for expression.
Wallace glanced at Saxton where he leaned against the spaceship's
ramp, the whites of his eyes contrasting sharply with the black of his
clean negroid skin. It was clear that he too sensed the odd quality in
the other. And that he was equally unable to decide whether the
savage that so incuriously regarded first one then the other of them
was to be feared, or accepted as amicable. But both already realized
that this was no ordinary meeting between humans and an outworld
native. They were on the verge of an unusual experience.
The savage had been kneeling with his forehead touching the ground
when they stepped out of the ship. However, now that he stood
before them, there was nothing abject in his demeanor. For a long
minute he did not speak or make any motion other than to regard
them. Casually then he raised his right hand and touched his chest.
"Al-fin," he said.
The meaning of the gesture was apparent: Wallace readily
understood that the savage was giving his name. He touched his own
chest. "Ivan," he murmured.
The native turned his gaze to Saxton.
"Gus," Saxton said, shifting his feet uncomfortably.
The native nodded. "Come!" he commanded. He turned his back and
walked away.
There was no question in Wallace's mind about obeying. It was only
his subconscious that moved his hand, to make certain that his gun
was in its holster, and to glance at Saxton to see that he too was
armed. He had walked several yards before the incongruity struck
him: the savage had spoken Earthian!

They followed the native for several miles over a faint game trail that
wound leisurely through brush and skimpy, small-leaved trees, before
either of the men recovered his composure enough to speak.
"He said 'Come'," Saxton mused. "Yet we're the first humans this far
over the Rim. Where did he learn our language?"
Wallace shrugged. "I've been wondering too," he answered.
"Should we try to talk to him?" Saxton asked, glancing ahead at their
companion.
The native, apparently, had no interest in their conversation. "Better
wait," Wallace suggested.
"I don't understand it." Saxton's tone was querulous. "No one's
allowed over the Rim ahead of us. A section has to be surveyed, and
worlds declared fit for habitation, before colonists can move in. Yet we
land here and find a native speaking our language."
"Perhaps he isn't a native," Wallace said.
"What do you mean?"
"When Earth first discovered spacebridge there were no laws
regulating its use. Limits were put on colonizing areas only after some
of the earlier expeditions failed to report back. One of them might
have been marooned here."
"Then this fellow's human?"
"He could be."
"If he is, would he be naked?" Saxton asked.
"Some of those lost expeditions disappeared as long as two thousand
years ago," Wallace answered. "A colony could have slipped back a
long ways in that time."
"But not this far," Saxton demurred. "They'd still have some traces of
their original culture left."
"A one-ship colony would have very limited mechanical resources,"
Wallace said. "And they'd be isolated here. As soon as the tools and
machines they brought with them wore out they'd be almost
impossible to replace. The odds are they'd slip back fast."
"I don't know." Clearly Saxton wasn't satisfied—but he let the subject
hang. "When we saw him kneeling on the ground, I thought that he
was worshipping us. But since then he's been acting as if he thought
he was the god instead of us."
They were halfway across a small clearing now and before Wallace
could answer the native ahead stopped abruptly. He stood
motionless, with his head tilted to one side, as though listening. After
a moment he motioned them to move to the left.
As Wallace and Saxton obeyed, Al-fin pointed urgently toward their
guns. They drew, and the native turned to stare at the bushes at the
far side of the clearing.
"What does he want?" Saxton asked.
"I don't—" Wallace's answer was cut off as a huge "cat," with long
stilt-like legs spread wide, sprang out of the bushes—directly at them.
Wallace and Saxton sprayed the beams of their guns across the cat's
chest, burning a wide, smoking gash. The beast landed, sprang
again, and died.

Saxton let out a long breath of relief. "Close," he said.

Wallace stood with a puzzled frown on his face. "How did he know
the animal was there?" he asked.
"He must have a good sense of hearing," Saxton answered
doubtfully.
"It can't be that good," Wallace protested.
"Maybe this is our chance to get some fresh meat," Saxton said. He
drew a knife from his belt and knelt beside the cat's carcass. He
made several rapid cuts. After a minute he looked up. "Nothing
edible," he said. "Nothing but skin, gristle, and tendons."
They walked on.

They entered another clearing, and found themselves in the midst of

a group of naked savages, obviously Al-fin's people.
"Where did they come from?" Saxton asked, resting his hand on the
grip of his gun.
Wallace looked his way and shook his head. "No guns," he said.
"We'll have to take the chance that they're friendly."
Most of the members of the group, Wallace observed, were lying on
the ground, or idling about at the edges of the small clearing. He
counted twenty-three—of both sexes, and varying ages. There was
no sign of clothing or ornament on any of them. They were naked,
filthy, and nondescript; yet each had the mark of that quality that had
puzzled them in Al-fin—the deep inner assurance. A few glanced
their way, but without any evidence of an unusual degree of interest.
Their attention returned to Al-fin. Streaks of sweat had made gray
trails on his grimy face, and he gave off an odor that was sharp and
rancid. He sat on the ground and motioned for Wallace and Saxton to
do the same.
Wallace hesitated, then spread his hands resignedly. "This is a
strange game," he said. "We'll let him make the first moves." He and
Saxton sat down together.
Al-fin began speaking, without inflection and with few pauses. Some
of the individual words sounded faintly familiar, but the two men could
make no sense of what he said.
"I'm afraid we can't understand you," Wallace told him. In an aside to
Saxton he said, "He won't understand me either, but I don't think we'd
better ignore him."
Saxton nodded. "I guess you are right about his being human," he
said. "Some of those words were definitely Earthian."
Al-fin raised his voice in a shout, "Il-ma!"
One of the women in the center of the clearing laughed and came
toward them. She was stick-thin, as were Al-fin and most of the
others, and very dirty. As she came near she smiled. Her teeth were
discolored and rotting. She giggled.
Al-fin indicated her with a sweep of his arm. "Mate?" he inquired.
Wallace felt himself reddening. "Is he offering her to us?" he asked
Saxton.
"I think so." Saxton smiled uneasily. "It looks like it's our move now."
"We'll have to risk offending them." Wallace looked at Al-fin and
shook his head vigorously. "No mate," he said.
The woman giggled again and walked away. Al-fin seemed to have
lost interest. He pulled himself jerkily to his feet and went across the
clearing to the fire that the two surveyors had noted earlier. A large
clay kettle rested on a flat rock over the fire.
"There's meat in that kettle," Saxton said, whimsically licking his lips.
"I hope he passes some around."
"I don't think we should eat any," Wallace cautioned.
"Why not?"
"You know the saying, one man's meat...."
"But I'm starved for fresh meat," Saxton argued.
"We'll see if we can get him to give us some," Wallace said. "We can
take it back to the ship and test it before we eat any."
They watched Al-fin as he dug in the kettle with a stick and placed the
food he speared on a large leaf. He carried it to where an old man sat
with his back resting against a tree trunk. The hoary veteran had a
long scar on his right arm that ran from shoulder to elbow; evidently
he had had a brush with one of the big cats sometime in the past.
Oddly enough, he was the only native that was not thin and hungry-
looking.
"He must be the chief," Saxton said. "At least he's well fed."
Wallace nodded.
When Al-fin returned Saxton said, "Meat." At the same time he
rubbed his stomach in a circular motion.
Al-fin paused, thinking over what Saxton had said, then nodded
several times. He made a gesture with his arm for them to follow and
led them to the fat old man. "Meat," Al-fin intoned expressionlessly,
and stood as though waiting for the old man's reply.
"I hope he's in a generous mood," Saxton said.
They had seen no sign from the old man, but Al-fin turned to them
and nodded once more. "Meat," he said. He made no further move.
"Why doesn't he get it?" Saxton asked finally. "Apparently he agrees
—but he just stands there."
"Maybe we're supposed to do something now," Wallace said. "But
what? Do you suppose we're expected to pay him some way?"
"That could be," Saxton answered. "Or maybe the chief's eating the
last of what they have now, and they'll give us a chunk when they get
some more. Anyway, let's not wait any longer. I'm starved. Even
canned concentrate would taste good to me now."

By morning the s-tracer had marked the tracking chart sufficiently to

give them some data on the bloodhound's actions. Wallace went over
it carefully.
Saxton stayed in his bunk and pretended to be still sleepy, but
Wallace could feel his gaze following the work closely. When at last
he looked up Saxton said, "Well?"
"We have something to work on," Wallace answered the question in
his voice. "But unless we get more, I don't see how it will help us.
"The bloodhound," he went on, not waiting for further inquiry from
Saxton, "is acting pretty much as we thought it would. It has no
straight line trajectory. At irregular intervals it circles, backtracks, or
goes off at a new tangent. Often it stays over a particular territory for
longer than the three hours we'd need to get away. It's probable that
at some time it will do this on the other side of the planet—where it
couldn't pick up the signal of our leaving. But...."
Saxton was sitting up now. "But what?"
"It's following a random pattern." Wallace studied his fingernails as he
sought for words to make the explanation clear. "The s-tracer will
show us when it is out of range—but there's no way for us to know
how long it will stay in any one place."
"In other words there will be intervals when it will be directly across
the planet from us. But unless it stayed there for close to three hours
—the time we'd need to clear the atmosphere—it would pick up our
signal as it came around, and run us down?"
"That's about it."
"Then we'll have to take the chance."
"We could. And if we can think of nothing better, we will. But the odds
would be heavily against us. Most of its locale changes are made in a
shorter period of time than we'd need to get away."
"We can't sit here for two years." Saxton was a man whose high-
strung nature demanded action, and was the more inclined of the two
to take chances. Wallace preferred weighing influencing factors
before making any decision.
"I think we'd better wait," Wallace said. "Perhaps we'll be able to think
of something that will give us a better chance."
Saxton pulled the sheet-blanket off his legs irritably, and climbed from
the bunk, but he did not argue.

During the morning Saxton killed a small rodent, but found its flesh as
inedible as that of the cat. Wallace stayed inside studying the charts
and instruments.
They had their noonday meal in a small clearing by the side of the
ship. Wallace had been able to find no way of solving their difficulty.
For want of a better plan they'd decided to wait—while keeping close
track of their stalker.
"I've been thinking about those natives," Wallace said, as they lay
stretched on the grass. "If they are lost colonists—have you
wondered how they managed to survive here so long?"
"I did wonder how they protected themselves against the cats,"
Saxton answered. "They don't seem to have any weapons."
"Al-fin demonstrated that they must have exceptionally good hearing,"
Wallace said. "But would that be enough? You'd think the cats would
get them—when they're sleeping, if not during the day—or kill off their
young."
"That's what I meant," Saxton said. "We saw no weapons, so they
must have some other means of defense."
"They live pretty much like animals," Wallace observed. "Maybe they
stay alive the same way. If animals aren't powerful, they're usually
swift. Or they have some other survival characteristics, such as
prolific propagation. But what do these savages have—except
perhaps the sharp hearing that you mentioned? That alone shouldn't
be a deciding factor. Yet they were able to survive here for two
thousand years."
"How about an instinct of dispersal?" Saxton asked. "There might be
hundreds of groups like the one we saw."
"That would help. But my thought was that if they don't use weapons
they might have gone at it from another angle: they adjusted
themselves, instead of their tools, to their environment."
"Special ability stuff?" Saxton asked.
Wallace glanced over at the other man. By the look of abstraction on
Saxton's face he knew that no answer was necessary. Saxton's
imagination was a moving force. When a subject intrigued him he
could no more abandon it and turn to something else than he could
stop breathing. The trait was one that made him an ideal partner for
Wallace, with his more logical reasoning, and his insistence on
weighing fact against fact and belief against belief. It was, in fact, the
reason the two men had been teamed. One was the intuitive, the
other the harmonizing, controlling, factor in their combination.
Saxton rose and stretched. "I think I'll go inside," he said. "I want to
poke around in the library a while."
Wallace smiled and followed his companion into the ship. This at
least would take Saxton's mind off their troubles. Their enforced
inactivity would be less tedious for the more imaginative man.
Saxton selected several tapes from the book shelf and put them in
the magnifier. "When I find something that sounds likely," he said, "I'll
read it. Stop me if you want to discuss anything I find."

A half-hour later Saxton said, "Socrates maintained that the fewer our
needs, the nearer we resemble gods. Do you suppose Al-fin and his
tribe are approaching godhood?"
Wallace's answer, from the bunk where he lay, was a discourteous
grunt.
"I thought so too," Saxton quipped. He went on reading.
Almost an hour went by before he spoke again. "This might help put
our savages in the proper place in their cycle," he said. "Quote:
'Giambattista Vica, a native of Naples, held a theory that human
history progressed in cycles, each of which followed the same
course. The first move in a civilization began when man, terrified by
the forces of nature, invented and worshipped gods in order to
placate them. Next, he made up myths of demi-gods and heroes, and
arrived at the idea of kingship. Finally, from kingship he came to
democracy, which degenerated into chaos; after which the next cycle
started and the process was repeated."
"Interesting," Wallace said. "But even if it fits, I think we understand
well enough where these people are in their cycle. What we want now
is a clue as to what makes them different."
Wallace was about to doze off when Saxton said, "Listen to this: '... in
which he first injected the hormone that produces milk in the breasts
of nursing mothers into the bloodstream of starved virgin rats and
then introduced newly hatched squabs into their cages. Instead of
devouring the luscious meal placed before them, the starved virgin
animals acted as tender foster mothers to the helpless creatures.'" He
looked across at Wallace expectantly.
"I'm afraid I don't—" Wallace began.
"Don't you see?" Saxton asked. "Something about the food here has
made the natives different. We've got to find that food."
"That might be true also," Wallace answered slowly. "But I'm not as
interested in finding what caused the difference as I am in finding the
difference itself."
"Find one and you find the other," Saxton argued. He held up his
hand as Wallace made as though to speak. "Sleep on it," he said.
"Maybe we'll have some ideas by tomorrow."

They were able to extract no new clues from the tracking of the
bloodhound by the next forenoon. Neither man could arrive at any
means of thwarting the alien machine. Wallace had checked the
graph track minutely, looking for signs of a cycle, or cycles, in its
movements. He ended up convinced that none existed. It apparently
operated entirely at random.
At the mid-day meal Saxton suggested, "Let's pay those fellows in the
woods another visit."
"We may as well," Wallace agreed. "We're helpless here until we can
come up with some new idea."
They finished eating and strapped on their sidearms. They were not
certain that the path they took through the woods was the same they
had taken with Al-fin two days before, but at least it led in the same
general direction.
An hour later they were lost. Their way had not led them to the tribe
of naked savages and they had no idea where else to look. They
were debating whether or not to return to their ship when they
stepped out into a clearing—one larger than any they had come on
earlier.
In the center of the clearing rested a spaceship! From where they
stood they could see that its hull was rusted and weather-beaten.
"That hasn't flown in a long time," Saxton said, after the first few
minutes of wonder.
"Probably not since it first landed here," Wallace answered.
The clearing about the vessel had been kept free of brush and
bushes, and when they went across, and through the open portal of
the ship, they found the inside immaculate.
"They certainly keep it clean," Saxton observed.
"It may be a shrine to them," Wallace said. "That would explain why
we found Al-fin kneeling when we landed, and yet why he treated us
so nonchalantly. He was worshipping our ship, not us."
"I hope they don't find us here," Saxton remarked. "We might be
violating some taboo."
Most of the interior fittings of the vessel, they found, had long ago
rotted away. Only the metal parts still remained intact. The instrument
board was unfamiliar to them. "Pretty definitely an early model,"
Wallace said.
Saxton found something on one wall that held his absorbed interest.
"Come here, Ivan," he called.
"What is it?" Wallace asked, going over to stand beside him.
"Read that."
Wallace read aloud from the engraved plaque: "Spring, 2676. We, the
Dukobors, leave our Earth homes in the hope that we may find a
dwelling place for ourselves and our children, where we may worship
our God as we believe proper. We place ourselves in His hands and
pray that He will watch over us on our journey, and in the time to
come."
"That's over nineteen hundred years ago," Saxton said.
"Soon after the discovery of spacebridge," Wallace added. Without
being aware of it they both spoke in whispers.
They inspected the vessel for some time more, but found little of any
further interest.

A short time after they left the ancient spaceship Wallace and Saxton
stumbled on Al-fin and his group of naked natives.
This time they made a concerted effort to communicate with Al-fin,
and one or two of the others, but with no more success than before.
Neither side could understand more than a few words of the other's
language, and they could accomplish very little with signs.
Al-fin sat with them for a time, until they saw him tilt his head in the
gesture they remembered. On his face was the same expression of
listening. After a moment he rose leisurely and indicated that they
were to follow him. Most of the other natives, Wallace noticed on
rising, had already gone over and bunched together at one end of the
clearing. They appeared restless, but not frightened.