Accepted Manuscript: Chemical Engineering Journal
Accepted Manuscript: Chemical Engineering Journal
Accepted Manuscript: Chemical Engineering Journal
Review
Surface functional groups of carbon-based adsorbents and their roles in the re-
moval of heavy metals from aqueous solutions: A critical review
Xiaodong Yang, Yongshan Wan, Yulin Zheng, Feng He, Zebin Yu, Jun Huang,
Hailong Wang, Yong Sik Ok, Yinshan Jiang, Bin Gao
PII: S1385-8947(19)30350-X
DOI: https://doi.org/10.1016/j.cej.2019.02.119
Reference: CEJ 21032
Please cite this article as: X. Yang, Y. Wan, Y. Zheng, F. He, Z. Yu, J. Huang, H. Wang, Y.S. Ok, Y. Jiang, B. Gao,
Surface functional groups of carbon-based adsorbents and their roles in the removal of heavy metals from aqueous
solutions: A critical review, Chemical Engineering Journal (2019), doi: https://doi.org/10.1016/j.cej.2019.02.119
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Surface functional groups of carbon-based adsorbents and their roles in the removal of
Xiaodong Yang a,b, Yongshan Wanc, Yulin Zhengb, Feng Hed, Zebin Yue, Jun Huangf,g, Hailong
32611, USA.
c
National Health and Environmental Effects Research Laboratory, US EPA, Gulf Breeze, FL
32561, USA.
d
College of Environment, Zhejiang University of Technology, Hangzhou 310014, China
e
School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China
f
Hualan Design & Consulting Group Co. Ltd., Nanning 530011, China
g
College of Civil Engineering and Architecture Guangxi University, Nanning 530004, China
h
School of Environmental and Chemical Engineering, Foshan University, Foshan, Guangdong
528000, China
i
Key Laboratory of Soil Contamination Bioremediation of Zhejiang Province, School of
Environmental and Resource Sciences, Zhejiang A&F University, Hangzhou, Zhejiang 311300,
China
j
Korea Biochar Research Center, O-Jeong Eco-Resilience Institute (OJERI) & Division of
Environmental Science and Ecological Engineering, Korea University, Seoul 02841, Republic of
Korea
*
Corresponding author: phone: (352) 392-1864 ext. 285; email: bg55@ufl.edu
1
Abstract
Carbon-based adsorbents such as graphene and its derivatives, carbon nanotubes, activated
carbon, and biochar are often used to remove heavy metals from aqueous solutions. One of the
important aspects of effective carbon adsorbents for heavy metals is their tunable surface
metal removal, a systematic documentation of their syntheses and interactions with metals in
aqueous solution is crucial. This work provides a comprehensive review of recent research on
various carbon adsorbents in terms of their surface functional groups and the associated removal
behaviors and performances to heavy metals in aqueous solutions. The governing removal
mechanisms of carbon adsorbents to aqueous heavy metals are first outlined with a special focus
on the roles of surface functional groups. It then summarizes and categorizes various synthesis
methods that are commonly used to introduce heteroatoms, primarily oxygen, nitrogen, and
sulfur, onto carbon surfaces for enhanced surface functionalities and sorptive properties to heavy
metals in aqueous solutions. After that, the effects of various functional groups on adsorption
behaviors of heavy metals onto the functionalized carbon adsorbents are elucidated. A
perspective of future work on functional carbon adsorbents for heavy metal removal as well as
2
1. Introduction
Water pollution by heavy metals poses a serious threat to both human health and the
environment [1, 2]. Most heavy metals are extremely toxic, seriously harming all forms of life
including human beings when exceeding their tolerance levels [3, 4]. Heavy metals are also not
biodegradable and tend to accumulate in living organisms [5]. Due to rapid global development
over the last century, elevated amount of heavy metals enter into surface and ground water
through discharges of wastewater produced from metallurgical, mining, chemical and battery
Many treatment methods have been developed for the removal of detrimental heavy metal
interaction, ion exchange, coagulation, and membrane filtration [8-14]. Adsorption using
cost-effective methods for removal of heavy metals from aqueous solutions [15-19].
Carbonaceous materials including activated carbon (AC), biochar, carbon nanotubes (CNTs),
and graphene oxide (GO) have been widely studied for adsorption of various environmental
contaminants [20-28]. Their performance for the removal of heavy metals from aqueous solution
has been widely reported [29-35], and most studies in the literature focus on sorption
characteristics of a specific carbon material. AC is the most widely used carbon adsorbent for
water and wastewater treatment. A wide range of AC adsorbents can be prepared to suit for
various environmental applications including the removal of heavy metals from aqueous
solutions [22, 36]. Due to the high cost associated with production of coal-based AC, biochar has
heavy metal adsorption [19, 37-39]. A variety of woody biomass including agricultural wastes or
3
byproducts such as peanut hull and dairy manure can be used to develop biochar [40-42]. Its
and CNTs have been studied intensively for their potential applications in removal of heavy
metals [34, 44, 45]. Graphene is a single sheet of 2D hexagonal network of carbon and GO is the
oxidized form of graphene synthesized through chemical or thermal reduction processes. GO has
high specific surface area and rich surface functional groups, ideal for adsorption of heavy
metals. CNTs are cylindrical carbon tubes rolled from one or multiple sheets of graphene. They
feature well-defined cylindrical hollow structure, large surface area, hydrophobic wall, and easily
modified surfaces. Both single-walled and multi-walled CNTs have been tested as adsorbent
materials [35, 46, 47]. With excellent electrical, thermal and mechanical properties, CNTs and
While every carbon adsorbent has its unique structure characteristics and functionality, one
common feature shared by all carbon adsorbents is that they all contain rich active surface
functional groups, which are crucial for the surface chemistry of carbon materials and the
adsorption of heavy metals [48, 49]. It is generally believed that the chemical/physical
interactions between heavy metals and functional groups of adsorbents contribute significantly to
the adsorption of heavy metals [37, 50]. Functional groups are typically bonded with
heteroatoms on carbon surfaces, commonly oxygen, nitrogen, sulfur, phosphorus and halogens.
groups, and sulfur-containing functional groups [51]. The functionality and quantity of each type
4
of functional groups can be enhanced by chemically and/or physically modifying the surface of
carbon materials to introduce the desired heteroatoms on carbon surfaces [22, 52-57]. Thus, one
key area of research deals with the modification of carbon materials to enhance their surface
chemistry for selective adsorption of target heavy metals [34, 38, 40, 58, 59]. While it is
generally known that such modifications may improve the surface properties of carbon
adsorbents (specific surface area, pore-size distribution or pore volume), increase the presence of
functional groups, and enhance their structural stability [23, 60, 61], a systematic documentation
of how surface functional groups of carbon adsorbents interact with aqueous heavy metals is
currently lacking.
research on carbon adsorbents in terms of their surface functional groups and the associated
removal behaviors and performances to heavy metals in aqueous solutions. The specific
objectives are as follows: 1) Outline and clarify the governing removal mechanisms of carbon
adsorbents to aqueous heavy metals with a focus on the interactions between functional groups
and heavy metals; 2) summarize and categorize various modification methods for introduction of
heteroatoms, primarily oxygen, nitrogen, and sulfur, onto carbon surfaces for enhanced surface
functionalities; and 3) elucidate the effects of various functional groups on adsorption behaviors
of heavy metals onto carbon adsorbents. Perspectives of future work on functional groups of
Despite a great number of reports in the literature about the adsorption of heavy metals by
carbon adsorbents [62-65], few have conducted quantitative evaluation of the roles of function
5
groups in heavy metal adsorption [66-69]. In general, the inter-molecular interactions between
functional groups and heavy metals are complex, depending on the heterogeneity and chemistry
of the carbon surface, ionic environments of the aqueous solution, and the nature of the adsorbate.
The mechanisms by which heavy metals are adsorbed onto carbon adsorbents may involve
precipitation (Fig. 1). The specific role of each mechanism in heavy metal adsorption varies
considerably, depending on the target metal ion, ionic environment of the solution, and the
carbon adsorbent [70-72]. Harvey et al. [73] highlighted that soft Lewis base functional groups
(e.g., carbonyl and aromatic structures) favor dipole-dipole interactions such as cation-π bonding
for Cd (II) adsorption while hard Lewis base functional groups (e.g., deprotonated carboxylic
acids and phenols) favor sorption via cation exchange. Another important factor is solution pH
because it influences not only metal speciation but also surface charge of carbon absorbents and
capacities and mechanism of major heavy metals onto selected carbon adsorbents. For each of
the metals, only the carbon adsorbent with the highest adsorption capacity from the research
papers reviewed in this study is listed in the table. In general, chemisorption (ion exchange,
surface complexation, precipitation) plays a more significant role in the removal of heavy metals
from aqueous solution than physisorption (electrostatic interaction and physical adsorption) [51,
74]. Also note that several mechanisms can be at work in a particular aqueous environment. For
example, ion exchange, electrostatic interaction, and surface complexation are closely related to
surface functional groups through electrostatic forces, formation of binding sites, and covalent
bonding [75-80]. The following discussion attempts to elucidate the linkages between each
adsorption mechanism and various functional groups along with supporting examples in the
6
literature.
Physical adsorption is a weak process involves diffusional movement of heavy metals into
the pores of carbon adsorbents and then deposition onto the carbon surface without forming
chemical bonds. In general, physical adsorption is strong affected by pore size distribution and
surface area of the adsorbents [81, 82]. Increases of micropores can dramatically increase surface
area to promote physical adsorption, while increase of mesoporous can facilitate contaminant
diffusion to accelerate adsorption kinetics [83, 84]. The type of feedstock materials and carbon
synthesis methodology such as carbonization/pyrolysis temperature for AC and biochar and the
graphitization process for GO and CNTs are common factors determining the pore structure of
carbon adsorbents [42, 85]. Thus, the heterogeneity and polarity of carbon surface in association
with functional groups can aid in physical adsorption, especially driving the physical movement
of heavy metals onto carbon surface via electrostatic attraction and ion-dipole forces.
Typically, physical adsorption is dependent on the surface properties and pore structure of
carbon materials as well as the nature of heavy metals. Physical adsorption is common but
unlikely serving as a predominant adsorption mechanism for heavy metals. Nevertheless, some
studies have pointed out the importance of physical adsorption to the adsorption of aqueous
heavy metals on carbon materials. For example, Nayak et al. reported that the removal of Cd(II)
and Ni(II) from aqueous solutions by two types of ACs is mainly controlled by both physical
adsorption and pore diffusion processes [85]. Xie et al. found that [48] physical force plays a role
in adsorption of Cu(II) onto walnut shell derived AC while ion-exchange is the dominant
mechanism [48]. Biochars produced from switchgrass (at 300 oC) or pyrolytic pinewood (at 700
7
o
C) can sorb U(VI) and Cu(II) partly through physical diffusion adsorption [86, 87]. Liu et al.
[88] revealed that adsorption of Pb(II) onto biochars prepared from hydrothermal liquefaction of
biomass is exactly a physical endothermic process. Zhang et al. [89] reported that Cu(II) ions are
Electrostatic interaction occurs between positively charged heavy metals and negatively
charged carbon adsorbents, especially with the presence of functional groups [90, 91]. As a
relative weak process, the contribution of electrostatic interaction to heavy metal adsorption onto
carbon adsorbents is only secondary [92-94]. Because most carbon surfaces are variably charged,
and the point of zero charge of the adsorbent [95, 96]. The charged interface between carbons
A few studies have attributed electrostatic interaction as one of the mechanisms for heavy
metal adsorption by carbon materials. For example, Lv et al. [91] found evidence of high
physical adsorption. Liang et al. [97] indicated that MnO2-biochar possesses superior adsorption
performance (maximum capacities: Pb(II) 268.0 mg/g and Cd(II) 45.8 mg/g) due to its
electrostatic attachment, specific complexation and ion exchange. Chen et al. [98] confirmed that
synergetic contribution of electrostatic attraction and ion exchange between hydroxyl groups and
metal ions plays a significant role in the adsorption of As(V) and Pb(II) ions onto 3D graphene
8
foams consisting of few-layered vertically-aligned graphene sheets with highly graphite structure.
Complexation, ion exchange, and electrostatic attraction have been found to be the main
mechanisms of Pb(II) ions adsorbed by a magnetic AC incorporated with amino groups [90]. Lu
and Chiu [99] investigated the adsorption of Zn(II) ions onto purified CNTs and indicated that
electrostatic attraction and adsorption of Zn(II) onto CNTs increase with increasing solution pH
Ion exchange between heavy metals and protons on oxygen containing functional groups
such as carboxyl and hydroxyl groups is one of the major mechanisms for adsorption of heavy
metals by carbon adsorbents [100-102]. The efficiency of ion exchange process in adsorbing
heavy metals onto carbon surfaces depends largely on the ion size of the metal contaminant and
surface functional group chemistry of the adsorbent [19, 102]. Cation exchange capacity (CEC)
is an important indicator of heavy metal adsorption when ion exchange is the predominant
mechanism.
Ion exchange occurs typically between divalent metals of M2+ and H+ on oxygen containing
OH M 2 OM H (2)
9
Obviously, solution pH is a key factor influencing ion exchange [103]. At acidic pH, more
protons (H+) are available to saturate metal-binding sites. The release of H+ from carbon surface
where metals are adsorbed alters solution pH [104, 105]. El-Shafey [106] revealed that sulfuric
acid treated carbonaceous sorbent derived from rice husk via (175-180 oC) exhibits strong
adsorption of Zn(II) and Hg(II) through deprotonation of H+ and subsequent ion exchange.
Thitame and Shukla [107] found that the efficient adsorption of Pb(II) onto AC is dominated by
ion exchange with acidic functional groups, and the adsorption capacity reaches maximum at pH
of 6. Wu et al. [108] indicated that cation exchange of hydrogen with Cd(II) is the main
mechanism for Cd(II) removal by 3D sulfonated reduced graphene oxide aerogel. Adsorption of
heavy metals can also involve with ion exchange with other cations including Na+, K+, Ca2+, and
Mg2+. Rio et al. [109] reported that the removal of aqueous Cu(II) by sludge-derived biochar is
mainly due to the exchange of the toxic heavy metal with the calcium ions on biochar surface.
Ion exchange has also been found to dominate the adsorption of heavy metals onto Canna
Surface complexation (inner- and outer-sphere) forms multiatom structures (i.e., complexes)
with unique metal-functional groups interactions [112], playing a predominant role in adsorption
of heavy metals onto carbon adsorbents [113, 114]. For example, heavy metals can be effectively
bound by complexation with the carboxyl, phenolic and lactonic functional groups in biochars
prepared at low temperature [115]. Surface complexation can also enhance the removal of Cu(II)
ions by calcium alginate immobilized CNTs, adsorption of As(V) ions onto iron(III) oxide loaded
10
ethylenediamine functionalized multi-walled CNTs (MWCNTs), and Th(IV) immobilization by
GOs [114, 116, 117]. Guo et al. [118] indicated that Cd(II) removal by carbon adsorbents derived
from phragmites australis through urea phosphate activation involves ion exchange, electrostatic
attraction, and surface complexation, whereby nitrogen containing functional groups are
primarily responsible for Cd(II) update. Pourbeyram [119] revealed that adsorption of Pb(II),
Cd(II), Cu(II), and Zn(II) onto GO-Zr-P nanocomposite is mainly through surface complexation.
Meena et al. [120] reported that surface complexation and ion exchange are the major removal
mechanisms of heavy metals from aqueous solutions by carbon aerogel adsorbent. Wang et al.
[121] revealed that strong chemical sorption and inner-sphere surface complexation dominate the
U(VI) sorption by graphene oxides at high pH. Wang et al. [122] found that electrostatic
interaction, precipitation, and surface complexation play important roles in controlling the
2.5 Precipitation
Precipitation involves the formation of solid products during the adsorption process,
occurring either in solution or on a surface [12, 123, 124]. For examples, the removal of Pb(II)
from aqueous solutions by biochars may be controlled by the precipitation mechanism that turns
the lead ions into minerals such as cerrusite (PbCO3) and hyddrocerrusite (Pb3(CO3)2(OH)2) on
biochar surface [12, 123]. As one of the major mechanisms for heavy metal removal,
precipitation often works synergistically with other mechanisms, such as ion exchange,
electrostatic interaction, and surface complexation [19]. Precipitation of heavy metals onto
carbon adsorbents may have faster kinetics than other processes [12, 123]. Surface functional
groups may only have little effect on the precipitation of heavy metals onto carbon adsorbent, but
11
they can indirectly promote the precipitation process by influencing other adsorption
mechanisms [19]. For example, surface functional groups contribute to several mechanisms
involved in Cr (III) adsorption onto biochar derived from municipal sludge and promote the
surface precipitation process to form Cr(OH)3 on biochar surface [125, 126]. Oxidized CNTs can
adsorb more heavy metals such as Pb2+, Cu2+ and Cd2+ than the pristine ones due to the
ions onto graphene oxide is dominated mainly by precipitation and inner-sphere surface
The surface chemistry of carbons is determined, to a large extent, by the number and the
nature of surface functional groups on carbon surface [49, 130]. Several studies have provided
evidences of the enhanced heavy metal adsorption capacity with modifications of carbon
adsorbents with functional groups [53, 56, 131-133]. The driving mechanism of the
modifications lies with the introduction of various functional groups into carbon materials
through doping heteroatoms onto carbon surface [134]. Ancillary benefits of grafting functional
groups onto carbon surface may include increased electrostatic stability for the exfoliation of
CNT bundles due to the charges created. From a practical standpoint of view, modifying the
surface chemistry of carbon materials is crucial for the development of novel adsorption
technology.
The synthesis route to modify surface functional groups involves post-treatment of the
carbon material with chemical agents to control the properties of the final product. Thus, the
method of modification and the type of raw carbon material from which the final adsorbent is
12
prepared influence the nature of these functional groups. Selection of modification methods
depends on the intended application and the chemical characteristics of target contaminants. In
generally, oxidation, nitrogenation, and sulfuration are the common modification techniques that
are employed to introduce oxygen, nitrogen, and sulfur heteroatoms on carbon surface for
generation of functional groups [135, 136]. Fig. 2 is a graphic exhibition of these modification
techniques, depicting the chemical agents used in each technique and the desired functional
groups generated. The following discussion pertains to the details of each modification treatment
along with supporting studies to demonstrate the enhanced adsorption of heavy metals.
3.1 Oxidation
Surface oxidation is the most common and the easiest technique to generate oxygen
containing functional groups (e.g., -OH, -COOH, -C=O and -C-O) onto the surface of carbon
adsorbents [137, 138]. Fig. 3 exhibits typical oxidation treatment methods to introduce oxygen
containing functional groups into carbon materials for enhanced adsorption of heavy metals.
a mixture of inorganic acids (e.g., HNO3 and H2SO4) and an oxidizing agent (e.g., H2O2, KMnO4,
and NaOCl) [37, 40, 139]. This acidic treatment is favorable for enhanced adsorption of heavy
metals. Regulating the amount of oxygen onto carbons with the right dosage of oxidation agents
and experimental conditions such as reaction time and temperature are essential for building
desired functional structures to targeted heavy metals. While the wet oxidation treatment applies
to all carbon materials, the refluxing acids can sometimes be too harsh or detrimental to the
physical aspects of carbons. Observations of shortening of CNTs, damage of CNT sidewalls, and
reduced the Brunauer–Emmett–Teller (BET) surface area and total pore volume of AC have been
13
reported with wet oxidation treatment [140, 141]. For example, Maroto-Valer et al. [140]
indicated that nitric acid oxidation of AC can reduce the BET surface area by 9.2% and total pore
volume by 8.8%.
To reduce the undesired physical damage induced by wet oxidation treatment, alternative
treatment methods have been explored. Oxygen plasma treatment has been used to incorporate
oxygen containing functional groups into the external surface of AC while maintaining the
internal surface intact [142-144]. Examples of enhancement of oxygen plasma treatment include
Lee et al. [145] treating AC with He/O2 plasma generated in a dielectric-barrier discharge reactor
and Chen et al. [146] functionalizing MWCNTs with microwave-excited Ar/O2 surface-wave
plasma treatment. While the external carbon surfaces become rougher with treatment, it should
be noted that the outcome changes with experimental conditions. Chen et al. [146] noted that the
efficiency of Ar/O2 plasma treatment in enhancing functional groups increases with increasing
plasma power and treatment time and Lee et al. [145] indicated a reduced BET surface area due
with a high-energy electron beam at an intensity of 6.25 mA to control oxygen content in the
formed GO [34] . The authors found that the oxygen-containing groups of GO increase with
increasing irradiation dosages, varying from 6.4 and 19.2 kGy obtained by changing the
realized by changing irradiation dosages. They further noted that the maximum Pb(II) sorption
capacity increases with irradiation dosages, confirming that oxygen-containing functional groups
Several studies have reported the enhanced sorption capacities of carbon adsorbents after
14
oxidation modifications [147-149]. For example, nitric acid, ozone, and electrochemical
oxidation techniques can enhance Cd(II) sorption capacity of AC cloth, CNTs, carbon nanofibres,
and AC [150, 151]. Cationic surfactant oxidation of AC can improve its adsorption rate and
capacity to Cr(VI) in aqueous solution [152]. Chitosan-coated phosphoric acid treated coconut
shell carbon also exhibits great effectiveness in the removal of aqueous Zn(II) [153].
3.2 Nitrogenation
(e.g., -NH2, -NH, -C=N and -C-N) onto the surface of carbon materials [154]. The introduction
with ammonia, urea or amines, and this can significantly enhance the polarity of its surface and
thus increase its specific interaction with polar adsorbates [132]. Fig. 4 exhibits typical
nitrogenation treatment methods to introduce nitrogen containing functional groups onto carbon
surface for enhanced adsorption of heavy metals. Typically, wet chemistry treatment involves
nitration of the carbon followed with reduction [52]. Nitration is carried out by refluxing carbons
with the nitrating mixture consisting of concentrated H2SO4 and concentrated HNO3 at a
specified volume ratio. The active nitrating species, nitronium ion (NO2+), is produced by
The NO2+ ion is very reactive and can attach to aromatic rings of carbon surface by electrophilic
aromatic substitution to form nitroaromatic compounds. These compounds are then reduced by
15
sodium dithionite (Na2S2O4) of a specified concentration. Among the two steps, nitration is the
slow process that controls the efficiency of the treatment. The mixed acid ratio has a significant
effect on nitration efficiency. An increase of the ratio from 1:1 to 2:1 or 3:1 can shorten the
reaction time to about 30 min. Like wet acid oxidation treatment, the nitration/reduction
treatment may result in reduction of BET surface area and pore volume though negligible effects
Thermal treatment of carbons in the presence of nitrogen supplying agent such as ammonia,
urea, melamine or nitrogen oxides may also produce nitrogen-enriched carbons. For example,
by ammoxidation at 350 ◦C for 2-3 h, by a mixture of ammonia and air at the ratio of 1:3 [156].
Similarly, a post synthesis treatment with ammonia to introduce nitrogen in CNTs can be
accomplished with first treating the CNTs in nitric acid at 100 ◦C for 2h followed with thermal
amino-functionalization of CNTs, has recently drawn a great deal of interest due to its potential
for multiple applications including absorbents for heavy metal removal. Alireza and Ali [158]
provided an excellent review on the synthesis of amino-functionalized CNTs. The most common
route of amino-functionalization of CNTs is firstly to produce oxidized CNTs via various agents,
such as HNO3, H2SO4, and H2O2 or oxidative coupling to generate carboxylic acid (COOH)
groups on the sidewalls of the CNTs, followed by converting carboxylated CNTs into
amino-functionalized CNTs in the presence of molecules containing the free amino groups [159].
The amide formation process can be accomplished by direct coupling of ethylenediamine with
carboxylic groups or reducing the carboxyl group to hydroxymethyl, followed by forming amino
16
groups [160]. Another commonly used method to create active sites for incorporating
amino-functional groups on the CNT surfaces is the NH3 plasma treatment and the
microwave-excited NH3/Ar surface wave plasma [161, 162]. Similar to the oxygen plasma
treatment, the power level and the gas flow rate are important factors influencing the number of
Many publications have reported the enhanced heavy metal sorption capacity through
nitrogenation treatment of carbon adsorbents [163]. For example, nitrogenation of AC under NH3
atmosphere after pre-oxidation with HNO3 can improve the adsorption rate and capacity of Cu(II)
ions due to the increased amount of nitrogen-containing functional groups on carbon surface
[155]. Nitric acid with thionyl chloride treatment and ethylenediamine reaction can effectively
incorporate N-, S-, and Cl-containing functional groups onto the surface of AC, resulting in great
adsorption rate and capacity for Hg(II) ions [164]. Amino-modified biochar exhibits excellent
adsorption performance for Cu(II) through strong chemical complexation [52]. Nitrogen-doped
magnetic carbon nanoparticles exhibit 10-fold increase in adsorption capacity for Cr(III) ion
3.3 Sulfuration
Sulfuration treatment is often used to introduce sulfur containing functional groups (e.g.,
C-S, C=S, or S=O) onto the surface of carbon adsorbents. The introduction of sulfur onto carbon
materials is accomplished through reactions of carbon with sulfurizing agents such as elemental
S, SO2, H2S, Na2S, K2S, and dimethyl disulfide. Such modifications have been typically done on
AC [54, 132] and recently on GO and CNTs [166-169]. Fig. 5 exhibits typical sulfuration
treatment methods to introduce sulfur containing functional groups onto carbon surface for
17
various applications. Similar to the nitrogenation treatment, sulfuration of carbon surface can
also be realized through different chemical reaction routes that often require heat or acid
treatments (Fig. 5). A large amount of sulfur (up to >30% wt) can be incorporated with most
carbon-sulfur surface groups existing in the form of thiocarbonyls [170]. In addition to the
benefit of introducing sulfur containing functional groups, sulfuration treatment may also change
the porous structure of carbons with reported increase or decrease in specific surface area and
pore volume, depending on the treatment conditions [171-173]. The decrease in surface area and
pore volume is likely caused by sulfur-containing particles that may plug the pores.
Several publications have reported the enhanced heavy metal sorption capacity through
sulfuration treatment of carbon adsorbents. For example, Tajar et al. [55] reported that surface
modification of nut shells derived AC with SO2 at ambient temperature can greatly enhance
removal of Cd(II) from aqueous solutions. Macıas-Garcıa et al. [174] indicated that AC treated
with SO2 at 900 oC can improve the adsorption capacity of Cd(II) ions by about 70%.
Macıas-Garcıa et al. [173] also examined adsorption of Pb(II) onto AC treated with SO2 and/or
H2S at varying temperature and found that the amount of Pb(II) adsorbed increases with
increasing sulfur content in the AC. Shen and Chen [175] treated graphene nanosheets with
sulfanilic acid to obtain sulfonated graphene, demonstrating an excellent adsorption capacity (58
mg/g) to Cd(II) in aqueous solutions . Zhao et al. [176] found that sulfhydryl groups can be
decorated onto GO surface through an easy reaction route and the sulfhydryl functionalized GO
18
kinetics and isotherms to evaluate the performance of carbon adsorbents. The pseudo second
order (PSO) model is perhaps the most widely used to fit the adsorption kinetics data, signifying
chemisorption dominated mechanisms for heavy metal adsorption by carbons. While both
Langmuir and Freundlich models are often used to simulate the isotherm data. The Langmuir
isotherm, suggesting monolayer adsorption onto carbon surface, is more popular than the
Freundlich isotherm, probably because it predicts the maximum adsorption capacity (Qmax). In
this section, we summarize heavy metal adsorption performance of various carbon adsorbents
with oxygen, nitrogen, sulfur, and other functional groups in to Table 2, Table 3, Table 4, and
Table 5, respectively.
Oxygen containing functional groups are so far the most important in influencing surface
reactions, surface behavior, hydrophilicity, electrical and catalytic properties of carbons. Table 2
summarizes the effects of oxygen containing functional groups on the removal of heavy metals
by carbon adsorbents in term of their maximum adsorption capacities, the best-fit kinetic and
isotherm models, and the specific functional groups. The hydroxy and carboxyl groups, among
the most common functional groups, have been found to contribute widely to the adsorption of
heavy metals, such as Pb(II), Cr(VI), Hg(II), Cd(II) and Ni(II) ions onto various carbon
adsorbents [177-180]. In addition, -C=O and -C-O functional groups have been reported more
likely to make effects on the surface of GO based adsorbents [181, 182]. Yang et al. [183]
revealed the great adsorption capacity of Cu(II) ions onto GO through an aggregation process
caused by oxygen containing functional groups binding to Cu(II) in aqueous solutions. Bai et al.
[34] and Bian et al. [50] have also pointed out the important role of oxygen-containing groups on
19
surfaces of GO played in the adsorption of Pb(II) and Cd(II), respectively. Adsorption of Cr (VI)
on H3PO4 treated biochar was through forming inner sphere complex with the surface oxygenic
functional groups on the biochar [97]. Wang et al. [184] noted that the adsorption capacity of
MWCNTs treated with concentrated HNO3 is significantly increased due to creation of oxygen
functional groups that can react with Pb2+ to form complex or salt precipitates on the CNTs
surface. In addition, the adsorption equilibrium time for the acidified CNTs is much shorter than
that for ACs. Different chemical and physical modification methods have been applied to oxidize
biochars derived from various feedstocks and the modifications dramatically increased the
contents of surface oxygen containing functional groups and thus biochars’ adsorption rates and
capacities to various heavy metals including Pb(II), Cd(II), Cu(II), Ni(II), etc. [19, 37].
Because incorporation of nitrogen groups onto carbon surface can increase its basic
properties to enhance the adsorption of heavy metals, the nitrogen containing functional groups
have received increasing attentions in the research of carbon adsorbents. On the other hand, the
introduction of nitrogen functional groups also had negligible effects on porous properties of
carbons [155]. Table 3 displays the related studies on heavy metal adsorption of carbon materials
with nitrogen containing functional groups, summarizing the relevant adsorption capacity and the
best-fit kinetic and isotherm models. The nitrogen containing functional groups, such as -NH2
and -NH, contribute mostly to selective adsorption of heavy metals onto carbon nanomaterials,
which are commonly synergistic with the oxygen containing functional groups. The
nitrogen-containing ACs derived from ammonium humates show high adsorption ability to
aqueous Cu(II) and Pb(II), even better than many commercial ACs [185].
20
Nitrogen-fictionalized carbon (biochar/AC) can be obtained directly from diammonium
hydrogen phosphate treatment biomass through pyrolysis and have strong sorption ability to
aqueous Cr(VI) [136]. Several other carbon materials including microporous carbon, mesoporous
carbon, magnetic carbon nanoparticles, and carbon film have been doped with nitrogen to
introduce nitrogen containing functional groups on carbon surfaces to increase their adsorption
ability to various heavy metals in aqueous solutions [93, 135, 165, 186, 187].
In general, sulfur containing functional groups on carbon adsorbents are beneficial to their
sulfur containing functional groups can either increase or decrease specific surface area and pore
volume of the carbon adsorbents [171-173], which may also affect their adsorption performances.
In addition, elemental sulfur has been loaded into carbon adsorbents through sulfuration
treatment such as solution infiltration and chemical reaction-deposition [188], which can expand
their adsorption ability to various aqueous heavy metals. Table 4 lists selected studies on the
effects of sulfuric groups on carbon adsorption of heavy metals, summarizing the corresponding
adsorption capacity as well as the best-fit kinetic and isotherm models. As can be seen, the
sulfuric functional groups significantly enhance the adsorption performance of heavy metals onto
carbons, especially with respect to the adsorption of Cu(II) and Cd(II) ions onto GO and CNT
based adsorbents. Feng et al. [56] revealed that the elemental sulfur species deposited on
carbonaceous surfaces after continuous exposure to hydrogen sulfide are the most effective
sulfur-functionalized ordered mesoporous carbons with sulfur bearing salts activating can
21
simultaneously increase its specific surface area (837-2,865 m2/g) and pore volume (0.71-2.3
cm3/g), the affinity of the sulfurized carbons towards heavy metals is in order of
only hold a relatively complete sp2-hybridized plane with a high affinity to aromatic pollutants in
water, but also have sulfonic acid groups and partial original oxygen-containing groups that
exhibit fast adsorption kinetic rate and superior adsorption capacity towards aqueous Cd(II)
[175]. It has also been reported that dithiocarbamate groups functionalized MWCNTs prepared
by ethylenediamine and carbon disulfide have very high adsorption capacities for Cd(II), Cu(II),
Selected studies about the effects of other functional groups on carbon adsorption for heavy
metals are summarized in Table 5 along with the corresponding adsorption capacity and the
best-fit kinetic and isotherm models. While oxygen, nitrogen and sulfur containing functional
groups are predominant for the adsorption of heavy metals, other functional groups (e.g., -C=C,
-CH2, -O-CH3 and -P-O-C) can also be introduced to carbon surface to promote heavy metal
adsorption (Table 5). Xu et al. [39] confirmed precipitation of Pb(II) with the CO32- group
released from waste-art-paper biochar to form PbCO3 and Pb2(OH)2CO3 crystals on its surface
and indicated that high temperature incineration of the spent biochar can turn it into value-added
(high purity >96%) PbO nanoparticles. Tounsadi et al. [191] revealed that ACs prepared from
Glebionis coronaria L. biomass by phosphoric acid activation are rich in phosphorus containing
surface functional groups, which are beneficial to the removal of Cd(II) from aqueous solution.
22
ions from nuclear industrial effluents, which was due to the binding contribution of different
Clearly, surface functional groups of carbon materials play important roles in the removal of
heavy metals from aqueous solutions. The interactions between the functional groups and the
heavy metals can directly or indirectly affect the adsorption mechanisms such as electrostatic
interaction, surface complexation, ion exchange, physical adsorption, and precipitation (Fig. 1).
environmental remediation. One key area of research deals with surface modification of carbon
materials by incorporating heteroatoms on carbon surfaces (Fig. 2), thereby selectively adsorbing
target heavy metals. Among the different chemical modification methods, oxidation,
nitrogenation, and sulfuration are the most commonly used ones and can effectively introduce
corresponding oxygen, nitrogen, and sulfur containing functional groups on the carbon surfaces
to promote the adsorption of heavy metals (Fig. 3-5). Overall, carbon materials with designed
surface functional groups are promising adsorbents for various environmental applications,
especially with respect to the removal of heavy metal ions from aqueous solutions. To advance
and further promote the research on functionalized carbon adsorbents, additional investigations
are needed in several directions, such as: 1) Current surface modification techniques of carbon
materials often require strong acid/base treatment, high heat/pressure treatment, or intensive
23
Despite the efforts by researchers to investigate the mechanism of adsorption, it is commonly
believed that more profound and comprehensive characterization methods on the surface
properties of carbon adsorbents are required to further explain and elucidate the adsorption
behaviors and mechanisms. 3) While the same functional group behaves similarly in the
adsorption process, quantitative evaluation of the role of each type of function groups in heavy
metal adsorption does not exist in the literature. 4) Because functionalized carbon materials have
unique and tunable physicochemical properties, their applications in other fields such as energy
Acknowledgments
This work was supported in part by the USDA through Grant 2018-38821-27751 and China
Scholarship Council (CSC). The views expressed in this article are those of the authors and do
not necessarily reflect the views or policies of the funding agencies or the U.S. Environmental
Protection Agency.
24
References
[1] R.W. Furness, Heavy Metals in the Marine Environment, CRC press, 2017.
[2] S. Ricordel, S. Taha, I. Cisse, G. Dorange, Heavy metals removal by adsorption onto peanut
husks carbon: characterization, kinetic study and modeling, Separation and purification
[3] D. Sud, G. Mahajan, M. Kaur, Agricultural waste material as potential adsorbent for
sequestering heavy metal ions from aqueous solutions - A review, Bioresource technology, 99
(2008) 6017-6027.
[4] I. Al-Saleh, N. Shinwari, A. Mashhour, G.E.D. Mohamed, A. Rabah, Heavy metals (lead,
cadmium and mercury) in maternal, cord blood and placenta of healthy women, International
[5] R. Xiao, S. Wang, R. Li, J.J. Wang, Z. Zhang, Soil heavy metal contamination and health
risks associated with artisanal gold mining in Tongguan, Shaanxi, China, Ecotoxicology and
[6] M. Kobya, E. Demirbas, E. Senturk, M. Ince, Adsorption of heavy metal ions from aqueous
solutions by activated carbon prepared from apricot stone, Bioresource technology, 96 (2005)
1518-1521.
[7] G. Zhao, J. Li, X. Ren, C. Chen, X. Wang, Few-layered graphene oxide nanosheets as
superior sorbents for heavy metal ion pollution management, Environmental science &
[9] J. Wang, B. Chen, Adsorption and coadsorption of organic pollutants and a heavy metal by
graphene oxide and reduced graphene materials, Chemical Engineering Journal, 281 (2015)
379-388.
[10] F. Fu, Q. Wang, Removal of heavy metal ions from wastewaters: a review, Journal of
[11] A. Demirbas, Heavy metal adsorption onto agro-based waste materials: a review, Journal of
Removal of heavy metals from aqueous solution by biochars derived from anaerobically digested
[13] S.S. Ahluwalia, D. Goyal, Microbial and plant derived biomass for removal of heavy metals
[14] S. Wan, J. Wu, S. Zhou, R. Wang, B. Gao, F. He, Enhanced lead and cadmium removal
[15] M. Hua, S. Zhang, B. Pan, W. Zhang, L. Lv, Q. Zhang, Heavy metal removal from
water/wastewater by nanosized metal oxides: a review, Journal of hazardous materials, 211 (2012)
317-331.
26
[16] X. Cao, L. Ma, B. Gao, W. Harris, Dairy-manure derived biochar effectively sorbs lead and
[17] S. Wang, B. Gao, A.R. Zimmerman, Y. Li, L. Ma, W.G. Harris, K.W. Migliaccio, Removal
of arsenic by magnetic biochar prepared from pinewood and natural hematite, Bioresource
[18] S. Wan, N. Qu, F. He, M. Wang, G. Liu, H. He, Tea waste-supported hydrated manganese
dioxide (HMO) for enhanced removal of typical toxic metal ions from water, Rsc Advances, 5
(2015) 88900-88907.
[19] M.I. Inyang, B. Gao, Y. Yao, Y.W. Xue, A. Zimmerman, A. Mosa, P. Pullammanappallil, Y.S.
Ok, X.D. Cao, A review of biochar as a low-cost adsorbent for aqueous heavy metal removal,
[21] R.F. Ribeiro, V.C. Soares, L.M. Costa, C.C. Nascentes, Production of activated carbon from
biodiesel solid residues: an alternative for hazardous metal sorption from aqueous solution,
[22] J. Fang, B. Gao, A. Mosa, L. Zhan, Chemical activation of hickory and peanut hull
hydrochars for removal of lead and methylene blue from aqueous solutions, Chemical Speciation
[24] X.Y. Zhang, B. Gao, A.E. Creamer, C.C. Cao, Y.C. Li, Adsorption of VOCs onto engineered
[25] A.E. Creamer, B. Gao, Carbon-based adsorbents for postcombustion CO2 capture: A critical
[26] J. Fang, L. Zhan, Y.S. Ok, B. Gao, Minireview of potential applications of hydrochar
[27] W. Zou, B. Gao, Y.S. Ok, L. Dong, Integrated adsorption and photocatalytic degradation of
[28] A.U. Rajapaksha, S.S. Chen, D.C.W. Tsang, M. Zhang, M. Vithanage, S. Mandal, B. Gao,
N.S. Bolan, Y.S. Ok, Engineered/designer biochar for contaminant removal/immobilization from
soil and water: Potential and implication of biochar modification, Chemosphere, 148 (2016)
276-291.
determination of some functional groups on Chlorella for the evaluation of their contribution to
28
[30] L. Yu, F. Ruiqi, L. Zimo, F. Wenzhe, W. Zhuoxing, X. Xinhua, Preparation of Functional
Carbon-Based Materials for Removal of Heavy Metals from Aqueous Solution, Progress in
[31] M.A.A. Zaini, Y. Amano, M. Machida, Adsorption of heavy metals onto activated carbons
derived from polyacrylonitrile fiber, Journal of Hazardous Materials, 180 (2010) 552-560.
[32] Z. Ahmad, B. Gao, A. Mosa, H.W. Yu, X.Q. Yin, A. Bashir, H. Ghoveisi, S.S. Wang,
Removal of Cu(II), Cd(II) and Pb(II) ions from aqueous solutions by biochars derived from
[33] B. Wang, B. Gao, A.R. Zimmerman, X.Q. Lee, Impregnation of multiwall carbon nanotubes
in alginate beads dramatically enhances their adsorptive ability to aqueous methylene blue,
[34] J. Bai, H.M. Sun, X.J. Yin, X.Q. Yin, S.S. Wang, A.E. Creamer, L.J. Xu, Z. Qin, F. He, B.
Synthesis, characterization, and removal of aqueous lead [Pb(II)], Acs Applied Materials &
[35] T.Z. Liu, B. Gao, J.N. Fang, B. Wang, X.D. Cao, Biochar-supported carbon nanotube and
graphene oxide nanocomposites for Pb(II) and Cd(II) removal, Rsc Advances, 6 (2016)
24314-24319.
29
[36] J. Fang, B. Gao, A.R. Zimmerman, K.S. Ro, J.J. Chen, Physically (CO2) activated
hydrochars from hickory and peanut hull: preparation, characterization, and sorption of
methylene blue, lead, copper, and cadmium, Rsc Advances, 6 (2016) 24906-24911.
[37] H.Y. Wang, B. Gao, S.S. Wang, J. Fang, Y.W. Xue, K. Yang, Removal of Pb(II), Cu(II), and
Cd(II) from aqueous solutions by biochar derived from KMnO4 treated hickory wood,
[38] Y.M. Zhou, B. Gao, A.R. Zimmerman, J. Fang, Y.N. Sun, X.D. Cao, Sorption of heavy
metals on chitosan-modified biochars and its biological effects, Chemical Engineering Journal,
[39] X. Xu, X. Hu, Z. Ding, Y. Chen, B. Gao, Waste-art-paper biochar as an effective sorbent for
recovery of aqueous Pb (II) into value-added PbO nanoparticles, Chemical Engineering Journal,
[40] Y. Xue, B. Gao, Y. Yao, M. Inyang, M. Zhang, A.R. Zimmerman, K.S. Ro, Hydrogen
peroxide modification enhances the ability of biochar (hydrochar) produced from hydrothermal
carbonization of peanut hull to remove aqueous heavy metals: batch and column tests, Chemical
[41] X. Xu, X. Cao, L. Zhao, H. Wang, H. Yu, B. Gao, Removal of Cu, Zn, and Cd from aqueous
solutions by the dairy manure-derived biochar, Environmental Science and Pollution Research,
20 (2013) 358-368.
30
[42] Y. Sun, B. Gao, Y. Yao, J. Fang, M. Zhang, Y. Zhou, H. Chen, L. Yang, Effects of feedstock
type, production method, and pyrolysis temperature on biochar and hydrochar properties,
[43] H. Yu, W. Zou, J. Chen, H. Chen, Z. Yu, J. Huang, H. Tang, X. Wei, B. Gao, Biochar
[44] S. Kumar, R.R. Nair, P.B. Pillai, S.N. Gupta, M. Iyengar, A. Sood, Graphene
oxide–MnFe2O4 magnetic nanohybrids for efficient removal of lead and arsenic from water,
[45] J. Liu, X. Ge, X. Ye, G. Wang, H. Zhang, H. Zhou, Y. Zhang, H. Zhao, 3D graphene/δ-MnO2
aerogels for highly efficient and reversible removal of heavy metal ions, Journal of Materials
[46] Y. Tian, B. Gao, V.L. Morales, L. Wu, Y. Wang, R. Munoz-Carpena, C. Cao, Q. Huang, L.
Yang, Methods of using carbon nanotubes as filter media to remove aqueous heavy metals,
[47] M. Inyang, B. Gao, A. Zimmerman, Y.M. Zhou, X.D. Cao, Sorption and cosorption of lead
31
[48] R. Xie, Y. Jin, Y. Chen, W. Jiang, The importance of surface functional groups in the
adsorption of copper onto walnut shell derived activated carbon, Water Science and Technology,
76 (2017) 3022-3034.
[49] V. Strelko Jr, D. Malik, M. Streat, Characterisation of the surface of oxidised carbon
[50] Y. Bian, Z.-Y. Bian, J.-X. Zhang, A.-Z. Ding, S.-L. Liu, H. Wang, Effect of the
oxygen-containing functional group of graphene oxide on the aqueous cadmium ions removal,
Makhlouf, M. Goodarzi, A. Garshasbi, Study on the removal of heavy metal ions from industry
waste by carbon nanotubes: effect of the surface modification: a review, Critical Reviews in
[52] G.-X. Yang, H. Jiang, Amino modification of biochar for enhanced adsorption of copper ions
32
[55] A.F. Tajar, T. Kaghazchi, M. Soleimani, Adsorption of cadmium from aqueous solutions on
sulfurized activated carbon prepared from nut shells, Journal of Hazardous Materials, 165 (2009)
1159-1164.
[56] W. Feng, E. Borguet, R.D. Vidic, Sulfurization of a carbon surface for vapor phase mercury
[57] M.F. El-Banna, A. Mosa, B. Gao, X.Q. Yin, Z. Ahmad, H.Y. Wang, Sorption of lead ions
[58] A.L. Cazetta, A.M. Vargas, E.M. Nogami, M.H. Kunita, M.R. Guilherme, A.C. Martins, T.L.
Silva, J.C. Moraes, V.C. Almeida, NaOH-activated carbon of high surface area produced from
coconut shell: kinetics and equilibrium studies from the methylene blue adsorption, Chemical
[59] X. Hu, Z.H. Ding, A.R. Zimmerman, S.S. Wang, B. Gao, Batch and column sorption of
arsenic onto iron-impregnated biochar synthesized through hydrolysis, Water Research, 68 (2015)
206-216.
1683-1689.
33
[61] H.H. Lyu, B. Gao, F. He, C. Ding, J.C. Tang, J.C. Crittenden, Ball-milled carbon
nanomaterials for energy and environmental applications, Acs Sustainable Chemistry &
adsorption using functional mesoporous silica and activated carbon, Journal of hazardous
[63] C. Liu, Z. Tang, Y. Chen, S. Su, W. Jiang, Characterization of mesoporous activated carbons
prepared by pyrolysis of sewage sludge with pyrolusite, Bioresource Technology, 101 (2010)
1097-1101.
from a native invasive wood on removal of trace toxic metals from wastewater, Journal of
[65] M. Guo, G. Qiu, W. Song, Poultry litter-based activated carbon for removing heavy metal
carbons from pecan nutshell and their application in the antagonistic adsorption of heavy metal
[67] L. Dong, W. Liu, R. Jiang, Z. Wang, Study on the adsorption mechanism of activated carbon
removing low concentrations of heavy metals, Desalination and Water Treatment, 57 (2016)
7812-7822.
34
[68] C.K. Ahn, D. Park, S.H. Woo, J.M. Park, Removal of cationic heavy metal from aqueous
[69] D. Mohan, K.P. Singh, V.K. Singh, Wastewater treatment using low cost activated carbons
derived from agricultural byproducts—a case study, Journal of Hazardous materials, 152 (2008)
1045-1053.
[70] H. Li, X. Dong, E.B. da Silva, L.M. de Oliveira, Y. Chen, L.Q. Ma, Mechanisms of metal
466-478.
[71] X. Yang, Y. Xu, B. Xue, Y. Jiang, F. Li, Cordierite reinforced graphite nanocomposite with
[73] O.R. Harvey, B.E. Herbert, R.D. Rhue, K. Li-Jung, Metal interactions at the biochar-water
35
[74] A. Swiatkowski, M. Pakula, S. Biniak, M. Walczyk, Influence of the surface chemistry of
modified activated carbon on its electrochemical behaviour in the presence of lead (II) ions,
[75] P. Miretzky, A.F. Cirelli, Hg (II) removal from water by chitosan and chitosan derivatives: a
[76] L. Zhang, F. Pan, X. Liu, L. Yang, X. Jiang, J. Yang, W. Shi, Multi-walled carbon nanotubes
[77] E.-A. Kim, A.L. Seyfferth, S. Fendorf, R.G. Luthy, Immobilization of Hg (II) in water with
[78] A.E. Chávez-Guajardo, J.C. Medina-Llamas, L. Maqueira, C.A. Andrade, K.G. Alves, C.P.
de Melo, Efficient removal of Cr (VI) and Cu (II) ions from aqueous media by use of
[79] Z. Aksu, A.B. Akın, Comparison of Remazol Black B biosorptive properties of live and
[80] P. Hadi, M. Xu, C. Ning, C.S.K. Lin, G. McKay, A critical review on preparation,
36
[81] S.L. Zuo, A review of the control of pore texture of phosphoric acid-activated carbons, New
[82] M. Kruk, M. Jaroniec, K.P. Gadkaree, Determination of the specific surface area and the
pore size of microporous carbons from adsorption potential distributions, Langmuir, 15 (1999)
1442-1448.
[83] A.A. Fomkin, I.E. Men'shchikov, A.A. Pribylov, V.V. Gur'yanov, A.V. Shkolin, D.S. Zaitsev,
A.V. Tvardovskii, Methane adsorption on microporous carbon adsorbent with wide pore size
[84] N.M.S. Buarque, H.L.D. Buarque, J. Capelo-Neto, Adsorption kinetics and diffusion of
lignocellulosic wastes for heavy metal wastewater remediation: Effect of activation conditions,
[86] S. Kumar, V.A. Loganathan, R.B. Gupta, M.O. Barnett, An assessment of U (VI) removal
[87] Z. Liu, F.-S. Zhang, J. Wu, Characterization and application of chars produced from
37
[88] Z. Liu, F.-S. Zhang, Removal of lead from water using biochars prepared from hydrothermal
[89] Y. Zhang, H. Chi, W. Zhang, Y. Sun, Q. Liang, Y. Gu, R. Jing, Highly efficient adsorption of
[90] R. Fu, Y. Liu, Z. Lou, Z. Wang, S.A. Baig, X. Xu, Adsorptive removal of Pb (II) by
magnetic activated carbon incorporated with amino groups from aqueous solutions, Journal of
[91] D. Lv, Y. Liu, J. Zhou, K. Yang, Z. Lou, S.A. Baig, X. Xu, Application of
EDTA-functionalized bamboo activated carbon (BAC) for Pb (II) and Cu (II) removal from
[92] L. Cui, Y. Wang, L. Gao, L. Hu, L. Yan, Q. Wei, B. Du, EDTA functionalized magnetic
graphene oxide for removal of Pb (II), Hg (II) and Cu (II) in water treatment: Adsorption
mechanism and separation property, Chemical engineering journal, 281 (2015) 1-10.
[93] K. Li, J. Cao, H. Li, J. Liu, M. Lu, D. Tang, Nitrogen functionalized hierarchical
microporous/mesoporous carbon with a high surface area and controllable nitrogen content for
[94] F. Fang, L. Kong, J. Huang, S. Wu, K. Zhang, X. Wang, B. Sun, Z. Jin, J. Wang, X.-J.
Huang, Removal of cobalt ions from aqueous solution by an amination graphene oxide
by biochar from sugar beet tailing, Journal of hazardous materials, 190 (2011) 909-915.
[97] J. Liang, X. Li, Z. Yu, G. Zeng, Y. Luo, L. Jiang, Z. Yang, Y. Qian, H. Wu, Amorphous
MnO2 modified biochar derived from aerobically composted swine manure for adsorption of Pb
(II) and Cd (II), ACS Sustainable Chemistry & Engineering, 5 (2017) 5049-5058.
[98] G. Chen, Y. Liu, F. Liu, X. Zhang, Fabrication of three-dimensional graphene foam with
high electrical conductivity and large adsorption capability, Applied Surface Science, 311 (2014)
808-815.
[99] C. Lu, H. Chiu, Adsorption of zinc (II) from water with purified carbon nanotubes,
adsorption mechanism of Ni (II) on graphene oxides by batch experiments and density functional
39
[102] L.H. Dong, L.A. Hou, Z.S. Wang, P. Gu, G.Y. Chen, R.F. Jiang, A new function of spent
activated carbon in BAC process: Removing heavy metals by ion exchange mechanism, Journal
[103] H. Wang, A.A. Keller, K.K. Clark, Natural organic matter removal by adsorption onto
magnetic permanently confined micelle arrays, Journal of hazardous materials, 194 (2011)
156-161.
[104] W. Peng, H. Li, Y. Liu, S. Song, Comparison of Pb (II) adsorption onto graphene oxide
prepared from natural graphites: diagramming the Pb (II) adsorption sites, Applied Surface
[105] G.P. Rao, C. Lu, F. Su, Sorption of divalent metal ions from aqueous solution by carbon
[106] E. El-Shafey, Removal of Zn (II) and Hg (II) from aqueous solution on a carbonaceous
sorbent chemically prepared from rice husk, Journal of hazardous materials, 175 (2010) 319-327.
[107] P.V. Thitame, S.R. Shukla, Removal of lead (II) from synthetic solution and industry
wastewater using almond shell activated carbon, Environmental Progress & Sustainable Energy,
36 (2017) 1628-1633.
[108] S. Wu, K. Zhang, X. Wang, Y. Jia, B. Sun, T. Luo, F. Meng, Z. Jin, D. Lin, W. Shen,
40
[109] S. Rio, C. Faur-Brasquet, L. Le Coq, P. Le Cloirec, Structure characterization and
(2005) 4249-4257.
[110] X. Cui, S. Fang, Y. Yao, T. Li, Q. Ni, X. Yang, Z. He, Potential mechanisms of cadmium
removal from aqueous solution by Canna indica derived biochar, Science of the Total
[111] T. Wang, W. Liu, L. Xiong, N. Xu, J. Ni, Influence of pH, ionic strength and humic acid on
competitive adsorption of Pb (II), Cd (II) and Cr (III) onto titanate nanotubes, Chemical
[112] W. Peng, H. Li, Y. Liu, S. Song, A review on heavy metal ions adsorption from water by
graphene oxide and its composites, Journal of Molecular Liquids, 230 (2017) 496-504.
[113] T. Liu, X. Han, Y. Wang, L. Yan, B. Du, Q. Wei, D. Wei, Magnetic chitosan/anaerobic
granular sludge composite: Synthesis, characterization and application in heavy metal ions
[114] Y. Li, F. Liu, B. Xia, Q. Du, P. Zhang, D. Wang, Z. Wang, Y. Xia, Removal of copper from
[115] D. Mohan, C.U. Pittman Jr, M. Bricka, F. Smith, B. Yancey, J. Mohammad, P.H. Steele,
41
chars produced from fast pyrolysis of wood and bark during bio-oil production, Journal of
[116] Z. Veličković, G.D. Vuković, A.D. Marinković, M.-S. Moldovan, A.A. Perić-Grujić, P.S.
Uskoković, M.Đ. Ristić, Adsorption of arsenate on iron (III) oxide coated ethylenediamine
functionalized multiwall carbon nanotubes, Chemical Engineering Journal, 181 (2012) 174-181.
[117] H. Xu, G. Li, J. Li, C. Chen, X. Ren, Interaction of Th (IV) with graphene oxides: Batch
experiments, XPS investigation, and modeling, Journal of Molecular Liquids, 213 (2016) 58-68.
[118] Z. Guo, X. Zhang, Y. Kang, J. Zhang, Biomass-derived carbon sorbents for Cd (II) removal:
activation and adsorption mechanism, ACS Sustainable Chemistry & Engineering, 5 (2017)
4103-4109.
[119] S. Pourbeyram, Effective removal of heavy metals from aqueous solutions by graphene
[120] A.K. Meena, G. Mishra, P. Rai, C. Rajagopal, P. Nagar, Removal of heavy metal ions from
aqueous solutions using carbon aerogel as an adsorbent, Journal of hazardous materials, 122
(2005) 161-170.
[121] X. Wang, Q. Fan, S. Yu, Z. Chen, Y. Ai, Y. Sun, A. Hobiny, A. Alsaedi, X. Wang, High
sorption of U (VI) on graphene oxides studied by batch experimental and theoretical calculations,
42
[122] S. Wang, B. Gao, A.R. Zimmerman, Y. Li, L. Ma, W.G. Harris, K.W. Migliaccio,
Physicochemical and sorptive properties of biochars derived from woody and herbaceous
[123] M.D. Inyang, B. Gao, W.C. Ding, P. Pullammanappallil, A.R. Zimmerman, X.D. Cao,
Enhanced lead sorption by biochar derived from anaerobically digested sugarcane bagasse,
[124] H.Y. Wang, B. Gao, J.E. Fang, Y.S. Ok, Y.W. Xue, K. Yang, X.D. Cao, Engineered biochar
derived from eggshell-treated biomass for removal of aqueous lead, Ecological Engineering, 121
(2018) 124-129.
[125] T. Chen, Z. Zhou, S. Xu, H. Wang, W. Lu, Adsorption behavior comparison of trivalent and
hexavalent chromium on biochar derived from municipal sludge, Bioresource technology, 190
(2015) 388-394.
[126] Z. Fan, Q. Zhang, B. Gao, M. Li, C. Liu, Y. Qiu, Removal of hexavalent chromium by
biochar supported nZVI composite: Batch and fixed-bed column evaluations, mechanisms, and
[127] Y.-H. Li, J. Ding, Z. Luan, Z. Di, Y. Zhu, C. Xu, D. Wu, B. Wei, Competitive adsorption of
Pb2+, Cu2+ and Cd2+ ions from aqueous solutions by multiwalled carbon nanotubes, Carbon,
41 (2003) 2787-2792.
43
[128] X. Li, X. Tang, Y. Fang, Using graphene oxide as a superior adsorbent for the highly
efficient immobilization of Cu (II) from aqueous solution, Journal of Molecular Liquids, 199
(2014) 237-243.
[129] H. Wang, X. Yuan, Y. Wu, H. Huang, G. Zeng, Y. Liu, X. Wang, N. Lin, Y. Qi, Adsorption
characteristics and behaviors of graphene oxide for Zn (II) removal from aqueous solution,
[130] X. Huang, Y. Liu, S. Liu, X. Tan, Y. Ding, G. Zeng, Y. Zhou, M. Zhang, S. Wang, B. Zheng,
[131] N. Zhao, N. Wei, J. Li, Z. Qiao, J. Cui, F. He, Surface properties of chemically modified
activated carbons for adsorption rate of Cr (VI), Chemical Engineering Journal, 115 (2005)
133-138.
Dias, Activated carbon modifications to enhance its water treatment applications. An overview,
[133] Q. Wang, B. Wang, X.Q. Lee, J. Lehmann, B. Gao, Sorption and desorption of Pb(II) to
biochar as affected by oxidation and pH, Science of the Total Environment, 634 (2018) 188-194.
[134] Y. Zou, X. Wang, A. Khan, P. Wang, Y. Liu, A. Alsaedi, T. Hayat, X. Wang, Environmental
remediation and application of nanoscale zero-valent iron and its composites for the removal of
heavy metal ions: a review, Environmental science & technology, 50 (2016) 7290-7304.
44
[135] L.-L. Ling, W.-J. Liu, S. Zhang, H. Jiang, Magnesium oxide embedded nitrogen self-doped
biochar composites: fast and high-efficiency adsorption of heavy metals in an aqueous solution,
adsorbent derived from biomass waste by diammonium hydrogen phosphate activation for Cr
[137] X. Lu, W.-L. Yim, B.H. Suryanto, C. Zhao, Electrocatalytic oxygen evolution at
surface-oxidized multiwall carbon nanotubes, Journal of the American Chemical Society, 137
(2015) 2901-2907.
[138] K.A. Wepasnick, B.A. Smith, K.E. Schrote, H.K. Wilson, S.R. Diegelmann, D.H.
[139] B. Sarkar, S. Mandal, Y.F. Tsang, P. Kumar, K.-H. Kim, Y.S. Ok, Designer carbon
nanotubes for contaminant removal in water and wastewater: A critical review, Science of The
(2004) 2655-2659.
45
[141] K. Salipira, B. Mamba, R. Krause, T. Malefetse, S. Durbach, Carbon nanotubes and
cyclodextrin polymers for removing organic pollutants from water, Environmental Chemistry
[143] Y.L. Wang, Z.H. Jiang, Z.P. Yao, Formation of titania composite coatings on carbon steel
[144] S.M.C. Alves, F.S. da Silva, M.V. Donadon, R.R. Garcia, E.J. Corat, Process and
1379-1398.
[145] D. Lee, S.H. Hong, K.H. Paek, W.T. Ju, Adsorbability enhancement of activated carbon by
dielectric barrier discharge plasma treatment, Surface & Coatings Technology, 200 (2005)
2277-2282.
FSM-16 with activated carbon derived from rice husk, Journal of Colloid and Interface Science,
organic dyes and pollutants in wastewater using different modified titanium dioxides: a
[149] X. Zhang, B. Gao, J. Fang, W. Zou, L. Dong, C. Cao, J. Zhang, Y. Li, H. Wang, Chemically
[151] F.A. Al-Khaldi, B. Abusharkh, M. Khaled, M.A. Atieh, M. Nasser, T.A. Saleh, S. Agarwal,
I. Tyagi, V.K. Gupta, Adsorptive removal of cadmium (II) ions from liquid phase using acid
[152] H.-D. Choi, W.-S. Jung, J.-M. Cho, B.-G. Ryu, J.-S. Yang, K. Baek, Adsorption of Cr (VI)
onto cationic surfactant-modified activated carbon, Journal of Hazardous Materials, 166 (2009)
642-646.
[153] O. Amuda, A. Giwa, I. Bello, Removal of heavy metal from industrial wastewater using
modified activated coconut shell carbon, Biochemical Engineering Journal, 36 (2007) 174-181.
[154] B. Li, L. Yang, C.-q. Wang, Q.-p. Zhang, Q.-c. Liu, Y.-d. Li, R. Xiao, Adsorption of Cd (II)
from aqueous solutions by rape straw biochar derived from different modification processes,
47
[155] M.H. Kasnejad, A. Esfandiari, T. Kaghazchi, N. Asasian, Effect of pre-oxidation for
introduction of nitrogen containing functional groups into the structure of activated carbons and
its influence on Cu (II) adsorption, Journal of the Taiwan Institute of Chemical Engineers, 43
(2012) 736-740.
Process on NO 2 Sorption Abilities of Active Carbons, Acta Physica Polonica A, 118 (2010)
493-499.
[157] R. Arrigo, M. Hävecker, R. Schlögl, D.S. Su, Dynamic surface rearrangement and thermal
(2008) 4891-4893.
[159] R. Das, S.B.A. Hamid, M.E. Ali, A.F. Ismail, M.S.M. Annuar, S. Ramakrishna,
Multifunctional carbon nanotubes in water treatment: The present, past and future, Desalination,
[160] T. Ramanathan, F.T. Fisher, R.S. Ruoff, L.C. Brinson, Amino-Functionalized Carbon
Nanotubes for Binding to Polymers and Biological Systems, Chemistry of Materials, 17 (2011).
[161] Y.Y. Ju, J. Jun, S. Kwak, Amino functionalization of carbon nanotube surfaces with NH 3
48
[162] C. Chen, B. Liang, D. Lu, A. Ogino, X. Wang, M. Nagatsu, Amino group introduction onto
[164] J. Zhu, B. Deng, J. Yang, D. Gang, Modifying activated carbon with hybrid ligands for
[165] K.-Y. Shin, J.-Y. Hong, J. Jang, Heavy metal ion adsorption behavior in nitrogen-doped
magnetic carbon nanoparticles: isotherms and kinetic study, Journal of hazardous materials, 190
(2011) 36-44.
[166] J. Liu, W. Liu, Y. Wang, M. Xu, B. Wang, A novel reusable nanocomposite adsorbent,
xanthated Fe3O4-chitosan grafted onto graphene oxide, for removing Cu (II) from aqueous
[167] X. Li, H. Zhou, W. Wu, S. Wei, Y. Xu, Y. Kuang, Studies of heavy metal ion adsorption on
[168] C.Z. Zhang, B. Chen, Y. Bai, J. Xie, A new functionalized reduced graphene oxide
adsorbent for removing heavy metal ions in water via coordination and ion exchange, Separation
49
[169] B. Chen, Z.L. Zhu, J. Ma, Y.L. Qiu, J.H. Chen, Iron oxide supported
[170] H.C. Chin, Preparation and characterization of carbon-sulfur surface compounds, Carbon,
19 (1981) 175-186.
[172] K.A. Krishnan, T. Anirudhan, Removal of mercury (II) from aqueous solutions and
chlor-alkali industry effluent by steam activated and sulphurised activated carbons prepared from
bagasse pith: kinetics and equilibrium studies, Journal of Hazardous Materials, 92 (2002)
161-183.
50
[175] Y. Shen, B. Chen, Sulfonated graphene nanosheets as a superb adsorbent for various
[176] D.L. Zhao, X. Gao, S.H. Chen, F.Z. Xie, S.J. Feng, A. Alsaedi, T. Hayat, C.L. Chen,
Interaction between U(VI) with sulfhydryl groups functionalized graphene oxides investigated
by batch and spectroscopic techniques, Journal of Colloid and Interface Science, 524 (2018)
129-138.
ultrahigh adsorption capacity for Pb (II) removal, Journal of Materials Chemistry A, 4 (2016)
11888-11896.
[179] H.H. Lyu, B. Gao, F. He, A.R. Zimmerman, C. Ding, H. Huang, J.C. Tang, Effects of ball
[180] H.H. Lyu, B. Gao, F. He, A.R. Zimmerman, C. Ding, J.C. Tang, J.C. Crittenden,
Experimental and modeling investigations of ball-milled biochar for the removal of aqueous
51
[181] M. Tan, X. Liu, W. Li, H. Li, Enhancing sorption capacities for copper (II) and lead (II)
[182] Y. Sun, Q. Wang, C. Chen, X. Tan, X. Wang, Interaction between Eu (III) and graphene
oxide nanosheets investigated by batch and extended X-ray absorption fine structure
6020-6027.
[183] S.-T. Yang, Y. Chang, H. Wang, G. Liu, S. Chen, Y. Wang, Y. Liu, A. Cao,
Folding/aggregation of graphene oxide and its application in Cu2+ removal, Journal of colloid
[184] H.J. Wang, A.L. Zhou, F. Peng, H. Yu, L.F. Chen, Adsorption characteristic of acidified
carbon nanotubes for heavy metal Pb(II) in aqueous solution, Materials Science & Engineering A,
[185] A.D. Budaeva, E.V. Zoltoev, Porous structure and sorption properties of
[186] Q.F. Zeng, G.N. Dong, Y.B. Xie, Influence of sulfidation treatment on the structure and
application for removal of copper ions, Journal of Materials Science, 50 (2015) 4600-4609.
52
[188] L. Ji, M. Rao, S. Aloni, W. Lei, Y. Zhang, Porous carbon nanofiber–sulfur composite
electrodes for lithium/sulfur cells, Energy & Environmental Science, 4 (2011) 5053-5059.
[189] D. Saha, S. Barakat, S.E. Van Bramer, K.A. Nelson, D.K. Hensley, J. Chen,
[190] Q. Li, J. Yu, F. Zhou, X. Jiang, Synthesis and characterization of dithiocarbamate carbon
nanotubes for the removal of heavy metal ions from aqueous solutions, Colloids and Surfaces A:
N. Barka, Highly efficient activated carbon from Glebionis coronaria L. biomass: optimization of
preparation conditions and heavy metals removal using experimental design approach, Journal of
[192] Y. Wang, Z. Gu, J. Yang, J. Liao, Y. Yang, N. Liu, J. Tang, Amidoxime-grafted multiwalled
carbon nanotubes by plasma techniques for efficient removal of uranium (VI), Applied Surface
multi-walled carbon nanotubes for high efficiency removal of Pb (II) from aqueous solution,
53
[194] R. Dubey, J. Bajpai, A. Bajpai, Green synthesis of graphene sand composite (GSC) as
novel adsorbent for efficient removal of Cr (VI) ions from aqueous solution, Journal of water
Wrzalik, Adsorption of divalent metal ions from aqueous solutions using graphene oxide, Dalton
ultrasonic-assisted adsorption of Pb (II), Cd (II), Ni (II) and Cu (II) ions from aqueous solutions
adsorbent for Co (II) removal from aqueous solution, Journal of colloid and interface science,
[198] J.H. Chen, H.T. Xing, H.X. Guo, W. Weng, S.R. Hu, S.X. Li, Y.H. Huang, X. Sun, Z.B. Su,
Investigation on the adsorption properties of Cr (VI) ions on a novel graphene oxide (GO) based
[199] K. Anitha, S. Namsani, J.K. Singh, Removal of heavy metal ions using a functionalized
single-walled carbon nanotube: a molecular dynamics study, The Journal of Physical Chemistry
54
[200] S. Mashhadi, R. Sohrabi, H. Javadian, M. Ghasemi, I. Tyagi, S. Agarwal, V.K. Gupta,
Rapid removal of Hg (II) from aqueous solution by rice straw activated carbon prepared by
[201] Y. Zhang, T. Yan, L. Yan, X. Guo, L. Cui, Q. Wei, B. Du, Preparation of novel cobalt
ferrite/chitosan grafted with graphene composite as effective adsorbents for mercury ions,
[202] H. Ge, J. Wang, Ear-like poly (acrylic acid)-activated carbon nanocomposite: A highly
efficient adsorbent for removal of Cd (II) from aqueous solutions, Chemosphere, 169 (2017)
443-449.
[203] X. Zhang, Y. Hao, X. Wang, Z. Chen, C. Li, Competitive Adsorption of Cadmium (II) and
Mercury (II) Ions from Aqueous Solutions by Activated Carbon from Xanthoceras sorbifolia
[204] S.Z. Mohammadi, H. Hamidian, Z. Moeinadini, High surface area-activated carbon from
Glycyrrhiza glabra residue by ZnCl2 activation for removal of Pb (II) and Ni (II) from water
[205] Q. He, Z. Hu, Y. Jiang, X. Chang, Z. Tu, L. Zhang, Preconcentration of Cu (II), Fe (III) and
55
[206] L. Tan, Q. Liu, X. Jing, J. Liu, D. Song, S. Hu, L. Liu, J. Wang, Removal of uranium (VI)
ions from aqueous solution by magnetic cobalt ferrite/multiwalled carbon nanotubes composites,
[207] Y. Zhou, B. Gao, A.R. Zimmerman, X. Cao, Biochar-supported zerovalent iron reclaims
silver from aqueous solution to form antimicrobial nanocomposite, Chemosphere, 117 (2014)
801-805.
[208] T. Wen, X. Wu, M. Liu, Z. Xing, X. Wang, A.-W. Xu, Efficient capture of strontium from
43 (2014) 7464-7472.
[209] L. Liu, C. Li, C. Bao, Q. Jia, P. Xiao, X. Liu, Q. Zhang, Preparation and characterization of
chitosan/graphene oxide composites for the adsorption of Au (III) and Pd (II), Talanta, 93 (2012)
350-357.
[210] D. Dinda, S.K. Saha, Sulfuric acid doped poly diaminopyridine/graphene composite to
remove high concentration of toxic Cr (VI), Journal of hazardous materials, 291 (2015) 93-101.
[211] H.T. Xing, J.H. Chen, X. Sun, Y.H. Huang, Z.B. Su, S.R. Hu, W. Weng, S.X. Li, H.X. Guo,
W.B. Wu, NH2-rich polymer/graphene oxide use as a novel adsorbent for removal of Cu (II)
[212] R. Sudha, K. Srinivasan, P. Premkumar, Removal of nickel (II) from aqueous solution
using Citrus Limettioides peel and seed carbon, Ecotoxicology and environmental safety, 117
(2015) 115-123.
56
[213] C.Y. Yin, M.K. Aroua, W.M.A.W. Daud, Review of modifications of activated carbon for
enhancing contaminant uptakes from aqueous solutions, Separation and Purification Technology,
52 (2007) 403-415.
[214] S.M. Mahurin, J. Gorka, K.M. Nelson, R.T. Mayes, S. Dai, Enhanced CO2/N2 selectivity
[215] C. Chen, G. Li, J. Zhu, Y. Lu, M. Jiang, Y. Hu, Z. Shen, X. Zhang, In-situ formation of
[216] H. Tang, D. Yan, T. Lu, L. Pan, Sulfur-doped carbon spheres with hierarchical
micro/mesopores as anode materials for sodium-ion batteries, Electrochimica Acta, 241 (2017)
63-72.
[217] W. Niu, Z. Li, K. Marcus, L. Zhou, Y. Li, R. Ye, K. Liang, Y. Yang, Surface-modified
porous carbon nitride composites as highly efficient electrocatalyst for Zn-air batteries,
[218] S. Feng, X. Li, J. Huo, Q. Li, C. Xie, T. Liu, Z. Liu, Z. Wu, S. Wang, Controllable
synthesis of CoS2@N/S-codoped porous carbon derived from ZIF‐67 for as a highly efficient
57
Table 1. Heavy metal adsorption onto selected carbon adsorbents with the highest capacity.
Heavy Capacity
Carbon Adsorbent Mechanism Reference
Metal (mg/g)
As(V) 3-dimensional graphene 177.6 Electrostatic attraction & ion exchange [98]
58
Table 2. Selected carbon adsorbents with oxygen containing functional groups for heavy
metal removal
Qmax Functional
Material Heavy Metal Kinetic model Isotherm Reference
(mg/g) Groups (FG)
Pseudo-second- Langmuir,
Polyrhodanine modified multi-walled CNTs Pb(II) 8118 -OH [193]
order (PSO) Freundlich
Lignosulfonate-modified graphene hydrogel Pb(II) 1210 PSO Langmuir -OH, -COOH [177]
-OH, -COOH,
GO Pb(II) 1119 PSO Langmuir [195]
-C=O, -C-O
Poly(m-phenylenediamine)-coated
Cr(VI) 346 PSO Langmuir -OH, -COOH [178]
Fe3O4/o-MWCNTs
EDTA functionalized magnetic GO Hg(II) 268.4 PSO Freundlich -OH, -COOH [92]
-OH, -COOH,
GO Cd(II) 530 PSO Langmuir [195]
-C=O, -C-O
Ear-like poly (acrylic acid)-AC Cd(II) 473.2 PSO Langmuir -COOH [202]
-OH, -COOH,
AC from Glycyrrhiza glabra residue Ni(II) 166.7 PSO Langmuir [204]
-C=O, -C-O
59
Zero valent iron (ZVI)/graphene composites Co(II) 134.27 PSO Freundlich -OH [197]
AC from Glebionis coronaria L. biomass Co(II) 45.75 - Langmuir -OH, -C-O [191]
-OH, -COOH,
GO Zn(II) 345 PSO Langmuir [195]
-C=O, -C-O
AC produced from Bambusa vulgaris striata Zn(II) 254.39 PSO Langmuir -COOH,-C=O [191]
-OH, -COOH,
Graphene Oxides U(VI) 1330 - Langmuir [121]
-C=O, -C-O-C
Magnetic cobalt ferrite/multiwalled CNTs U(VI) 212.7 PSO Langmuir -OH [206]
-OH, -COOH,
Graphene oxides Th(IV) 58.59 PSO Langmuir [117]
-C=O
-OH, -COOH,
GO Nanosheets Eu(III) 175.44 - Langmuir [182]
-C=O, -C-O
60
Table 3. Selected carbon adsorbents with nitrogen containing functional groups for heavy
metal removal
Material Heavy Metal Qmax (mg/g) Kinetic model Isotherm FG Reference
Langmuir,
Polyrhodanine modified multi-walled CNTs Pb(II) 8118 PSO -NH2 [193]
Freundlich
Poly(m-phenylenediamine)-coated
Cr(VI) 346 PSO Langmuir -NH [178]
Fe3O4/o-MWCNTs
61
Table 4. Selected carbon adsorbents with sulfur containing functional groups for heavy
metal removal
Material Heavy Metal Qmax (mg/g) Kinetic model Isotherm FG Reference
Pb(II) 29.98
Ni(II) 1.2
Pb(II) 226
Chitosan/Sulfydryl-functionalized
Cd(II) 117 PSO Freundlich -SH [167]
GO composite
Cu(II) 235
Cd(II) 202.429
Zn(II) 16.625
Citrus Limettioides peel carbon Ni(II) 38.46 PSO Langmuir -S=O [212]
62
Table 5. Selected carbon adsorbents with other functional groups for heavy metal removal.
Kinetic
Material Heavy Metal Qmax (mg/g) Isotherm FG Reference
model
Zero valent iron (ZVI)/graphene composites Co(II) 134.27 PSO Freundlich -C=C [197]
-C=C,
AC from Glebionis coronaria L. biomass Co(II) 45.75 - Langmuir [191]
-P-O-C
63
Fig. 1. Schematics of adsorption mechanisms of heavy metals onto carbon adsorbents.
64
Fig. 2. Modification techniques to functionalize carbon adsorbents with various functional
groups.
65
Fig. 3. Typical oxidation synthesis routes to introduce oxygen containing functional groups into
carbon adsorbents [34, 141, 146, 213].
66
Fig. 4. Typical nitrogenation synthesis routes to introduce nitrogen containing functional groups
into carbon adsorbents [52, 159, 214].
67
Fig. 5. Typical sulfuration synthesis routes to introduce sulfur containing functional groups
68
Governing adsorption mechanisms of heavy metals onto carbon adsorbents are
summarized
Various methods for introduction of oxygen, nitrogen, and sulfur functional groups onto
Effects of various functional groups on heavy metal adsorption onto different carbon
Perspectives of future work on functionalized carbon adsorbents for heavy metal removal
is also presented
69
Graphic Abstract
70