Accepted Manuscript: Chemical Engineering Journal

Download as pdf or txt
Download as pdf or txt
You are on page 1of 71

Accepted Manuscript

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

To appear in: Chemical Engineering Journal

Received Date: 9 January 2019


Revised Date: 14 February 2019
Accepted Date: 15 February 2019

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

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Surface functional groups of carbon-based adsorbents and their roles in the removal of

heavy metals from aqueous solutions: A critical review

Xiaodong Yang a,b, Yongshan Wanc, Yulin Zhengb, Feng Hed, Zebin Yue, Jun Huangf,g, Hailong

Wangh,i, Yong Sik Okj, Yinshan Jianga, Bin Gaob,*


a
Key Laboratory of Automobile Materials, Ministry of Education, Department of Materials

Science and Engineering, Jilin University, Changchun 130025, China


b
Department of Agricultural and Biological Engineering, University of Florida, Gainesville, FL

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

functional groups. To promote the applications of functionalized carbon adsorbents in heavy

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

other potential applications is also presented at the end.

Keywords: carbonaceous adsorbents; biochar; carbon nanomaterials; heavy metal

contamination; surface functionalization; adsorption mechanism

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

manufacturing industries [6, 7].

Many treatment methods have been developed for the removal of detrimental heavy metal

ions from aqueous solutions, including adsorption, chemical precipitation, electrostatic

interaction, ion exchange, coagulation, and membrane filtration [8-14]. Adsorption using

carbonaceous materials as adsorbents (carbon adsorbents) is perhaps one of the most

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

recently emerged as a low-cost alternative of AC with comparable or superior performance for

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

multifunctionalities including carbon sequestration, soil fertility improvement, and

environmental remediation are also well recognized [25, 43].

With the advent of nanotechnology, graphene-based materials including GO or reduced GO

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

GO possess great potential in adsorption technology for removal of heavy metals.

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.

Therefore, functional groups are conventionally classified according to heteroatoms bonded to

the surface of carbon i.e., oxygen-containing functional groups, nitrogen-containing functional

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.

The overarching objective of this work is to provide a comprehensive review of recent

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

carbon adsorbents for heavy metal removal is also presented.

2. Mechanisms of heavy metal adsorption

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

physical adsorption, electrostatic interaction, ion exchange, surface complexation, and

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

complexation behavior of functional groups. Table 1 lists selected studies on adsorption

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.

2.1 Physical adsorption

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

significantly attracted by carbon atoms in reduced polyvinylpyrrolidone- modified GO through

physical adsorption processes.

2.2 Electrostatic interaction

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,

prevalence of electrostatic interaction in heavy metal adsorption was dependent on solution pH

and the point of zero charge of the adsorbent [95, 96]. The charged interface between carbons

and the solution depends strongly on ionization of surface groups.

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

efficiency for removal of Pb(II) and Cu(II) by EDTA-functionalized bamboo AC through

synergetic interactions of strong complexation, electrostatic attraction, ion exchange, and

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

(in the range of 1-8).

2.3 Ion exchange

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

functional groups. The processes can be represented as follows:

 COOH  M 2  COOM   H  (1)

 OH  M 2  OM   H  (2)

 2COOH  M 2  COOMOOC  2H  (3)

 2OH  M 2  OMO  2H  (4)

 COOH  M 2  OH  COOMO  2H  (5)

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

indica-derived biochar and titanate nanotubes [110, 111].

2.4 Surface complexation

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

adsorption of both As(V) and Pb(II) onto biochar.

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

combination of adsorption-precipitation and electrostatic attraction [127]. The uptake of Cu(II)

ions onto graphene oxide is dominated mainly by precipitation and inner-sphere surface

complexation at high pH (pH > 7.0) [128, 129].

3. Functionalization of Carbon Materials

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.

Conventionally, oxidation is performed under a refluxing condition in the presence of a single or

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

to destruction of pore walls by the plasma treatment.

Another example of physical treatment to facilitate oxidation is the irradiation of graphite

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

irradiation time [34]. In other words, oxygen-content-controllable synthesis of GO can be

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

are responsible for sorption of Pb(II).

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

Nitrogenation is a widely used technique to generate nitrogen containing functional groups

(e.g., -NH2, -NH, -C=N and -C-N) onto the surface of carbon materials [154]. The introduction

of nitrogen onto carbon materials is conventionally accomplished through reactions of carbon

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

protonation and dissociation of nitric acid:

HNO3 + 2H2SO4  NO2++ H3O+ + 2HSO4- (6)

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

on porous properties of carbons were also reported [155].

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,

nitrogenation of AC can be accomplished by activation of AC with KOH at 800-850 ◦C, followed

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

treatment of the oxidized-CNTs in ammonia flow at 600 ◦C for 4h [157].

Producing amino (-NH2) functional groups onto the surface of CNTs, or

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

amino groups created onto the surfaces of CNTs.

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

compared to AC with naphthalenesulfonic acid [165].

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

can effectively remove U(VI) from aqueous solutions.

4. Effects of functional groups

Research on sorption of heavy metals in aqueous solutions typically examines adsorption

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.

4.1 Oxygen containing functional groups

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].

4.2 Nitrogen containing functional groups

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].

4.3 Sulfur containing functional groups

In general, sulfur containing functional groups on carbon adsorbents are beneficial to their

adsorption of heavy metals. Depending on the experimental conditions, however, introducing

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

mercury uptake sorbents comparing thiophene and sulfate. The preparation of

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

Hg(II)>Pb(II)>Cd(II)>Ni(II) at pH of 7 or greater [189]. Sulfonated graphene nanosheets not

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),

and Zn(II) in aqueous solutions [190].

4.4 Other functional groups

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.

Amidoxime-grafted MWCNTs synthesized by plasma techniques can selectively adsorb U(VI)

22
ions from nuclear industrial effluents, which was due to the binding contribution of different

functional groups especially -C=N-OH [192].

5. Conclusions and perspectives

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).

From a practical standpoint, surface modification of carbon adsorbents in optimizing their

physicochemical and sorptive properties is essential in developing new technologies for

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

oxidation/reduction reactions; therefore, it is necessary to develop novel, facile, cost-effective,

and environmentally-friendly surface modification methods to functionalize carbon adsorbents. 2)

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

and environmental applications should also be explored.

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

Technology, 24 (2001) 389-401.

[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

journal of hygiene and environmental health, 214 (2011) 79-101.

[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

environmental safety, 141 (2017) 17-24.

[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 &

technology, 45 (2011) 10454-10462.


25
[8] M.K. Uddin, A review on the adsorption of heavy metals by clay minerals, with special focus

on the past decade, Chemical Engineering Journal, 308 (2017) 438-462.

[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

environmental management, 92 (2011) 407-418.

[11] A. Demirbas, Heavy metal adsorption onto agro-based waste materials: a review, Journal of

hazardous materials, 157 (2008) 220-229.

[12] M. Inyang, B. Gao, Y. Yao, Y. Xue, A.R. Zimmerman, P. Pullammanappallil, X. Cao,

Removal of heavy metals from aqueous solution by biochars derived from anaerobically digested

biomass, Bioresource technology, 110 (2012) 50-56.

[13] S.S. Ahluwalia, D. Goyal, Microbial and plant derived biomass for removal of heavy metals

from wastewater, Bioresource technology, 98 (2007) 2243-2257.

[14] S. Wan, J. Wu, S. Zhou, R. Wang, B. Gao, F. He, Enhanced lead and cadmium removal

using biochar-supported hydrated manganese oxide (HMO) nanoparticles: Behavior and

mechanism, Science of the Total Environment, 616 (2018) 1298-1306.

[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

atrazine, Environmental science & technology, 43 (2009) 3285-3291.

[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

technology, 175 (2015) 391-395.

[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,

Critical Reviews in Environmental Science and Technology, 46 (2016) 406-433.

[20] M. Inyang, B. Gao, A. Zimmerman, M. Zhang, H. Chen, Synthesis, characterization, and

dye sorption ability of carbon nanotube–biochar nanocomposites, Chemical Engineering Journal,

236 (2014) 39-46.

[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,

Journal of environmental management, 162 (2015) 123-131.

[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

and Bioavailability, 29 (2017) 197-204.


27
[23] B. Wang, B. Gao, J. Fang, Recent advances in engineered biochar productions and

applications, Critical Reviews in Environmental Science and Technology, 47 (2017) 2158-2207.

[24] X.Y. Zhang, B. Gao, A.E. Creamer, C.C. Cao, Y.C. Li, Adsorption of VOCs onto engineered

carbon materials: A review, Journal of Hazardous Materials, 338 (2017) 102-123.

[25] A.E. Creamer, B. Gao, Carbon-based adsorbents for postcombustion CO2 capture: A critical

review, Environmental Science & Technology, 50 (2016) 7276-7289.

[26] J. Fang, L. Zhan, Y.S. Ok, B. Gao, Minireview of potential applications of hydrochar

derived from hydrothermal carbonization of biomass, Journal of Industrial and Engineering

Chemistry, 57 (2018) 15-21.

[27] W. Zou, B. Gao, Y.S. Ok, L. Dong, Integrated adsorption and photocatalytic degradation of

volatile organic compounds (VOCs) using carbon-based nanocomposites: A critical review,

Chemosphere, 218 (2019) 845-859.

[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.

[29] T. Saitoh, N. Nakagaki, Y. Uchida, M. HIRAIDE, C. MATSUBARA, Spectrophotometric

determination of some functional groups on Chlorella for the evaluation of their contribution to

metal uptake, Analytical sciences, 17 (2001) 793-795.

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

Chemistry, 27 (2015) 1665-1678.

[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

potassium-rich biomass, Journal of Cleaner Production, 180 (2018) 437-449.

[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,

Chemical Engineering Research & Design, 133 (2018) 235-242.

[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.

Gao, Oxygen-content-controllable graphene oxide from electron-beam-irradiated graphite:

Synthesis, characterization, and removal of aqueous lead [Pb(II)], Acs Applied Materials &

Interfaces, 8 (2016) 25289-25296.

[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,

Bioresource Technology, 197 (2015) 356-362.

[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,

231 (2013) 512-518.

[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,

308 (2017) 863-871.

[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

Engineering Journal, 200 (2012) 673-680.

[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,

Chemical Engineering Journal, 240 (2014) 574-578.

[43] H. Yu, W. Zou, J. Chen, H. Chen, Z. Yu, J. Huang, H. Tang, X. Wei, B. Gao, Biochar

amendment improves crop production in problem soils: A review, Journal of Environmental

Management, 232 (2019) 8-21.

[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,

ACS applied materials & interfaces, 6 (2014) 17426-17436.

[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

Chemistry A, 4 (2016) 1970-1979.

[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,

Chemical Engineering Journal, 210 (2012) 557-563.

[47] M. Inyang, B. Gao, A. Zimmerman, Y.M. Zhou, X.D. Cao, Sorption and cosorption of lead

and sulfapyridine on carbon nanotube-modified biochars, Environmental Science and Pollution

Research, 22 (2015) 1868-1876.

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

adsorbents, Carbon, 40 (2002) 95-104.

[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,

Applied Surface Science, 329 (2015) 269-275.

[51] V. Gupta, O. Moradi, I. Tyagi, S. Agarwal, H. Sadegh, R. Shahryari-Ghoshekandi, A.

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

Environmental Science and Technology, 46 (2016) 93-118.

[52] G.-X. Yang, H. Jiang, Amino modification of biochar for enhanced adsorption of copper ions

from synthetic wastewater, Water research, 48 (2014) 396-405.

[53] P. Nowicki, R. Pietrzak, H. Wachowska, Influence of the precursor metamorphism degree

on preparation of nitrogen-enriched activated carbons by ammoxidation and chemical activation

of coals, Energy & Fuels, 23 (2009) 2205-2212.

[54] J. Wang, B. Deng, X. Wang, J. Zheng, Adsorption of aqueous Hg (II) by sulfur-impregnated

activated carbon, Environmental Engineering Science, 26 (2009) 1693-1699.

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

removal–II: Sulfur forms and mercury uptake, Carbon, 44 (2006) 2998-3004.

[57] M.F. El-Banna, A. Mosa, B. Gao, X.Q. Yin, Z. Ahmad, H.Y. Wang, Sorption of lead ions

onto oxidized bagasse-biochar mitigates Pb-induced oxidative stress on hydroponically grown

chicory: Experimental observations and mechanisms, Chemosphere, 208 (2018) 887-898.

[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

Engineering Journal, 174 (2011) 117-125.

[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.

[60] T. Garcıa, R. Murillo, D. Cazorla-Amoros, A. Mastral, A. Linares-Solano, Role of the

activated carbon surface chemistry in the adsorption of phenanthrene, Carbon, 42 (2004)

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 &

Engineering, 5 (2017) 9568-9585.

[62] M. Machida, B. Fotoohi, Y. Amamo, T. Ohba, H. Kanoh, L. Mercier, Cadmium (II)

adsorption using functional mesoporous silica and activated carbon, Journal of hazardous

materials, 221 (2012) 220-227.

[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.

[64] J. De Celis, N. Amadeo, A. Cukierman, In situ modification of activated carbons developed

from a native invasive wood on removal of trace toxic metals from wastewater, Journal of

Hazardous Materials, 161 (2009) 217-223.

[65] M. Guo, G. Qiu, W. Song, Poultry litter-based activated carbon for removing heavy metal

ions in water, Waste Management, 30 (2010) 308-315.

[66] I. Aguayo-Villarreal, A. Bonilla-Petriciolet, R. Muñiz-Valencia, Preparation of activated

carbons from pecan nutshell and their application in the antagonistic adsorption of heavy metal

ions, Journal of Molecular Liquids, 230 (2017) 686-695.

[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

solution by activated carbon impregnated with anionic surfactants, Journal of hazardous

materials, 164 (2009) 1130-1136.

[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

sorption by biochars: biochar characteristics and modifications, Chemosphere, 178 (2017)

466-478.

[71] X. Yang, Y. Xu, B. Xue, Y. Jiang, F. Li, Cordierite reinforced graphite nanocomposite with

superior adsorption capacity synthesized by in-situ carbon-bed pyrolysis method, Microporous

and Mesoporous Materials, 265 (2018) 219-226.

[72] M. Shariful, T. Sepehr, M. Mehrali, B. Ang, M. Amalina, Adsorption capability of heavy

metals by chitosan/poly (ethylene oxide)/activated carbon electrospun nanofibrous membrane,

Journal of Applied Polymer Science, 135 (2018).

[73] O.R. Harvey, B.E. Herbert, R.D. Rhue, K. Li-Jung, Metal interactions at the biochar-water

interface: energetics and structure-sorption relationships elucidated by flow adsorption

microcalorimetry, Environmental Science & Technology, 45 (2011) 5550.

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,

Carbon, 42 (2004) 3057-3069.

[75] P. Miretzky, A.F. Cirelli, Hg (II) removal from water by chitosan and chitosan derivatives: a

review, Journal of hazardous materials, 167 (2009) 10-23.

[76] L. Zhang, F. Pan, X. Liu, L. Yang, X. Jiang, J. Yang, W. Shi, Multi-walled carbon nanotubes

as sorbent for recovery of endocrine disrupting compound-bisphenol F from wastewater,

Chemical engineering journal, 218 (2013) 238-246.

[77] E.-A. Kim, A.L. Seyfferth, S. Fendorf, R.G. Luthy, Immobilization of Hg (II) in water with

polysulfide-rubber (PSR) polymer-coated activated carbon, water research, 45 (2011) 453-460.

[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

polypyrrole/maghemite and polyaniline/maghemite magnetic nanocomposites, Chemical

Engineering Journal, 281 (2015) 826-836.

[79] Z. Aksu, A.B. Akın, Comparison of Remazol Black B biosorptive properties of live and

treated activated sludge, Chemical Engineering Journal, 165 (2010) 184-193.

[80] P. Hadi, M. Xu, C. Ning, C.S.K. Lin, G. McKay, A critical review on preparation,

characterization and utilization of sludge-derived activated carbons for wastewater treatment,

Chemical Engineering Journal, 260 (2015) 895-906.

36
[81] S.L. Zuo, A review of the control of pore texture of phosphoric acid-activated carbons, New

Carbon Materials, 33 (2018) 289-302.

[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

distribution, Colloid Journal, 79 (2017) 144-151.

[84] N.M.S. Buarque, H.L.D. Buarque, J. Capelo-Neto, Adsorption kinetics and diffusion of

Saxitoxins on granular-activated carbon: influence of pore size distribution, Journal of Water

Supply Research and Technology-Aqua, 64 (2015) 344-353.

[85] A. Nayak, B. Bhushan, V. Gupta, P. Sharma, Chemically activated carbon from

lignocellulosic wastes for heavy metal wastewater remediation: Effect of activation conditions,

Journal of colloid and interface science, 493 (2017) 228-240.

[86] S. Kumar, V.A. Loganathan, R.B. Gupta, M.O. Barnett, An assessment of U (VI) removal

from groundwater using biochar produced from hydrothermal carbonization, Journal of

environmental management, 92 (2011) 2504-2512.

[87] Z. Liu, F.-S. Zhang, J. Wu, Characterization and application of chars produced from

pinewood pyrolysis and hydrothermal treatment, Fuel, 89 (2010) 510-514.

37
[88] Z. Liu, F.-S. Zhang, Removal of lead from water using biochars prepared from hydrothermal

liquefaction of biomass, Journal of Hazardous Materials, 167 (2009) 933-939.

[89] Y. Zhang, H. Chi, W. Zhang, Y. Sun, Q. Liang, Y. Gu, R. Jing, Highly efficient adsorption of

copper ions by a PVP-reduced graphene oxide based on a new adsorptions mechanism,

Nano-Micro Letters, 6 (2014) 80-87.

[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

the Taiwan Institute of Chemical Engineers, 62 (2016) 247-258.

[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

aqueous solutions, Applied Surface Science, 428 (2018) 648-658.

[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

enhanced lead (II) adsorption, RSC Advances, 6 (2016) 92186-92196.

[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

nanocomposite, Journal of hazardous materials, 270 (2014) 1-10.


38
[95] X. Dong, L.Q. Ma, Y. Li, Characteristics and mechanisms of hexavalent chromium removal

by biochar from sugar beet tailing, Journal of hazardous materials, 190 (2011) 909-915.

[96] A. Mukherjee, A. Zimmerman, W. Harris, Surface chemistry variations among a series of

laboratory-produced biochars, Geoderma, 163 (2011) 247-255.

[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,

Chemical Engineering Science, 61 (2006) 1138-1145.

[100] H. Shokry, H. Hamad, Effect of superparamagnetic nanoparticles on the physicochemical

properties of nano hydroxyapatite for groundwater treatment: adsorption mechanism of Fe (II)

and Mn (II), RSC Advances, 6 (2016) 82244-82259.

[101] Y. Chen, W. Zhang, S. Yang, A. Hobiny, A. Alsaedi, X. Wang, Understanding the

adsorption mechanism of Ni (II) on graphene oxides by batch experiments and density functional

theory studies, Science China Chemistry, 59 (2016) 412-419.

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

of Hazardous Materials, 359 (2018) 76-84.

[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

Science, 364 (2016) 620-627.

[105] G.P. Rao, C. Lu, F. Su, Sorption of divalent metal ions from aqueous solution by carbon

nanotubes: a review, Separation and Purification Technology, 58 (2007) 224-231.

[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,

Enhanced adsorption of cadmium ions by 3D sulfonated reduced graphene oxide, Chemical

Engineering Journal, 262 (2015) 1292-1302.

40
[109] S. Rio, C. Faur-Brasquet, L. Le Coq, P. Le Cloirec, Structure characterization and

adsorption properties of pyrolyzed sewage sludge, Environmental science & technology, 39

(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

Environment, 562 (2016) 517-525.

[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

Engineering Journal, 215 (2013) 366-374.

[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

removal, Journal of colloid and interface science, 508 (2017) 405-414.

[114] Y. Li, F. Liu, B. Xia, Q. Du, P. Zhang, D. Wang, Z. Wang, Y. Xia, Removal of copper from

aqueous solution by carbon nanotube/calcium alginate composites, Journal of Hazardous

Materials, 177 (2010) 876-880.

[115] D. Mohan, C.U. Pittman Jr, M. Bricka, F. Smith, B. Yancey, J. Mohammad, P.H. Steele,

M.F. Alexandre-Franco, V. Gómez-Serrano, H. Gong, Sorption of arsenic, cadmium, and lead by

41
chars produced from fast pyrolysis of wood and bark during bio-oil production, Journal of

colloid and interface science, 310 (2007) 57-73.

[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

oxide–zirconium phosphate (GO–Zr-P) nanocomposite, Industrial & Engineering Chemistry

Research, 55 (2016) 5608-5617.

[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,

Chemical Engineering Journal, 287 (2016) 448-455.

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

biomass, Chemosphere, 134 (2015) 257-262.

[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,

Separation Science and Technology, 46 (2011) 1950-1956.

[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

secondary contamination prevention, Chemosphere, 217 (2019) 85-94.

[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,

Applied Surface Science, 279 (2013) 432-440.

[130] X. Huang, Y. Liu, S. Liu, X. Tan, Y. Ding, G. Zeng, Y. Zhou, M. Zhang, S. Wang, B. Zheng,

Effective removal of Cr (VI) using β-cyclodextrin–chitosan modified biochars with

adsorption/reduction bifuctional roles, Rsc Advances, 6 (2016) 94-104.

[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.

[132] J. Rivera-Utrilla, M. Sánchez-Polo, V. Gómez-Serrano, P. Alvarez, M. Alvim-Ferraz, J.

Dias, Activated carbon modifications to enhance its water treatment applications. An overview,

Journal of hazardous materials, 187 (2011) 1-23.

[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,

Environmental Science & Technology, 51 (2017) 10081-10089.

[136] Z. Guo, J. Zhang, H. Liu, Y. Kang, Development of a nitrogen-functionalized carbon

adsorbent derived from biomass waste by diammonium hydrogen phosphate activation for Cr

(VI) removal, Powder Technology, 318 (2017) 459-464.

[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.

Fairbrother, Surface and structural characterization of multi-walled carbon nanotubes following

different oxidative treatments, Carbon, 49 (2011) 24-36.

[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

Total Environment, 612 (2018) 561-581.

[140] M.M. Maroto-Valer, I. Dranca, T. Lupascu, R. Nastas, Effect of adsorbate polarity on

thermodesorption profiles from oxidized and metal-impregnated activated carbons, Carbon, 42

(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

Letters, 5 (2007) 13-17.

[142] M. Domingo-Garcia, F.J. Lopez-Garzon, M. Perez-Mendoza, Modifications produced by

O-2 plasma treatments on a mesoporous glassy carbon, Carbon, 38 (2000) 555-563.

[143] Y.L. Wang, Z.H. Jiang, Z.P. Yao, Formation of titania composite coatings on carbon steel

by plasma electrolytic oxidation, Applied Surface Science, 256 (2010) 5818-5823.

[144] S.M.C. Alves, F.S. da Silva, M.V. Donadon, R.R. Garcia, E.J. Corat, Process and

characterization of reclaimed carbon fiber composites by pyrolysis and oxidation, assisted by

thermal plasma to avoid pollutants emissions, Journal of Composite Materials, 52 (2018)

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.

[146] C. Chen, B. Liang, A. Ogino, X. Wang, M. Nagatsu, Oxygen functionalization of multiwall

carbon nanotubes by microwave-excited surface-wave plasma treatment, The Journal of Physical

Chemistry C, 113 (2009) 7659-7665.

[147] M.M. Mohamed, Acid dye removal: comparison of surfactant-modified mesoporous

FSM-16 with activated carbon derived from rice husk, Journal of Colloid and Interface Science,

272 (2004) 28-34.


46
[148] H. Zangeneh, A. Zinatizadeh, M. Habibi, M. Akia, M.H. Isa, Photocatalytic oxidation of

organic dyes and pollutants in wastewater using different modified titanium dioxides: a

comparative review, Journal of Industrial and Engineering Chemistry, 26 (2015) 1-36.

[149] X. Zhang, B. Gao, J. Fang, W. Zou, L. Dong, C. Cao, J. Zhang, Y. Li, H. Wang, Chemically

activated hydrochar as an effective adsorbent for volatile organic compounds (VOCs),

Chemosphere, 218 (2019) 680-686.

[150] J. Rangel-Mendez, M. Streat, Adsorption of cadmium by activated carbon cloth: influence

of surface oxidation and solution pH, Water Research, 36 (2002) 1244-1252.

[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

modified carbon-based adsorbents, Journal of Molecular Liquids, 204 (2015) 255-263.

[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,

Chemosphere, 175 (2017) 332-340.

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.

[156] P. Nowicki, R. Pietrzak, M. Dobkiewicz, H. Wachowska, The Effect of Ammoxidation

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

stability of nitrogen functional groups on carbon nanotubes, Chemical Communications, 40

(2008) 4891-4893.

[158] Y. Alireza, R. Ali, Synthesis of Amino-functionalized Carbon Nanotubes and their

Applications, Current Organic Chemistry, 22 (2018) 1505-1522.

[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,

354 (2014) 160-179.

[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

plasma treatment, Applied Surface Science, 256 (2010) 6941-6944.

48
[162] C. Chen, B. Liang, D. Lu, A. Ogino, X. Wang, M. Nagatsu, Amino group introduction onto

multiwall carbon nanotubes by NH/Ar plasma treatment, Carbon, 48 (2010) 939-948.

[163] S. Biniak, M. Pakuła, G. Szymański, A. Światkowski, Effect of activated carbon surface

oxygen-and/or nitrogen-containing groups on adsorption of copper (II) ions from aqueous

solution, Langmuir, 15 (1999) 6117-6122.

[164] J. Zhu, B. Deng, J. Yang, D. Gang, Modifying activated carbon with hybrid ligands for

enhancing aqueous mercury removal, Carbon, 47 (2009) 2014-2025.

[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

solutions, Applied Surface Science, 367 (2016) 327-334.

[167] X. Li, H. Zhou, W. Wu, S. Wei, Y. Xu, Y. Kuang, Studies of heavy metal ion adsorption on

Chitosan/Sulfydryl-functionalized graphene oxide composites, Journal of colloid and interface

science, 448 (2015) 389-397.

[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

Science and Technology, 53 (2018) 2896-2905.

49
[169] B. Chen, Z.L. Zhu, J. Ma, Y.L. Qiu, J.H. Chen, Iron oxide supported

sulfhydryl-functionalized multiwalled carbon nanotubes for removal of arsenite from aqueous

solution, Chempluschem, 80 (2015) 740-748.

[170] H.C. Chin, Preparation and characterization of carbon-sulfur surface compounds, Carbon,

19 (1981) 175-186.

[171] J.D.D. Lopez‐Gonzalez, C. Moreno‐Castilla, A. Guerrero‐Ruiz, F. Rodriguez‐

Reinoso, Effect of carbon‐oxygen and carbon‐sulphur surface complexes on the adsorption of

mercuric chloride in aqueous solutions by activated carbons, Journal of Chemical Technology

and Biotechnology, 32 (1982) 575-579.

[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.

[173] A. Macıas-Garcıa, C. Valenzuela-Calahorro, A. Espinosa-Mansilla, A. Bernalte-Garcıa, V.

Gómez-Serrano, Adsorption of Pb2+ in aqueous solution by SO2-treated activated carbon,

Carbon, 42 (2004) 1755-1764.

[174] A. Macıas-Garcıa, V. Gomez-Serrano, M. Alexandre-Franco, C. Valenzuela-Calahorro,

Adsorption of cadmium by sulphur dioxide treated activated carbon, Journal of hazardous

materials, 103 (2003) 141-152.

50
[175] Y. Shen, B. Chen, Sulfonated graphene nanosheets as a superb adsorbent for various

environmental pollutants in water, Environmental science & technology, 49 (2015) 7364-7372.

[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.

[177] F. Li, X. Wang, T. Yuan, R. Sun, A lignosulfonate-modified graphene hydrogel with

ultrahigh adsorption capacity for Pb (II) removal, Journal of Materials Chemistry A, 4 (2016)

11888-11896.

[178] Z. Tian, B. Yang, G. Cui, L. Zhang, Y. Guo, S. Yan, Synthesis of poly

(m-phenylenediamine)/iron oxide/acid oxidized multi-wall carbon nanotubes for removal of

hexavalent chromium, Rsc Advances, 5 (2015) 2266-2275.

[179] H.H. Lyu, B. Gao, F. He, A.R. Zimmerman, C. Ding, H. Huang, J.C. Tang, Effects of ball

milling on the physicochemical and sorptive properties of biochar: Experimental observations

and governing mechanisms, Environmental Pollution, 233 (2018) 54-63.

[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

methylene blue, Chemical Engineering Journal, 335 (2018) 110-119.

51
[181] M. Tan, X. Liu, W. Li, H. Li, Enhancing sorption capacities for copper (II) and lead (II)

under weakly acidic conditions by L-tryptophan-functionalized graphene oxide, Journal of

Chemical & Engineering Data, 60 (2015) 1469-1475.

[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

spectroscopy and by modeling techniques, Environmental science & technology, 46 (2012)

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

and interface science, 351 (2010) 122-127.

[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,

466 (2007) 201-206.

[185] A.D. Budaeva, E.V. Zoltoev, Porous structure and sorption properties of

nitrogen-containing activated carbon, Fuel, 89 (2010) 2623-2627.

[186] Q.F. Zeng, G.N. Dong, Y.B. Xie, Influence of sulfidation treatment on the structure and

tribological properties of nitrogen-doped diamond-like carbon films, Applied Surface Science,

254 (2008) 3859-3866.

[187] Z. Li, S. Ren, Preparation of nitrogen-functionalized mesoporous carbon and its

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,

Noncompetitive and competitive adsorption of heavy metals in sulfur-functionalized ordered

mesoporous carbon, ACS applied materials & interfaces, 8 (2016) 34132-34142.

[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:

Physicochemical and Engineering Aspects, 482 (2015) 306-314.

[191] H. Tounsadi, A. Khalidi, A. Machrouhi, M. Farnane, R. Elmoubarki, A. Elhalil, M. Sadiq,

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

Environmental Chemical Engineering, 4 (2016) 4549-4564.

[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

Science, 320 (2014) 10-20.

[193] B. Alizadeh, M. Ghorbani, M.A. Salehi, Application of polyrhodanine modified

multi-walled carbon nanotubes for high efficiency removal of Pb (II) from aqueous solution,

Journal of Molecular Liquids, 220 (2016) 142-149.

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

process engineering, 5 (2015) 83-94.

[195] R. Sitko, E. Turek, B. Zawisza, E. Malicka, E. Talik, J. Heimann, A. Gagor, B. Feist, R.

Wrzalik, Adsorption of divalent metal ions from aqueous solutions using graphene oxide, Dalton

transactions, 42 (2013) 5682-5689.

[196] R. Zare-Dorabei, S.M. Ferdowsi, A. Barzin, A. Tadjarodi, Highly efficient simultaneous

ultrasonic-assisted adsorption of Pb (II), Cd (II), Ni (II) and Cu (II) ions from aqueous solutions

by graphene oxide modified with 2, 2′-dipyridylamine: central composite design optimization,

Ultrasonics sonochemistry, 32 (2016) 265-276.

[197] M. Xing, J. Wang, Nanoscaled zero valent iron/graphene composite as an efficient

adsorbent for Co (II) removal from aqueous solution, Journal of colloid and interface science,

474 (2016) 119-128.

[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

composite adsorbent, Journal of Materials Chemistry A, 2 (2014) 12561-12570.

[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

A, 119 (2015) 8349-8358.

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

microwave-assisted H2SO4 activation: Kinetic, isotherm and thermodynamic studies, Journal of

Molecular Liquids, 215 (2016) 144-153.

[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,

Journal of Molecular Liquids, 198 (2014) 381-387.

[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

Bunge Hull, Journal of Chemistry, 2016 (2016).

[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

samples, Journal of Industrial and Engineering Chemistry, 20 (2014) 4112-4118.

[205] Q. He, Z. Hu, Y. Jiang, X. Chang, Z. Tu, L. Zhang, Preconcentration of Cu (II), Fe (III) and

Pb (II) with 2-((2-aminoethylamino) methyl) phenol-functionalized activated carbon followed by

ICP-OES determination, Journal of Hazardous materials, 175 (2010) 710-714.

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,

Chemical Engineering Journal, 273 (2015) 307-315.

[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

aqueous solutions using graphene oxide–hydroxyapatite nanocomposites, Dalton Transactions,

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)

from aqueous solution, Chemical Engineering Journal, 263 (2015) 280-289.

[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

in amidoxime-modified porous carbon, Carbon, 67 (2014) 457-464.

[215] C. Chen, G. Li, J. Zhu, Y. Lu, M. Jiang, Y. Hu, Z. Shen, X. Zhang, In-situ formation of

tin-antimony sulfide in nitrogen-sulfur Co-doped carbon nanofibers as high performance anode

materials for sodium-ion batteries, Carbon, 120 (2017) 380-391.

[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,

Advanced Energy Materials, 8 (2018) 1701642.

[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

catalyst for the hydrogen evolution reaction, ChemCatChem, 10 (2018) 796-803.

57
Table 1. Heavy metal adsorption onto selected carbon adsorbents with the highest capacity.
Heavy Capacity
Carbon Adsorbent Mechanism Reference
Metal (mg/g)

Pb(II) Polyrhodanine modified multi-walled CNTs 8118 Chemical adsorption [193]


Cr(VI) Graphene sand composite 2859 Chemical adsorption [194]

Cr(III) Nitrogen-doped magnetic CNTs 638 Chemical adsorption [165]

Cd(II) GO 530 Chemical adsorption [195]

Zn(II) GO 345 Chemical adsorption [195]

Ni(II) GO 180 Surface complexation [196]

Cu(II) Polyvinylpyrrolidone-reduced GO 1689 Physical adsorption [89]

Co(II) zero valent iron/graphene composites 134 Chemical adsorption [197]

Fe(III) chitosan/poly(ethylene-oxide)/AC 217.4 Surface complexation & ion exchange [72]

U(VI) Graphene oxides 1330 Surface complexation [121]

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

Graphene sand composite Cr(VI) 2859.38 - - -OH, -COOH [194]

Polyethyleneimine and GO Cr(VI) 539.53 PSO Langmuir -COOH [198]

Poly(m-phenylenediamine)-coated
Cr(VI) 346 PSO Langmuir -OH, -COOH [178]
Fe3O4/o-MWCNTs

CNT-COO− Hg(II) 661.9 - Langmuir -COOH [199]

Rice straw AC Hg(II) 500 PSO Freundlich -OH, -C-O [200]

CoFe2O4-chitosan-graphene Hg(II) 361 PSO Langmuir -OH, -COOH [201]

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]

AC Cd(II) 388.7 - Langmuir -OH, -COOH [203]

GO Ni(II) 180.893 PSO Langmuir C=O [196]

-OH, -COOH,
AC from Glycyrrhiza glabra residue Ni(II) 166.7 PSO Langmuir [204]
-C=O, -C-O

Polyvinylpyrrolidone-reduced GO Cu(II) 1689 - - -OH [89]

L-Tryptophan functionalized GO Cu(II) 588 PSO Langmuir -C=O, -C-O [181]

Xanthated Fe3O4-chitosangrafted onto GO Cu(II) 426.8 PSO Langmuir -COOH [166]

59
Zero valent iron (ZVI)/graphene composites Co(II) 134.27 PSO Freundlich -OH [197]

Amination GO Co(II) 116.35 PSO Langmuir -COOH [94]

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]

chitosan/poly(ethylene-oxide)/AC Zn(II) 186.2


- Langmuir -COOH [72]
electrospun nanofibrous membrane Fe(III) 217.4

AC-AMP Fe(II) 67.1 - - -OH [205]

-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]

Three-dimensional graphene foam As(V) 177.6 - - [98]

Fe(III) oxide coated ethylene-diamine


As(V) 23.47 PSO Freundlich -OH [116]
modified MWCNTs

Biochar-supported zerovalent iron Ag(II) 655.4 - - -OH [207]

-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

GO-hydroxyapatite Sr(II) 702.18 PSO Langmuir -OH [208]

Chitosan/GO Au(II) 1076.65 PSO Langmuir -OH, -COOH [209]

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

Nitrogen-doped hierarchical microporous /


Pb(II) 212 PSO Langmuir -NH [93]
mesoporous carbons

Sulfuric acid doped poly


Cr(VI) 609.76 PSO Langmuir -NH [210]
diaminopyridine/graphene composite

polyethyleneimine and GO Cr(VI) 539.53 PSO Langmuir -NH2 [198]

Poly(m-phenylenediamine)-coated
Cr(VI) 346 PSO Langmuir -NH [178]
Fe3O4/o-MWCNTs

CoFe2O4-chitosan-graphene Hg(II) 361 PSO Langmuir -NH2 [201]

CNT-CONH2 Hg(II) 332.6 - Langmuir -NH2 [199]

EDTA functionalized magnetic GO Hg(II) 268.4 PSO Freundlich -NH2 [92]

AC Cd(II) 388.7 - Langmuir -NH [203]

GO Ni(II) 180.893 PSO Langmuir -C=N, -C-N [196]

L-Tryptophan functionalized GO Cu(II) 588 PSO Langmuir -NH [181]

Xanthated Fe3O4-chitosangrafted onto GO Cu(II) 426.8 PSO Langmuir -NH [166]

NH2-rich polymer/GO Cu(II) 349.04 PSO Langmuir -NH2 [211]

Chitosan/poly(ethylene oxide)/AC electrospun


Cu(II) 195.3 - Langmuir -NH2 [72]
nanofibrous membrane

Amination GO Co(II) 116.35 PSO Langmuir -NH2 [94]

Chitosan/poly(ethylene oxide)/AC electrospun Zn(II) 186.2


- Langmuir -NH2 [72]
nanofibrous membrane Fe(III) 217.4

Amidoxime-graftedmultiwalled CNTs U(VI) 145 PSO Langmuir -NH2 [192]

Chitosan/GO Au(II) 1076.65 PSO Langmuir -NH2 [209]

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

Sulfur-Functionalized Ordered Hg(II) 70.75 -C-S, -C=S,


PSO - [189]
Mesoporous Carbon Cd(II) 4.96 -COS, -SOx

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

Dithiocarbamate CNTs Cu(II) 101.523 PSO Langmuir -C=S [190]

Zn(II) 16.625

Low-cost sulfurized AC derived


Cd(II) 142.86 - Frendlich -C=S [55]
from nut shells

Sulfonated Graphene Nanosheets Cd(II) 58 PSO Langmuir -SO3H [175]

Citrus Limettioides peel carbon Ni(II) 38.46 PSO Langmuir -S=O [212]

Xanthated Fe3O4-chitosan grafted


Cu(II) 426.8 PSO Langmuir -C-S [166]
onto GO

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

Waste-art-paper biochars Pb(II) 1555 PSO Langmuir -CO32- [167]

Graphene sand composite Cr(VI) 2859.38 - - -O-CH3 [194]

Sulfuric acid doped poly diaminopyridine /


Cr(VI) 609.76 PSO Langmuir -C=C [210]
graphene

Nitrogen-doped magnetic CNTs Cr(III) 638.56 PSO Langmuir -C-C, [165]

Polyvinylpyrrolidone-reduced GO Cu(II) 1689 - - -C=C [89]

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

AC-AMP Fe(II) 67.1 - - -CH2 [205]

Amidoxime-grafted multiwalled CNTs U(VI) 145 PSO Langmuir -C=N-OH [192]

GO-hydroxyapatite Sr(II) 702.18 PSO Langmuir -HPO42- [208]

Chitosan/GO Au(II) 1076.65 PSO Langmuir -C=C [209]

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

into carbon adsorbents [175, 215-218].

68
 Governing adsorption mechanisms of heavy metals onto carbon adsorbents are

summarized

 Various methods for introduction of oxygen, nitrogen, and sulfur functional groups onto

carbon surfaces are categorized

 Effects of various functional groups on heavy metal adsorption onto different carbon

materials are discussed

 Perspectives of future work on functionalized carbon adsorbents for heavy metal removal

is also presented

69
Graphic Abstract

70

You might also like