Journal of Water Process Engineering 37 (2020) 101339

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Journal of Water Process Engineering

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Removal of heavy metals from aqueous solution using carbon-based T

adsorbents: A review
Chengyu Duana, Tianyu Maa, Jianyu Wanga, Yanbo Zhoua,b,*
a
State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China University of Science and Technology, No.
130 Meilong Road, Shanghai, 200237, China
b
National Engineering Laboratory for Industrial Wastewater Treatment, East China University of Science and Technology, No. 130 Meilong Road, Shanghai, 200237,
China

A R T I C LE I N FO A B S T R A C T

Keywords: Heavy metal contamination has been a serious threat to environment and human health. Carbon-based mate-
Heavy metal rials, from biochar/activated carbon to modified materials (i.e. carbon nanotubes-based materials, and gra-
Adsorption phene-based materials), have been widely studied as efficient adsorbents for the heavy metal removal from
Carbon-Based materials aqueous solutions. This review discussed the recent achievements in adsorption isotherms, adsorption kinetics
Desorption
and adsorption mechanism according to the existing forms of heavy metals in water. The effect of process
conditions, such as temperature, pH value, and coexisting ions, on adsorption performance are combed, and the
universal guidance law is obtained. The physical adsorption, electrostatic interaction, ion exchange, surface
complexation, and precipitation/coprecipitation play important roles in heavy metals adsorption process. In
addition to the common activated carbon(AC), biochar(BC) and the emerging carbon nanotubes(CNTs) and
graphene(GN) adsorbent show good development potentials. Meanwhile, though the modified carbonaceous
materials can achieve high adsorption capacity and removal efficiency of heavy metals, the modification op-
eration is complex, especially chemical modification. Acid and alkali solution are often used to regenerate spent
materials in desorption, however, further studies of other desorption reagent are really needed. This review
highlights the removal of heavy metal ions from aqueous solution using carbon-based materials as adsorbents,
and discusses the existing deficiencies and suggestions on further study.

1. Introduction
The development of mining, smelting, chemical industry, battery
manufacturing and the extensive use of pesticides and fertilizers caused
a huge emission of heavy metals in surface water and ground water
[1,2]. Pb, Cu, Cr, Cd, Hg, Zn, Ni, As, and other heavy metals could be
refractory and accumulated in organisms [2,3] to trigger poisoning or
chronic diseases. In United States, Japan, India, and Turkey, it was
reported that some rivers, wetlands, or bays suffered from heavy metal
contamination [4–7]. In recent years, heavy metals pollution accidents
occurred frequently in China: Taihu Lake, Chaohu Lake, Dongting Lake,
Poyang Lake, tributaries of Songhua River, Pearl River, Jiulong River,
and other freshwater resources are polluted by heavy metals in different
degrees [3,8–12]. Heavy metal pollution has become a great danger to
human health and the safety of water-drinking and water-using.
Today, chemical precipitation, electrochemical method, ion
exchange, membrane filtration, and adsorption are used to the removal
of heavy metals in water, and these technologies show their advantages
and disadvantages in real situations (Please refer to Table A1). Con-
sidering the removal capacity, energy consumption, sensitivity of op-
eration conditions and secondary pollution, adsorption method is the
best choice [1]. Common adsorbents include low-cost materials, car-
bonaceous materials, and modified materials [13], and these adsorbents
have so wide ranges of variety and sources that they can be selected
according to local conditions by different countries and regions
[14–16]. Importantly, easy operation, renewable adsorbent, and low
toxicity are main characteristics of adsorption [17,18], which bring a
broad application prospects to adsorption in heavy metals remove in
water.
Carbon-based materials, are powdered or bulk non-metallic solid
materials with carbon as the main ingredient, which includes activated
carbon/biochar (AC/BC), carbon nanotubes (CNTs) and graphene (GN)

⁎
Corresponding author at: State Environmental Protection Key Laboratory of Environmental Risk Assessment and Control on Chemical Process, East China
University of Science and Technology, No. 130 Meilong Road, Shanghai, 200237, China.
E-mail address: zhouyanbo@ecust.edu.cn (Y. Zhou).

https://doi.org/10.1016/j.jwpe.2020.101339
Received 1 March 2020; Received in revised form 4 May 2020; Accepted 6 May 2020
2214-7144/ © 2020 Elsevier Ltd. All rights reserved.
C. Duan, et al. Journal of Water Process Engineering 37 (2020) 101339

analogues, etc. They have the outstanding advantages of large specific often used to fit the adsorption process [29,30].
surface area, abundant pore structure, good thermal stability, high
mechanical strength [19], high adsorption capacity and controllable 2.1.1. Adsorption isotherm
morphology [20]. In order to better meet the requirements of water Under certain temperature conditions, there are some certain re-
quality, a lot of development and improvement work has been done; lationships between adsorbate and unabsorbed adsorbate on the ad-
therefore, various carbonaceous materials and their derivatives were sorbent surface in water. These relationships can be described by iso-
developed. Many modification methods have been developed for the thermal model, as shown below [15,31–34]:
enhanced removal of heavy metal ions, such as oxidization, magneti- Ce C 1
zation, functional group graft, and compositing with inorganic sub- Langmuir adsorption isotherm: = e +
Qe Qm kL Qm (1)
stances [21]. Some studies have reviewed modified AC / BC, CNTs, or
GN analogues adsorbents, respectively, but the certain guidelines for 1
Freundlich adsorption isotherm:Qe = KF ∙Ce n (2)
modification and the inherent mechanisms are not clearly stated
[22,23]. In fact, the modification methods or adsorption mechanisms Qm,i KL, i Ce, i
Extended Langmuir isothermal:Qe, i =
involved in these studies are similar, thus, a summarization can be 1 + ∑ KL, i⋅Ce, i (3)
meaningful to examine carbon-based adsorbents as a whole for heavy
metal removal, and the regeneration strategy also should be system- Ce 1 k − 1 Ce
BET isotherm: = + ⋅
atically considered. Qe (Cs − Ce ) kQm kQm Cs (4)
This review aims to highlight the removal of heavy metals from Temkin isotherm:Qe = B ln KT + B ln Ce Qe (5)
aqueous solution using carbon-based adsorbents. The adsorption be-
havior, model fitting, process factors, as well as the adsorption me- D− R model: q = qmexp(−βε 2), ε = RTln (1 +
1
)
chanism are briefly introduced. The universal modification methods C (6)
and the regeneration process of several typical carbon materials (e.g. where Qe denotes the amount adsorbed at equilibrium, mg g−1; Qm
AC/BC, CNTs, and GN adsorbent) are classified and summarized. This represents the maximum adsorption capacity, mg g−1; Ce is the equi-
review provides clue for three typical carbonaceous materials to de- librium concentration of remaining heavy metal ions in the solution,
velop carbon-based adsorbents in heavy metal removal, and the per- mg·L−1; kL is Langmuir constants that represents the affinity between
spectives of further research are presented. solute and adsorbent, L mg−1; kF is Freundlich constants that are re-
lated to the sorption capacity, (mg g−1)(L mg−1)1/n; 1 is Freundlich
n
2. Adsorption behavior of heavy metals in aqueous solution constants that are related to the sorption intensity; Cs is the con-
centration of adsorptive at equilibrium, mg·L−1; k is a parameter re-
Heavy metal has been regarded as extremely dangerous environ- lated to the difference in adsorption heat between the first and each of
mental pollution, which are toxic to human beings even at low con- the subsequent layers, L mg−1; B is a constant related to the heat of
centrations level and possible to trigger poisoning or chronic diseases sorption; KT is the equilibrium binding constant corresponding to the
[23,24]. When the heavy metals enter the water, they always exist in maximum binding energy, L mg−1; q is the amount of metal ions ad-
different forms, such as cations, anions, and hydroxide complexes sorbed on per weight unit of adsorbents after equilibrium, mol/g; qm is
[25,26] depending on the conditions of dissolved oxygen, pH and or- the maximum adsorption capacity at complete monolayer coverage,
ganic matter content. The insoluble metal oxide or easily deposited mol/g; β is the activity coefficient related to mean sorption energy,
heavy metal salt, such as CuO, PbO, ZnS, and PbSO4 [27], are not the mol2/kJ2; ε is the Polanyi potential; R is ideal gas constant, 8.3145 J
key targets for adsorption; relatively, as shown in Table 1, the ad- mol−1 K−1; T is the absolute temperature, K.
sorption behavior of soluble heavy metals (such as Pb(II), Cd(II), Cr(VI), Among these formulas, Langmuir isotherm, Freundlich isotherm
Cu(II), Zn(II), Ni(II), Hg(II), and As(V)) are most studied [28]. and extended Langmuir isotherm models are often used in the study of
adsorption of heavy metals on carbon materials [21,35]. As shown in
2.1. Common adsorption models of carbon-based adsorbents Table 1, Langmuir isotherm is more frequently used in heavy metal
adsorption studies of carbon-based materials, which implies chemical
With the adsorption process going on, the adsorption and desorption monolayer adsorption and the adsorption performance of adsorbent
rate will eventually reach the same state, that is, adsorption equili- surface is uniform [17,31,36]. However, some carbon-based adsorbents
brium, in relative studies, adsorption isotherm and kinetic model are do not meet that ideal uniform condition [16], and Freundlich isotherm

Table 1
Reported adsorption isotherm and kinetics model of carbon-based adsorbents in heavy metal removal.
Adsorbent Heavy metal Best-fit isotherm model Best-fit kinetics model Ref

Rice husk carbon Cr Langmuir The pseudo-second-order model [50]

Corn straw porous carbon Cr Langmuir The pseudo-second-order model [46]
Sesame straw BC Pb, Cd, Cr, Cu, Zn Langmuir – [52]
Discarded mushroom-stick BC Pb, Cu, Cd, Ni Langmuir The pseudo-second-order model [53]
Anerobic digestion sludge BC Pb, Cd, Cu, Ni, Zn, Cr Langmuir, the competitive Langmuir The pseudo-second-order model [54,55]
Water hyacinth BC Cd Langmuir, The pseudo-second-order model [56]
Oxidized MWCNTs Pb Freundlich, D–R model The pseudo-second-order [37]
Thiol-derivatized SWCNT Hg Langmuir, Freundlich The first-order model [57]
Polyhydroxylbutyrate functionalized CNTs As, Pb, Cr, Cd, Ni, Cu, Fe, Zn Temkin The pseudo-second-order model [41]
Magnetic MWCNT Hg Langmuir The pseudo-second-order model [58]
GO Cu, Cd, Zn, Pb Langmuir The pseudo-second-order model [59]
rGO Pb Langmuir The pseudo-second-order model [60]
GO-chitosan composite Cr, As Langmuir The pseudo-second-order model [38,61]
β-cyclodextrin modified magnetic GO Pb, Cu Langmuir The pseudo-second-order model [62]
β-cyclodextrin/ethylenediamine/magnetic GO Cr Langmuir The pseudo-second-order model [63]
GO-MgO nanohybrid Pb Langmuir The pseudo-second-order model [64]
nZVI-rGO composites As Langmuir The pseudo-second-order model [65]

2
C. Duan, et al.
Table 2
Adsorption performance of carbon-based adsorbents under different pH.
Adsorbent Heavy metal pH Change of removal efficiency
Corn straw porous carbon Cr(VI) 1−9 A decline within pH = 1∼9. The removal efficiencies were 99.9 %, 98.32 %, and 32.22 %, when pH =
1, 3, and 9, respectively.
Oxidized MWCNTs Pb(II) 6−12 A quickly increase within pH = 6∼7, a maintainable level within pH = 7∼10, and an increase within
pH = 10∼12.
Magnetic MWCNT Hg(II) 1−8 There is an obvious decline of removal efficiency within pH = 2∼8
rGO Pb(II) 2, 3, 4 The removal efficiencies were 96.6 %, 96.3 %, and 53.4 %, at pH = 2, 3, and 4, respectively.
GO-chitosan composite Cr(VI) 1−11 A significant improvement within pH = 1∼4, but a decline when pH above 7.3.
As(III) 2−12 A significant improvement within pH = 2∼7.3, but a decline above 4.
can be used as an empirical formula without hypothetical conditions for
multilayer adsorption [34]; for example, Xu et al. found that Freundlich
simulated the Pb(II) adsorption data of oxidized multiwalled CNTs
better than Langmuir [37]. In addition, real water body might be binary
system or multi-system, Hayati et al. found that when used CNTs
modified by amination to adsorb Cu(II) and Pb(II) in their binary
system, the adsorption data was fitted better by extended Langmuir
isotherm than Langmuir isotherm [32]. Although Sherlala et al. found
that Temkin isotherm provided an evidence for ion exchange by one
kind of functionalized CNTs and showed higher R2 than that of Lang-
muir or Freundlich isotherm in their study [38], there are few mentions
of Temkin isotherm in other studies for heavy metal adsorption, and
also D–R model is rare. In studies, it is noteworthy that to determine
which model the adsorption process conform to should not only rely on
R2 of the fitting equation, but also judged by its basic hypothesis;
however, the basic hypothesis of some adsorbents is unclear, and the
data meets two isotherms well, then the estimation of adsorption ca-
pacity requires other reports [39,40].
2.1.2. Adsorption kinetics
The adsorption kinetics are elucidated by studying the change of
adsorptive capacity or adsorptive rate of adsorbent. The commonly
used kinetic models are shown in follow equations [31,41,42]：
k1 t
The pseudo-first-order model: log(Qe − Qt ) = logQ e −
2.303
t 1 t electrostatic repulsion, the adsorption of heavy metal cations would
The pseudo− second− order model: = +
Qt k2 Qe2 Qe
The Weber Morris equation:Qt = kWM t + c
Elovich kinetic model:Qt = (1/ β )ln(αβ ) + (1/ β )ln t (10)
where Qt is the amount adsorbed at time t, mg g−1; Qe denotes the
amount adsorbed at equilibrium, mg g−1; k1 is the rate constant of
pseudo-first-order adsorption, min−1; t is time, min; k2 is the rate
constant of pseudo-second-order adsorption, g·(mg min−1; kWM is the
intraparticle diffusion rate constant, mg·(g·min1/2)−1; c is a constant
related to thickness and boundary layer; αis the initial rate of adsorp-
tion, mg·(g min−1; βis desorption constant, g mg−1.
Adsorption behavior of heavy metals in water by carbon materials is
often described using the pseudo-first-order and the pseudo-second-
order kinetic models, while the latter is used more frequently [43] (see
Table 1). Wang et al. found the adsorption data of using willow wood
BC and cattle manure BC to adsorb Ni, Cu, and Cd, fitted well the
pseudo-first-order model [44]. In general, the pseudo-first-order model
assumes that there is reversible physical adsorption in the adsorption
processes [45], however, the pseudo-second-order model is most fre-
quently used in the adsorption of heavy metals by carbon materials in
this review, which means that the adsorption of carbon materials is
mostly chemical [46–49]. Elovich kinetic model describes adsorption in
heterogeneous systems influenced by reaction rate and diffusion factor
together [41], and there are few carbon-based adsorbents studies about
it for heavy metal removal. The application of the Weber Morris
Journal of Water Process Engineering 37 (2020) 101339
Optimum pH Ref
3 [46]
7−10 [37]
2 [58]
4 [60]
2 [61]
7.3 [38]
equation is mainly to further determine whether the adsorption process
is dominated by internal diffusion only [42].
In these kinetic models, contact time obviously is an important
variable which relates to adsorption capacity [50]. Exactly, due to the
time to meet that equilibrium is different for various heavy metals, the
contact time should be considered especially when there is a binary
system or multi-system of heavy metals [51].
2.2. Effects of process factors on heavy metals removal
pH, temperature, initial concentration, and coexisting ions are main
factors of adsorption for heavy metals, which affect the performance of
carbon-based adsorbent material in heavy metals removal.
2.2.1. Effect of pH
The pH value reflects the concentration level of H+ in water, and
ion exchange and electrostatic interaction are greatly influenced by H+
concentration. Different carbon-based materials possess different pHPZC
values, which refer to the pH value when the zeta potential of ad-
sorbents reaches zero [35]. As shown in Table 2, the effect of pH is
obvious for adsorption performance of carbon-based adsorbents. When
the pH value is lower than pHPZC value, it is not only meaning that more
H+ could exchange with heavy metal cations [21]; but also the high
concentration of H+ would protonate the surface functional groups
(e.g. -NH2, −OH) of carbon-based materials, so that the number of
(7)
surface positive charges obtains an increase [46,62]. Then, due to the
meet a decrease in water, meanwhile the adsorption effect of anions
(8)
(e.g. HCrO4−) becomes better [63]. When pH value increases, even
(9) higher than pHPZC, deprotonation brings back the negative charge for
functional groups [46], thus showing the opposite effect of cations and
anions. Therefore, in heavy metal cation adsorption, the pHPZC of
carbon-based adsorbents should be more acidic for a wider operational
range of pH; on the contrary, the pHPZC should be more alkaline for
anionic [35]. In addition, the ionic form of heavy metal ions also
connects with H+ concentration [36,66], these different forms of ions
have different affinity to functional groups [67], which ultimately affect
the adsorption capacity.
2.2.2. Effect of temperature
The influence of temperature on adsorption is generally related to
the thermodynamic nature of the adsorption process, and some para-
meters, such as enthalpy change (ΔH), free energy change (ΔG), and
entropy (ΔS) [68], which are evaluated from thermodynamic equations
[64]:
ΔH ΔS
lnkc = − +
RT R (11)
ΔG = −RTlnkc (12)
Where R is the universal gas constant (8.314 J/mol) and T (K) is the
absolute temperature.
ΔG and ΔH can be auxiliary explanation of adsorption behavior by
evaluating the isotherm data [59]. In this review, negative ΔG and
3
C. Duan, et al.
Fig. 1. Main Mechanisms of heavy metal by carbon-based materials.
positive ΔH in most adsorption of heavy metals by carbon materials,
indicating that the adsorption process are spontaneous, and the ad-
sorption capacity would increase with increasing temperature in certain
range [69]. For instance, Mohan et al. confirmed the adsorption of Pb
(II) by MgO-loaded graphene oxide at 20℃ is lower than the state at
30℃ [64]. However, Hadavifar et al. found that Hg(II) adsorption onto
MWCNTs-SH was more efficient at lower temperatures with the nega-
tive ΔG° and negative ΔH° [70]; therefore, the adsorption process of one
carbon-based material also could be exothermic reaction [36]. Fur-
thermore, Peng et al. believed that temperature can cause changes in
solubility and intermolecular interactions, and it might be the reason of
the temperature influencing the adsorption processes [69]. However, it
is favorable that adsorption taking place at normal temperature for real
situation (see in Table A2), so extra heating or cooling of solution
should be avoided as far as possible.
2.2.3. Effect of initial concentration
Within a certain concentration range, the adsorption capacity for
heavy metals keeps increasing with an increase of initial concentration,
when carbon-based adsorbent has not met a saturation. One reason for
this is that higher initial concentration contributes to an increases of the
transfer power from solution to carbon-based materials surface [32].
But when the initial concentration is set at a higher level, all adsorption
sites would be occupied and/or the adsorbent surface is covered by the
firstly adsorbed heavy metal ions [64], then, the interaction between
those unabsorbed heavy metal ions and carbon-based adsorbents would
be hindered. So, an exorbitant initial concentration of target heavy
metal ions will meet a decrease in the adsorption efficiency for later
adsorption stage. In addition, the change of pollutant concentration will
also affect the fitting degree of adsorption isotherm model. In some
cases, increasing the initial concentration of pollutants will make the
adsorption transition from single molecular layer to multi-molecular
layer, which will lead to the change of the best fitted adsorption model.
2.2.4. Effect of coexisting ions
In solution, ionic strength can represent the background electrolyte
concentration, which affects the interface potential and thickness of the
double layer [36]. Some coexisting cations or anions with different
strength would play a role in heavy metal ions removal by carbon-based
adsorbents in three aspects. Firstly, different heavy metal ions coex-
isting in a certain space compete with each other for adsorption sites,
the adsorption capacity or removal efficiency of adsorbent would per-
form a relative decrease when the system containing two or more kinds
of cations (or anions) compared with single system. Park et al. con-
firmed that the adsorption capacity of BC in a mixed system of (Cd2+ +
Pb2+) was lower than that of Cd2+ or Pb2+ single metal system,
4
Journal of Water Process Engineering 37 (2020) 101339
respectively [52]; and the existence and difference of this competitive
adsorption behaviors are decided by electric charges and hydrated ra-
dius of those cations, which cause different affinity to adsorption sites
on carbon-based adsorbents in binary system or multi-system [42].
Secondly, high concentration of K+, Na+, Ca2+, and Mg2+ in waters
can also compete with heavy metal cations to bring a decrease of the
heavy metal adsorption efficiency [53,71,72]. Thirdly, anions would
interact with heavy metal cations to form coordination ions or pre-
cipitation, and compete with heavy metal anions for adsorption sites.
For instance, the existence of SO42− in the solution can enhance the
precipitation and reduction of Cr(VI) while the existence of HCO3- could
affect the valence transition of Fe and inhibit the Cr(VI) removal [67].
However, SO42− can result a decline of Cr(VI) removal efficiency duo to
competition behavior, and smaller negative charges of NO3-and Cl-
make them show weak effects in adsorption of Cr(VI) [36]. And more
studies of coexisting anions need to be developed furtherly, for ex-
ample, the possibility and effect of Hg2Cl2 precipitation formed by Cl-
and Hg+ in Hg(II) adsorption process have not been defined clearly
[66].
In aqueous solution, duo to the most of heavy metal ions are cations,
the pHPZC of carbon-based adsorbents should be acidic for a wider
operational range of pH, but the differences of pHPZC of carbon-based
materials require various pH in real situation. And current researches
should be further developed in effect of coexisting anions, and a normal
temperature for adsorption process should be considered.
2.3. Adsorption mechanisms
There are five main types of adsorption for heavy metal on carbon-
based materials as shown in Fig. 1:
(1) Physical adsorption: A process about diffusion and deposition of
heavy metal ions in the pore of the adsorbent material, does not
form chemical bonds, which depends on the pore size distribution
and surface area of the adsorbent itself; exactly, the increases of
micropores and mesoporous can increase surface area and facilitate
contaminant diffusion, which can promote physical adsorption and
accelerate adsorption kinetics [73]. For instance, Fahmi et al. stu-
died the adsorption performance of grated empty fruit bunch BC
and found that higher surface area and more exposed microporous
can bring a promotion of Pb(II) adsorption capacity [74].
(2) Electrostatic interaction: When negative or positive charges are
carried on the adsorbent surface, the electrostatic attraction would
play a role in adsorption process between adsorbent and opposite
charged ions. Previous studies confirmed that electrostatic inter-
action is one of mechanisms for heavy metal adsorption by AC,
C. Duan, et al. Journal of Water Process Engineering 37 (2020) 101339

CNTs, and GN [21]. The surfaces of most carbon-based materials
are variably charged, and as mentioned in 2.2.1, solution pH and
pHPZC of adsorbents can influence the electrostatic interaction. And
the interaction between protonated or deprotonated functional
groups and heavy metal ions can be available on carbon-based
adsorbents surface, such as the electrostatic attraction between
protonated -NH3+ with HCrO4−, Cr2O72-, and CrO42- [63].
(3) Ion exchange: Ion exchange usually occurs between divalent metal
cations (M2+) and the proton of oxygen−COntaining functional
groups (−COOH, −OH), and cation exchange capacity (CEC) is an
indicator of this [21]. Lai et al. found this removal mechanism
contributes a lot to the adsorption of heavy metals by AC/BC [75].
However, according the research of Peng et al, the metal mineral
ions (such as K+, Na+, Ca2+, Mg2+) contained in graphene oxide
also showed capability to exchange with heavy metal cations [69].
(4) Surface complexation: On the adsorbents surface, functional groups
(such as −OH, −COOH, -O-, and −CO-NH-) react with heavy
metal ions (especially M2+) or complexes (such as Cd (OH)+, Pb
(OH)+) for heavy metals enrichment from aqueous solution [66],
and surface complexation forms multiatom structures in reaction
processes [21]. There are many reports have mentioned that Cd2+,
Cu2+, and Ni2+ could complex with −OH and −COOH [76–78].
For instance, Li et al. found that surface complexation might was an
important mechanism in Cd, Pb, and Hg removal, which con-
tributed by −OH or −COOH on BC surface [66]. And Hadavifar
et al. found that -SH can complex with Hg2+ on thiol-derivatized
CNTs surface [70].
(5) Precipitation/coprecipitation: Heavy metal ions can form solid
precipitates or coprecipitate with other ions and groups on ad-
sorbent surface to dissociate from water. Liu et al. found that the
coprecipitation can be observed obviously in adsorption systems
with high concentration of heavy metal ions [17], and it can occurs
on carbon-based adsorbents surface repeatedly [21]; such as the
precipitation or coprecipitation as CdCO3, Cd3(PO4)2, and probably
Cd(OH)2 on BC in Cd removal [56].
or chemical properties of carbon-based materials often make them
perform different adsorption behavior, and the properties of various
carbon-based materials are usually determined by their preparation
process. BC, for example, Deng et al. [78] and Yu et al. [80] found that
the higher porosity, larger specific surface area, more obvious graphite
crystal structure and higher pH value can be obtained at higher pyr-
olysis temperature, meanwhile less oxygen-containing functional
groups affects physical or chemical adsorption efficiency. In addition, it
can be notable that most studies concentrated on the heavy metal ions,
and the removal studies of hydroxide complexes or other heavy metal
complexes ions are inadequate [81].
3. Application of carbon-based adsorbents in adsorption of heavy
metals
Carbonaceous materials have abundant pores and functional
groups, which can be used for heavy metal removal in water and
roughly classified into three categories: AC/BC based materials, CNTs
based materials and GN based materials. Namely, the development of
various modified materials based on AC/BC, CNTs and GN are the three
main lines for the development of carbon-based adsorbent.
3.1. AC/BC based materials
AC is produced by pyrolysis and activation of wood, coal, lignite,
and other carbon-containing raw materials [82,83], and it is amorphous
carbon solid with black powder, granular, massive and honeycomb
shapes. AC can be obtained by pyrolysis and activation of most carbon-
rich substances in principle, so the sources of it are very wide. BC, a
porous solid materials [80] with carbon as the main component, were
obtained by biomass pyrolysis [84], such as botanic materials and
agricultural waste. BC is similar to AC, or there is no clear boundary
between them in the studies and utilization of them in heavy metal
adsorption.

Sometimes, reduction plays a role in the heavy metal removal: Some
high-valent heavy metal ions are not directly adsorbed but reduced to
low-valent states firstly (such as Cr(VI) being reduced to Cr(III), Hg2+
being reduced to Hg2Cl2) due to the electronegativity of the carbon
materials themselves, and then removed by complexation and ion ex-
change [66]. Table 3 shows the contributions of those mechanisms in
adsorption processes taking place on carbon-based materials.
For these mechanisms, they are universal for most of carbon-based
adsorbents; however, while precipitation/coprecipitation may occur in
adsorption processes, it is not commonly regarded as the main me-
chanisms of heavy metals adsorption. In fact, the differences in physical
3.1.1. AC and BC
3.1.1.1. Agricultural waste-derived AC/BC. Rice husk carbon. Khan et al.
[85] mixed dried rice husk and sulfuric acid, and heated the mixture for
a period of time, then the rice husk carbon was obtained. After the
adsorption experiment of Cr(VI) removal, it was found that when the
initial concentration of Cr(VI) was 80 mg/L and pH = 2, Cr(VI) would
be completely adsorbed after 120 min. Deng et al. [78] carried out the
adsorption experiments of Cd(II) and Ni(II) with rice husk carbon. The
equilibrium adsorption capacity of Cd(II) and Ni(II) was 65.40 mg/g
and 54.60 mg/g, respectively, but in the binary system of Cd(II) and Ni
(II), the competition of these two heavy metals for the adsorption sites
leaded to the decrease of adsorption capacity. In addition, ion exchange

Table 3
Adsorption mechanism of heavy metal ions on carbon-based adsorbents.
Ions Mechanisms Instances

cations -Surface complexation Functionalized BC or CNTs: Complexation of -OH with Cd2+, Cu2+, Pb2+, Ni2+, and Hg2+ [76,77,78]
-Ion exchange Functionalized BC or MWCNTs: Complexation of -COOH with Cd2+, Cu2+, Hg2+, Zn2+, and Ni2+ [58,76]
-Electrostatic interaction Functionalized AC or BC: Complexation of -NH2 with Cu2+, Pb2+, and Hg2+ [76,79]
-Precipitation Functionalized MWCNTs: Complexation of -SH with Hg2+ [70]
BC: Exchange of some inherent cations (such as K+、Na+、Ca2+、Mg2+) of carbon-based adsorbents with Pb2+, Cu2+,
Cd2+, and Ni2+ [53,74]
The formation of Cd-Cπbonding between lone-pair π electrons of adsorbents with Cd2+ [40]
GO: Zn precipitation as Zn(OH)2(s) on adsorbents [47]
Hydroxide complexes -Surface complexation GO or magnetic GO: Complexation of -OH with Zn(OH)+ and H3AsO3 [38,47]
-Coprecipitation BC: Cd precipitation or coprecipitation with inherent carbonate or phosphate on the surface of adsorbent, as CdCO3, Cd3(PO4)2
or Cd(OH)2 [56]
anions -Physical adsorption BC: HCrO4−、Cr2O72- were trapped in the micropores because of less radiuses than the pore size of adsorbents [46]
-Ion exchange BC: Ion exchange between Cr(VI) and the -COOH on the porous carbon adsorbent surface [46]
-Electrostatic interaction Magnetic GO: The electrostatic attraction between -NH3+ with HCrO4−, Cr2O72-, and CrO42- [63]
nZVI-rGO: Electrostatic interactions between adsorbents and H2AsO4−, HAsO42−, and AsO43− [65]

5
C. Duan, et al.
adsorption and precipitation were main adsorption mechanism.
Corn straw porous carbon. Ma et al. [46] used corn straw as raw
material to prepare corn straw porous carbon, and carried out related
adsorption experiment of Cr(VI). The results showed that maximum
adsorption capacity of Cr(VI) was 175.44 mg/g, and the removal effi-
ciency was 70.65 % after three adsorption-desorption cycles. Several
mechanisms were included in the adsorption process: (1)HCrO4− and
Cr2O72- were trapped in micropores; (2) Ion exchange and complexa-
tion took place between Cr(VI) and oxygen−COntaining functional
groups (e.g. −COOH, −OH and -C-O-C); (3) Cr(VI) was reduced to Cr
(III) by ReOeR or ReOH. The removal efficiency of Cr(VI) in real
electroplating wastewater was 97.9 % with an obvious selectivity
compared with Ni2+ and Cu2+ in water.
Discarded mushroom-stick BC. Wang et al. [53] pyrolyzed the dis-
carded mushroom-stick at 300, 500, and 800 ℃, respectively, to get BC
marked DMB3, DMB5, and DMB8. The adsorption of the BC on Pb(II),
Cu(II), Cd(II), and Ni(II) was studied. DMB8 provided the maximum
adsorption capacity of those heavy metals, and it probably was that
higher pyrolysis temperature help the DBM to form more aromatic
structure, and allowed larger number of initial mineral ions (e.g. Na+,
Ca2+ and Ma2+) to exchange with heavy metal ions.
3.1.1.2. Other botanic material based BC. Some plants are not regarded
as crops because of their low economic value, but thanks to their large
carbon-rich biomass, it is possible that considering those botanic
materials as raw materials to prepare BC. Take water hyacinth as
example:
Zhang et al. [56] used water hyacinth as raw material to pyrolysis it
in N2 atmosphere to produce BC. They studied the Cd(II) adsorption on
the BC, and found that when the initial concentration of Cd2+ was ≤50
mg/L, the removal efficiency of Cd2+ was close to 100 % in a short
time, and the maximum adsorption capacity was 70.31 mg/g. Ion ex-
change and surface complexation was dominant mechanisms in
Cd2+adsorption, and the coprecipitation of Cd2+ or Cd(OH)+ with BC
and the electrostatic adsorption of Cd2+ by BC also played a role. The
results of the report made by Ding et al. [86] showed the adsorption
capacity and activity of water hyacinth BC to Pb are stronger than that
of Cd in the binary system, and cation-π interaction was also one of
adsorption mechanisms.
3.1.1.3. Sludge-based BC. Ho et al. [54] pyrolyzed anaerobic digestion
sludge to prepare anerobic digestion sludge biochar (ADSBC) for the
utilization to remove Pb(II), Cd(II), Cu(II), Ni(II), Zn(II) and Cr(VI) from
water. The adsorption capacities were in the order of Pb(II) > Cd
(II) > Cu(II) > Zn(II) > Ni(II) > Cr(VI). Ion exchange, precipitation,
complexation and electrostatic interaction were main adsorption
mechanisms, whose contribution in the removal process of Pb(II)
were 33.4 %, 53.5 %, 83 % and 4.8 %, respectively. Ni et al. [55]
studied the competitive adsorption between Pb (II) and Cd (II) on
ADSBC. The affinity of Pb2+ to adsorption sites was stronger than that
of Cd2+, so some Pb2+ arrived at ADSBC surface would replace
adsorbed Cd(II), and occupied the sites to prevent the Cd2+ adsorption.
3.1.2. Modified AC/BC
The adsorption capacity of one carbonaceous material can be im-
proved by changing its properties, that is, modification [84]. The
modification of AC/BC can be achieved by grafting functional groups
(including amino-functionalization, sulfur-functionalization, and other
group functionalization) [19] or compounding/supporting inorganic
substances.
3.1.2.1. Functional groups grafted AC/BC. Some chemical method can
be used to increase the number or species of functional group on AC/BC
surface. The amino-functionalization (e.g. NH3-) and sulfur-
functionalization (e.g. C–S, C]S or S]O) are grafting nitrogen-
containing groups and sulfur-containing groups respectively on the
6
Journal of Water Process Engineering 37 (2020) 101339
carbonaceous materials surface. Other functionalization refers to
transforming certain functional groups on carbonaceous materials
surface into others, or grafting side chain to introduce other
functional groups [21].
(1) Amino-functionalization. Faheem et al. [76] used chemical
method (impregnation method) to graft amino group on the surface of
corncob BC to increase the adsorption capacity of Hg(II) to about twice
as much as the unmodified: The corncob BC was slightly oxidized by
H2O2 to transform some hydroxyl groups into carboxyl group, and
immersed and stirred in a mixture solution of ultrapure water, urea, and
NaOH; then a specific amount of EDTA was added to obtained amino-
grafted modified BC. According to the adsorption experiment, the
maximum removal efficiency of Hg(II) was 97.6 %, and it was con-
firmed that Hg(II) interacted with −OH, −COOH, -NH2, -NH- respec-
tively on modified corncob BC via electrostatic attraction, surface
complexation, and ion exchange. Saleh et al. [79] prepared poly-
ethyleneimine functionalized AC to study the Hg(II) adsorption, and
found that the adsorption might be caused by the interaction between
Hg(II) and C]O, -NH2.
(2) Sulfur-functionalization. Li et al. [87] studied the adsorption of
Cu(II), Pb(II), Cd(II), and Ni(II) on thiol-functionalized AC. The AC was
prepared from coal-blended sewage sludge, and oxidized by nitric acid,
then the oxidized AC was mixed with DMF (n, N-dimethylformamide).
After that, NaHSO4·H2O and mercaptoacetic acid were added to react
with the AC for a period of time under heating conditions. Finally, the
AC was treated with Na2S·9H2O and 95 % ethanol, washed with deio-
nized water and dried to obtain SH-AC. The adsorption capacity of this
material was much higher than that of unmodified AC, the maximum
adsorption capacities of Cu(II), Pb(II), Cd(II), and Ni(II) were 238.1 mg/
g, 96.2 mg/g, 87.7 mg/g, and 52.4 mg/g, respectively. In addition to
the reduction reaction of Cu(II), complex adsorption was main me-
chanism for other heavy metal ions.
Modification by functional groups graft has obvious advance of
adsorption capacity, specific adsorption for certain ions(e.g. -SH to
Hg2+) [76], different processes with different chemical modifier, sig-
nificantly ratio-influenced adsorption capacity, and complex prepara-
tion process.
3.1.2.2. AC/BC-inorganic substance composite. (1) nZVI-AC/BC
composite. The specific surface area of nZVI is large, which can be
used as heavy metal remover by reduction and adsorption, but nZVI is
easy to agglomerate and form larger particles when it is used alone and
the removal efficiency would be disturbed. Given this defect, AC/BC is
used to support nZVI to overcome the agglomeration of nZVI, and this
composite has complex structure, so the adsorption ability is enhanced
[67]. There are two common chemical methods to prepare ZVI-AC
composite: one is pyrolysis-liquid phase reduction method, the other is
one-step pyrolysis method. The former is to use BC as support material
and immerse it in ferrous salt (e.g. FeSO4‧7H2O) solution, and use some
reducing agent to reduce iron ion to zero valent iron on BC surface. The
latter is let ferrous salt precipitate on biomass (e.g. rice husk, coconut
husk) by air drying, and then pyrolyze the air dried biomass to get BC,
at the same time, BC reduces Fe(II) to Fe0 [88].
Shang et al. [67] prepared BC/Fe° by liquid-phase reduction
method: The herbal residue was pyrolyzed to obtain BC, and the nZVI
was reduced and supported on BC using NaBH4. According the ad-
sorption experiment of Cr(VI), the maximum adsorption capacity ob-
tained was 98.71 ± 0.04 %, and the removal of Cr(VI) was one com-
bination of reduction process and precipitation process: A part of Cr(VI)
was reduced to Cr(III) by nZVI, and then Cr(III) and residual Cr(VI)
interacted with oxygen-containing functional groups on BC/Fe° surface.
However, pyrolysis-liquid phase reduction process is time-consuming
and requires additional reductant, so it is not superior to one-step
pyrolysis in cost [88]. Wang et al. [89] synthesized ZVI-AC composite
by ball milling to avoid a complicated and costly chemical preparation
process, and the experiment confirmed that the Cr(VI) removal
C. Duan, et al.
efficiency was 94.01 % within 120 min under acidic and anaerobic
conditions.
(2) Metal oxide-AC/BC composites. Nano single metal oxides and
binary metal oxide (consist of MnO2, MgO, and FeOx) are also often
used to get carbon-based composite materials [66,90]. Yu et al. [80]
impregnated water hyacinth BC in Zn(NO3)2 solution, and after drying
and calcination, they obtained the BC-ZnO composite. The adsorption
experiment of Cr(VI) by the composite showed that the optimal content
of ZnO in the composite was 30 wt%, and the removal rate of Cr(VI)
could be maintained above 95 % at natural pH value. Reduction and
precipitation were the main mechanisms. Zhou et al. [90] dispersed BC
in the mixture of KMnO4 and Fe(NO3)3 by ultrasound and pyrolyzed it
to obtain BC loading Fe-Mn binary oxide. The results show that the
maximum adsorption capacity of Cu(II) and Cd(II) were 64.9 mg/g and
101.0 mg/g respectively, which much as three times of capacities of BC.
The complexation of divalent metal ion (Cu2+ or Cd2+) with Fe-MnOx,
−COOH, and −OH was the main adsorption mechanism, while cation-
π bounding also plays a role in adsorption process.
Inorganic substances being supported on carbon base is one method
for carbon-based materials modification [67], but objectionable ag-
glomeration of zero-valent metal or other nonmagnetic metal com-
pounds would not be completely evitable [65], which need further
research.
3.2. CNTs based materials
3.2.1. CNTs
Due to the revolution of nanotechnology, CNTs perform obvious
operability for better heavy metal adsorption efficiency compared to
AC/BC, and met an extensive utilization in environmental remediation
[91].
CNTs are a kind of hollow cylinder formed by a net composed of
large number of carbon atoms covalently combined each other with
hexagonal structure. According to the number of net layers, CNTs can
be divided into single-walled carbon nanotube (SWCNT) and multi-
walled carbon nanotube (MWCNT) [92]. CNTs have hydrophobicity,
electrode, abundant pore structure and functional groups, and performs
a broad-spectrum adsorption for heavy metals, such as Pb, Cu, Cd and
Zn in water [93]. However, due to the strong hydrophobicity and low
affinity, CNTs are often not directly applied in aqueous solution, which
limits the application of themselves [58]. After modification, the deri-
vative materials obtained broaden the application range, in other
words, CNTs is often used as raw materials for the production of their
derivatives.
3.2.2. Modified CNTs
3.2.2.1. Oxidized CNTs. The common modification of CNTs includes
oxidation, functional group graft, and magnetism. Oxidized CNTs can
be obtained by strong oxidants (e.g. strong acid, potassium
permanganate, ozone) treating to enhance their hydrophilicity and
solubility, which is conducive to the heavy metal adsorption. The
common method is considering of acid oxidation, and the mixed acid or
single acid of concentrated sulfuric acid and concentrated nitric acid is
often used [92,94]. The process of acid oxidation can increase the
number of oxygen-containing functional groups (e.g. carboxyl group,
hydroxyl group) on carbon-based adsorbents surface to enhance the
hydrophilicity for better performance of heavy metal adsorption
[37,57,92].
Xu et al. [37] prepared MWCNTs by chemical vapor deposition, and
then oxidized them with nitric acid. They used MWCNTs to adsorb Pb
(II), and found that the adsorption performance was largely influenced
by pH value: The removal efficiency was only 10–20 % when pH < 6.5,
but 90 % in the range of pH 7−10. The adsorption reached equilibrium
very quickly, and the surface complexation was main adsorption me-
chanism of oxidized MWCNTs for Pb(II) removal. Wang et al. [95] and
Sun et al. [96] respectively confirmed that oxidized MWCNTs can be
7
Journal of Water Process Engineering 37 (2020) 101339
used for the adsorption and removal of U or Co in water. And, Tofighy
et al. [97] found that the preference order of oxidized CNT sheets to
adsorption heavy metal was Pb(II) > Cd(II) > Co(II) > Zn(II) > Cu(II).
In a words, oxidation means rich oxygen-containing functional
groups, satisfactory hydrophily [98], and obvious advance of adsorp-
tion capacity; furtherly, what noteworthy is that oxidized CNTs can be
further modified to achieve more targeted optimization or modification
by functional groups transforming. In many cases, the realization of
amination and thiol-functionalization requires acid oxidation treatment
first [70,99], and oxidation is commonly regarded as the previous step
for other modification methods [41,76,87].
3.2.2.2. CNTs grafting functional groups. Amino-derivatized CNTs.
Hayati et al. [32] used concentrated nitric acid and sulfuric acid to
oxidize CNTs, and prepared poly-amidoamine-CNTs by the reactions
with 2,4-diisocyanate and ethylenediamine. The experiment showed an
excellent performance of this modified CNTs: At pH 7, the adsorption
capacity of Cu2+ and Pb2+ can reach 3333 mg/g and 4870 mg/g,
respectively.
Thiol-derivatized CNTs. Bandaru et al. [57] treated SWCNT using
concentrated nitric acid and sulfuric acid to obtain carboxyl-functio-
nalized CNTs powder. Then added the powder to the coupling agent of
1-ethyl-(3−3’-dimethylaminopyl) carbodiimide and N-hydro-
xysuccinimide, and heated the mixture in the ethanol solution of cy-
stine hydrochloride to get thiol-derivatized SWNT-SH. According to the
adsorption experiment of Hg(II) in aqueous solution, the adsorption
capacity of this material is about three times of that of unmodified
carbon nanotubes, and four times of that of AC. Furthermore, the
complexation between mercapto and Hg2+ ions took place in this
chemical adsorption process, and the maximum adsorption capacity
predicted was 131 mg/g.
Other functionalized CNTs. Bankole et al. [41] dispersed the CNTs
purified by concentrated nitric acid and concentrated sulfuric acid in
dimethylformamide (DMF), then added titanium chloride solution and
heated the mixture. After drying, polyhydroxylbutyrate (PHB) and di-
methylformamide (DMF) were added for reheating to obtain PHB
functionalized CNTs (PHB-CNTs). The results of adsorption experiments
show that the heavy metal removal efficiency of PHB-CNTs are higher
than that of the non-functionalized CNTs, and the removal efficiency of
Cd, Pb, Cu, Cr, and As were higher than 98 %. In addition, low toxic
PHB functionalized CNTs are easy to product to remove heavy metals in
electroplating wastewater effectively.
3.2.2.3. Magnetic CNTs. In general, CNTs are suspended in water after
adsorption, which is difficult to collect and treat; therefore, the starting
point of magnetization of carbonaceous materials is to facilitate the
subsequent separation from the solution [100], and to realize rapid
dosing-separation cycle in an external magnetic field [101]. Common
magnetization method is to use FeCl3 [101], FeCl2‧4H2O [38],
FeSO4‧7H2O [62], or other iron salts to generate magnetic Fe3O4 [91]
on adsorbents.
Sadegh et al. [58] used nitric acid and microwave radiation to treat
MWCNTs firstly, and then, MWCNTs and Fe3O4 nanoparticles were
immersed in ethanol solution to prepare magnetic MWCNTs. According
to the adsorption research of Hg(II), the −COOH group on MWCNTs
and Fe3O4 nanoparticles form a large network structure, and the max-
imum adsorption capacity of 238.78 mg/g. The Hg(II) adsorption on
magnetic MWCNTs was mainly caused by electrostatic adsorption and
complexation. In addition, the network structure of this material pro-
vides a large number of binding sites for heavy metal adsorption.
Magnetization makes carbon-based materials convenient for effi-
cient separation from treatment-finished solution and accessible for
mechanized operation; so, magnetic metal compounds are commonly
chosen to be supported by CNTs or other carbon-based materials, which
has been widely applied in magnetization [101].
C. Duan, et al.
Table 4
Differences among graphene, graphene oxide and reduced graphene oxide
[102].
Materials C:O ratio Color
Graphene(GN) 89:6 Dark
Reduced graphene oxide(rGO) 8−246 Dark-brown
Graphene oxide(GO) 2−4 Slight-brown
3.3. GN based materials
3.3.1. GN analogues
GN based materials are GN and its derivatives, including GN, gra-
phene oxide (GO), reduced graphene oxide (rGO) and their compounds
with organic or inorganic substances, respectively. Among them, GN,
GO and rGO are typical GN analogues [102], and most of the other
derivatives are based on the modification of these three materials.
GN, GO and rGO are closely related, and the main difference among
them are their C:O. As shown in Table 4, it is considered that the oxygen
content of GO is the highest and that of GN is very low, while the
oxygen content of rGO has a large span [102]. GO and rGO have more
oxygen-containing functional groups than GN; therefore, they have
more obvious hydrophilicity and dispersion to combine with heavy
metal ions through covalent bond and electrostatic action [64].
3.3.1.1. GN. GN is one of the latest carbon nano material. In a narrow
sense, GN refers to a two-dimensional single-layer graphite hybridized
by carbon atom sp2, with a specific surface area of nearly 2630 m2/g
[64]. But nowadays, GN is a generalized concept, and some three-
dimensional materials with multi-layer carbon atomic layer structure
are also called GN [102], or 3D GN [103]. There are two ways to
prepare GN: One is the top-down method including mechanical
exfoliation of bulk pristine graphite or chemically treated graphite,
GO reducing and microwave-assisted method [104]. The other is the
bottom-up method including pyrolysis method [105], chemical
deposition [103] and epitaxial growth on SiC [106]. The so-called
top-down approach is that the preparation process of GN is
accompanied by the reduction of the dimension of raw materials (e.g.
graphite), such as the conversion from 3D to 2D or 2D to 1D; while the
bottom-up approach, on the contrary, is the process of the dimension
increasing, such as the conversion from carbon atom or carbon
containing molecule to GN with 2D or 3D structure [107].
In fact, it is rare to use raw graphene as adsorbent to remove heavy
metals in water. The preparation process of GN is usually used as a
reference for the production of graphene-based materials; by compar-
ison, the structure of 3D GN can be artificially controlled by the choice
of substrate, so, 3D GN is prepared directly (e.g. the preparation of foam
graphene by chemical deposition) for more wider utilization [103].
3.3.1.2. GO. GO is usually prepared by oxidation of graphite or GN
with strong oxidant. It has high oxygen content, a large number of
oxygen-containing functional groups such as C]O, CeOeC, eOH and
eCOOH on the surface, and has stronger hydrophilicity than carbon
nanotubes [98]. GO is superior to GN in heavy metal adsorption due to
its rich oxygen-containing functional groups. Typical oxidation
methods include Hummers method, Brodie method, Staudenmaier
method and improved method based on these methods [69].
Traditional Brodie method and Staudenmaier method have longer
reaction time and are more prone to explosion than Hummers
method; relatively, Hummers method is safer and faster [108].
However, these three methods are able to produce harmful gases,
such as NO2, N2O2 and ClO2, more or less. So, the current oxidation
methods are mostly based on the improvement of Hummers method
[109]. In the improved Hummers method, the mixed acid of
concentrated sulfuric acid and phosphoric acid (9:1) is used instead
8
Journal of Water Process Engineering 37 (2020) 101339
of concentrated sulfuric, and compared with Hummers method, the
modified Hummers method brought higher oxidation degree, more
oxygen-containing functional groups, and larger layer spacing to GO
[108].
Raghubanshi et al. [108] prepared GO by Hummers method, and
found that the adsorption capacity of GO benefited from the interaction
between Pb(II) and functional groups on GO, and the large specific
surface area and lamellar structure of graphene oxide also played a
crucial role.
Tan et al. [71] used modified Hummers to prepare GO powder for
Cu(II) adsorption. The experiment results showed that a higher oxida-
tion degree brought a larger adsorption capacity to GO. The com-
plexation and electrostatic attraction between Cu2+ and oxygen-con-
taining functional groups were main adsorption mechanism in that
process. In addition, they found that Na+ would influence the adsorp-
tion by competitive adsorption behavior.
Jun et al. [59] confirmed that Cu(II), Cd(II), Zn(II), and Pb(II) can
be effectively removed in their single metal solution by GO, respec-
tively, and found the removal efficiency of Pb(II) was highest with a
maximum adsorption capacity of 555 mg/g. GO could effectively ad-
sorb Pb(II) mainly due to its oxygen-containing functional groups, and
the order of metal ions adsorption was
Pb2+ > Cu2+ > > Cd2+ > Zn2+.
3.3.1.3. rGO. rGO, as the name indicates, is one more stable product of
reducing and removing some oxygen-containing functional groups from
GO, yet, some oxygen-containing functional groups still are remained.
And there are two reduction methods: One is heat treatment, such as
microwave heating or strong flash evaporation, to decompose oxygen-
containing functional groups into CO or CO2 gas to escape from solid
matter. The other is chemical reduction, which can reduce oxygen-
containing functional groups on the surface of GO by chemical reducing
agent of hydrazine, metal hydride and hydrohalic acid [98] or plant
extract [60].
Due to the toxicity of hydrazine, Lin et al. [60] thought that plant
extracts should be considered as reducing agent of GO, which contains
reducing substances such as phenols, amino acids, caffeine, and vita-
mins, and have no biological toxicity; so, green tea extract was used to
prepare rGO for Pb(II) removal in water. The experimental results show
that whole adsorption process was exothermic, and high temperature
counted against adsorption. The main mechanism of Pb(II) adsorption
was cation-π bonding. In experiment, at 30 °C, the adsorption removal
efficiency of Pb(II) reached 96.6 %, when the solution pH = 4.5, the
dosage of rGO was 0.4 g/L, and the initial concentration of Pb(II) in the
solution was 10 mg/L.
3.3.2. GN analogues grafting functional groups
GN, GO and rGO can be compounded with organic compounds to
introduce certain functional groups to prepare GN analogue-based
materials. Some organic compounds (e.g. chitosan, β-cyclodextrin)
have strong adsorption capacity [34], so the composites can play the
adsorption properties of both organic materials and GN analogue to
improve the adsorption.
3.3.2.1. Chitosan-GO composite. Chitosan is the N-deacetylation
product of chitin, which is a kind of natural polysaccharide. Its
molecules are rich in amino and hydroxyl groups [34]; so in recent
years, it often participates in the modification of graphene-based
materials as aminated materials [61].
Samuel et al. [61] dispersed GO in distilled water and added chit-
osan and NaBH4 to obtain GO-chitosan composite. The maximum ad-
sorption capacity of Cr(VI) was 104.16 mg/g, and the main mechanism
was the complexation between Cr(VI) and −OH, -NH. In addition, GO-
chitosan composite performed good regeneration ability because the
adsorption efficiency of Cr(VI) on GO-chitosan composite decreased
from 96 % to 82 % after 10 adsorption desorption cycle. Sherlala et al.
C. Duan, et al.
[38] used magnetic chitosan-GO material to studied the As(III) removal.
The adsorption experiment showed that the neutral water environment
was conducive to the adsorption of As(III), and the main adsorption
mechanism was the complexation of As(III) (in the form of H3AsO3)
with -NH2, −OH, and −OH2 on the surface of magnetic chitosan-GO.
3.3.2.2. β-cyclodextrin-GO composite. β-cyclodextrin is a kind of cyclic
oligosaccharide which is composed of seven glucose units, it has a
hydrophilic cavity with hydrophobic internal surface and hydrophilic
external surface. The hydrophobic cavity of β-cyclodextrin can form
host-guest inclusion with many kinds of organics and metal ions [110]
and the surface hydroxyl can also form complex with metal ions
[48,63,111], which has been used to be modifier [112] to develop
eco-friendly adsorbents.
Ma et al. [62] used β-cyclodextrin modified magnetic GO to carried
out adsorption experiments of Pb(II) and Cu(II). They found that the
adsorption capacities of Pb(II) and Cu(II) could rapidly increase to a
higher level in a short time, and the removal efficiency of Pb(II) reached
82.67 % in 15 min. The estimated maximum adsorption capacities of
Pb2+ and Cu2+ were 279.21 mg/g and 93.97 mg/g, respectively, and
the complexation between GO and heavy metal ions contribute a lot.
And Huang et al. [111] confirmed that the −COOH on β-cyclodextrin
can provide adsorption sites for Cu(II). Wang et al. [63] prepared β-
cyclodextrin-ethylenediamine-magnetic GO to carried out the adsorp-
tion experiment of Cr(VI). Surface diffusion and internal diffusion exist
in the adsorption process, and the adsorption of Cr(VI) (HCrO4−) in
water by this material was attributed to three aspects: the electrostatic
interaction between HCrO4− anion and composite material, the host-
guest interaction with β-cyclodextrin hydrophobic cavity, and the
combination with hydroxyl groups on GO.
3.3.3. GN analogues compounding/supporting inorganic substance
Similar to BC/AC, zero valent metals and metal compounds are
typical substance often supported by carbonaceous materials.
3.3.3.1. D GN compounding polymetallic compound. Wang et al. [113]
studied the NiFe-layered double hydroxide, and inserted a MoS42− into
the lamellar structure to form a polymetallic compound. The
polymetallic compound was assembled on the surface of 3D GN foam
to get a porous lamellar mixed block (NiFe-MoS42−-LDH/CF) for Hg2+,
Pb2+, and Cu2+ removal. It was found that the rougher surface
provided a large number of adsorption sites, so that the calculated
maximum adsorption capacities of Hg2+, Pb2+, and Cu2+ were 462,
299, and 128 mg/g, respectively, and their adsorption efficiency could
exceed 99 %, and the adsorption mechanism was mainly the
complexation of MoS42− to heavy metals. Due to the superior
adsorption performance, this porous lamellar mixed block could be
applied in the drinking water purification.
3.3.3.2. GO-metal oxide nanohybrid. Mohan et al. [64] prepared GO-
MgO nanohybrid by precipitation, and the adsorption experiment
indicated this composites could remove Pb2+ ions from drinking
water without pH and temperature changes nearly with a high
adsorption capacity of Pb2+ (190 mg/g), and the ideal conditions
concluded was low dosage (0.4 g/L), 30℃, and pH = 6.5. The internal
diffusion and external diffusion dominated the adsorption process, and
ion exchange and complexation took place on GO-MgO nanohybrid
(between Pb2+ and −COOH or −OH), and Mg2+ ions in the materials
also provided many sites for exchanging with Pb2+.
3.3.3.3. ZVI-rGO composite. Wang et al. [65] prepared the nZVI-rGO
composite. In the adsorption experiment of As, the maximum
adsorption capacity of As3+ and As5+ are 35.83 mg/g and 29.04 mg/
g, respectively; and the adsorption of As3+ was mainly caused by
surface complexation, while the adsorption of As5+ was realized by
complexation and electrostatic interaction. It was noteworthy that pH
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Journal of Water Process Engineering 37 (2020) 101339
value of the solution had a great influence on the adsorption of As3+
and As5+: the forms of As(VI) could be H2AsO4−, HAsS42−, and AsO43−
with the increase of pH; adsorption efficiency of As(III) would be
variable due to the form of As(III), which could be H3AsO3 and/or
H2AsO3− under different pH values.
3.4. Regeneration of carbon-based materials
The carbon-based adsorbents could keep their adsorption capacity
at a high level after several adsorption-desorption cycles. At present,
acid or alkali are generally applied to the desorption and regeneration
of carbon-based materials.
3.4.1. Regeneration in acid solution
Acid-method regeneration means that the carbon-based materials,
after adsorption, are immersed in acid solution for desorption, thor-
oughly washed, and dried, then became available for the next adsorp-
tion. Sulfuric acid, nitric acid, and hydrochloric acid solution can be
used to desorb heavy metals from carbon-based materials. And general
regeneration are as follows steps: (1) Carbon-based adsorbents are
immersed in acid solution with certain concentration or pH [32], and
sonicated for several minutes. (2) After filtration, the adsorbents are
washed with ethanol and deionized water. (3) The adsorbents are dried
at certain temperature for the next adsorption-desorption cycle [57].
3.4.1.1. Regeneration in nitric acid or sulfuric acid solution. After
repeated adsorption-desorption cycles, though there are slightly
decreases in adsorption efficiency of carbon-based adsorbent, the high
values of adsorption capacity and removal efficiency still are accessible
when the regeneration process under the most appropriate
concentration of acid solution. Saleh et al. [79] used 0.1 M, 0.25 M,
and 0.5 M nitric acid solution to establish the regeneration performance
of AC after adsorbing Hg(II), respectively, and the recovery of
adsorption capacity were 50 %, 80 % and 95 %. Tahir et al. found
that after three adsorption-desorption cycles, the removal efficiency of
magnetic Hydroxypropyl graphene for Pb(II) and Cu(II) was still above
80 % with a small loss of adsorptive capacity, and sulfuric acid was used
desorption reagent [114].
When the heavy metals exist in water as anions, the sulfuric acid-
method is more worthy to be considered. Samuel et al. found that
SO42− may decrease Cr(VI) adsorption due to the opposition among
anions, which can be beneficial to Cr(VI) desorption efficiency [61]. In
addition, Shang et al. found that SO42− improved the removal of Cr(VI)
by increasing the number of reactive sites and corrosion rate of ZVI
[67]. For nitric acid-method：in comparison, the opposition among
anions NO3- and heavy metal anions is weak; therefore, nitric acid so-
lution is used more frequently in the adsorption of cation.
3.4.1.2. Regeneration in hydrochloric acid solution. Hydrochloric acid
solution is the most frequently-used desorption reagent in acid-method
regeneration, because it has no oxidation property and Cl− has little
influence on the adsorption of most heavy metal ions. The regeneration
of BC [86], CNTs-SH [57], and GO [47] can be regenerated by
hydrochloric acid with high desorption efficiency. Wang et al. proved
that hydrochloric acid solution can effectively desorb Zn on GN and the
desorption efficiency reached 91.6 % [47]. Jun et al. [59] found that
the adsorption efficiency of GO for Pb(II) was nearly invariable during
three adsorption-desorption cycles.
To the regeneration in acid solution, a selection of desorption agent
is significant to regeneration of carbon-based materials. For example,
Peng et al. used 0.1 M HCl solution, 0.1 M HNO3 solution, and deio-
nization to desorb Zn2+ adsorbed on GO and found the desorption ef-
ficiency were 91.6 %, 73.4 %, and 53.2 %, respectively [69].
3.4.2. Regeneration in alkali solution
The alkali-method is similar to the acid-method, which regenerate
C. Duan, et al.
carbon-based materials by immersing. Ma et al. [46] found that after
the first regeneration of BC in 1 M NaOH solution, the adsorption ef-
ficiency of Cr(VI) decreased from 97.9% to 91.57%, and after three
adsorption-desorption cycles, the adsorption rate of Cr(VI) reached
70.65 %. Samuel et al. [61] used 1 M NaOH as desorption reagent to
regenerate GO/chitosan. After 10 adsorption-desorption cycles, the
adsorption capacity of Cr(VI) decreased slightly, and the removal effi-
ciency decreased from 96 % to 82 %. In addition to NaOH, Yu et al.
successfully regenerated ZnO/BC composite with dilute ammonia
water, and the adsorption efficiency of Cr(VI) was 67.1 % after 5 ad-
sorption-desorption cycles [80]. Actually, NaOH solution is used more
frequently than dilute ammonia solution in alkali-method regeneration,
and the regeneration research of other alkali solutions for carbon-based
is inadequate.
Acid-method and alkali-method are main strategies to regenerate
carbon-based materials. Although EDTA [69] and Na2EDTA [115] were
also used to respectively regenerate GN and GO, there are few related
studies. In addition to solvent regeneration methods such as acid and
alkali, in-situ regeneration technology such as catalysis can also be
considered [119]. The regeneration method with high desorption rate,
cheap desorption reagent, simple regeneration process and suitable for
industrial application needs to be developed.
4. Conclusion and outlook
AC/BC, CNTs, and GN analogues are three typical carbonaceous
materials which are used to develop carbon-based adsorbents. For
carbon-based adsorbents, surface complexation, ion exchange, and
electrostatic interaction are main mechanisms for heavy metal removal,
and pH play a key role in adsorption. The Langmuir or Freundlich ad-
sorption isotherms often have better fitness than other models in studies
of carbon-based adsorbents, so they have been applied in more cases.
The pseudo-first-order and the pseudo-second-order kinetic model are
also universal, and the latter is more common. For desorption, acid-
method and alkali-method still are main strategies to regenerate
carbon-based adsorbents. Though adsorption mechanism, modification,
and regeneration have been studied in some literatures for removing
heavy metal from aqueous solution, there still are some issues:
（1） Current researches on the adsorption and removal of various
heavy metals in water mostly focus on the heavy metal cation,
but few specific adsorption studies of their hydroxy compound
ions or other complex ions; usually, the adsorption of complex
Appendix A
Table A1
Several heavy metal removal technologies in water.
Technologies Advantages
Chemical precipitation - Easy operation and high degree of selectivity
[53,116] - Precipitants are relatively inexpensive
Electrochemical treatment - Rapid and well-controlled process with less sludge
[13] - Fewer chemicals are required
Ion exchange - Fast kinetic
[13,116] - High sorption capacity
- Resin can be regenerated
Adsorption - Easy operation, low cost and high sorption capacity
[22,116] - Wide selection of adsorbents
- Adsorbents can be regenerated
Membrane filtration - High degree and efficient of selectivity for removing heavy
[13,22,117,118] metal ions
- Space saving
10
Journal of Water Process Engineering 37 (2020) 101339
ions is mentioned as a small part in documents.
（2） On the one hand, the modified carbonaceous materials can
achieve high adsorption capacity and removal efficiency of
heavy metals; on the other hand, the modification operation is
complex, especially chemical modification. Considering the cost,
yield and/or operation complexity, these preparation methods of
modified materials are not conducive to industrial production,
and some new modifiers may also bring new pollutions.
（3） Many carbon-based materials are powders. Even after magneti-
zation, they may migrate and lose in the water with strong
fluidity, resulting in lower recovery rate and secondary pollu-
tion.
（4） Current regeneration of acid or alkali used in carbon-based ma-
terials will cause mass loss, strength reduction and adsorption
capacity reduction, which need to be further optimized; while
other regeneration methods are lack of systematic research. In
addition, waste desorption reagent treatment is also need to be
studied.
Given the above issues, more attention should be paid to the fol-
lowing directions. The selective adsorption and the competitive ad-
sorption behavior among heavy metal ions are worth to further study.
The combination and simplification of modification operations can
make the industrial large-scale production of carbon-based adsorbents
come true, which meet actual cases better but with lower cost. In order
to facilitate the collection and prevent secondary pollution, 3D GN, GO
sponge, and other new carbon-based materials with three-dimensional
structure are prospective heavy metal adsorbents. As for regeneration,
the properties of carbon-based materials, operation conditions of re-
generation process, and the development of desorption solution, are
significant and practical in future research, for making full use of
carbon-based adsorbents.
Declaration of Competing Interest
None.
Acknowledgements
This work was financially supported by the National Natural Science
Foundation of China (51778230) and National key research and de-
velopment program (2017YFB06026).
Disadvantage
-A large amount of precipitate agents is needed
- Chemical stabilization of precipitant is needed with high cost and secondary
pollution is possible
- High initial capital investment
- Expensive electricity supply
- Only suitable for low concentration of metals
- Highly sensitive to pH
- Chemicals are required for regenerating resin
- Secondary pollution
- Expensive
- Adsorption efficiency and capacity depend on the type of adsorbents.
- Synthesis processes of some adsorbents are high costed
- External pressure is required in operation process
- High cost of operation and membrane maintaining
C. Duan, et al. Journal of Water Process Engineering 37 (2020) 101339

Table A2
Different carbon-based adsorbents for heavy metal removal.
Adsorbent Heavy metal Temperature (K) pH Adsorption capacity (mg/g) Reference

Rice husk carbon Cr(VI) 295 2 47.61 [50]

Corn straw porous carbon Cr(VI) 298 3 175.44 [46]
Water hyacinth BC Cd(II) 298 70.3 [56]
Oxidized MWCNTs Pb(II) 298 7−10 2.67−11.70 [37]
Thiol-derivatized SWCNT Hg(II) 298 5 131 [57]
Magnetic MWCNT Hg(II) 298 2 238.78 [58]
rGO Pb(II) 303 4.5 [60]
GO-chitosan composite Cr(VI) 300 2 104.16 [61]
As(III) 298 7.3 45 [38]
β-cyclodextrin modified magnetic GO Pb(II) 298 4−7 279.21 [62]
Cu(II) 298 51.29
β-cyclodextrin/ethylenediamine/magnetic GO Cr(VI) 303 2.5 89.5 [63]
GO-MgO nanohybrid Pb(II) 303 6.5 190 [64]
nZVI-rGO composites As(III) 303 4-10 35.83 [65]
As(V) 2 20.94

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