Chemosphere 195 (2018) 351e364

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

A review of functionalized carbon nanotubes and graphene for heavy

metal adsorption from water: Preparation, application, and
mechanism
Jiang Xu a, b, Zhen Cao a, Yilin Zhang b, Zilin Yuan b, Zimo Lou c, Xinhua Xu c, *,
Xiangke Wang d
a
State Key Laboratory of Estuarine and Coastal Research, East China Normal University, Shanghai, 200062, China
b
Department of Civil and Environmental Engineering, Carnegie Mellon University, Pittsburgh, 15213, USA
c
Department of Environmental Engineering, Zhejiang University, Hangzhou, Zhejiang 310058, China
d
School of Environment and Chemical Engineering, North China Electric Power University, Beijing, 102206, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Removal of heavy metals from water

has drawn wide attention.

Various functionalized carbon nano-
tube and graphene nanomaterials
were stated.

Effects of water environmental
chemistry on heavy metals removal
were discussed.

Adsorption isotherms, kinetics, ther-
modynamics, and pathways were
discussed.

Some research prospects were pro-
posed for future studies and
application.

a r t i c l e i n f o a b s t r a c t

Article history: Carbon-based nanomaterials, especially carbon nanotubes and graphene, have drawn wide attention in
Available online 19 December 2017 recent years as novel materials for environmental applications. Notably, the functionalized derivatives of
Handling Editor: Chang-Ping Yu
carbon nanotubes and graphene with high surface area and adsorption sites are proposed to remove
heavy metals via adsorption, addressing the pressing pollution of heavy metal. This critical revies as-
sesses the recent development of various functionalized carbon nanotubes and graphene that are used to
Keywords:
Heavy metals remove heavy metals from contaminated water, including the preparation and characterization methods
Functionalized of functionalized carbon nanotubes and graphene, their applications for heavy metal adsorption, effects
Carbon nanotube of water chemistry on the adsorption capacity, and decontamination mechanism. Future research di-
Graphene rections have also been proposed with the goal of further improving their adsorption performance, the
Adsorption feasibility of industrial applications, and better simulating adsorption mechanisms.
© 2017 Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: [email protected] (X. Xu).

https://doi.org/10.1016/j.chemosphere.2017.12.061
0045-6535/© 2017 Elsevier Ltd. All rights reserved.
352 J. Xu et al. / Chemosphere 195 (2018) 351e364

List of acronyms nZVI Nanoscale zero-valent iron

DES Deep eutectic solvents
AA Activated alumina OMC Ordered mesoporous carbon
LDH Layered double hydroxide DFT Density functional theory
AC Activated carbon PAA Polyacrylic acid
M-CHAP magnetic carbonate hydroxyapatite EDA Ethylenediamine
BET Brunauer-Emmett-Teller PANI Polyaniline
MC-N magnetic carbon-iron reduced by Fe(NO3)3 Fe2O3 Maghemite
CB[6] Cucurbit[6]uril RGO Reduced graphene oxide
MC-O magnetic carbon-iron reduced by Fe3O4 GO Graphene oxide
CMK Nanoporous carbons SMG Smart magnetic graphene
MIO Magnetic iron oxide HA Humic acid
CMPEI Carboxymethylated polyethyleneimine VP 2-vinylpyridine
MPTS Mercaptopropyltriethoxysilane HEG Hydrogen exfoliated graphene
CNTs Carbon nanotubes WHO World Health Organization
MWCNTs Multi-walled carbon nanotubes HMO Hydrous manganese dioxide
CS Chitosan XPS X-ray photoelectron spectroscopy
NPs Nanoparticles IL Ionic liquid
DBSA Dodecyl-benzene-sulfonic-acid

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 352
2. Functionalized carbon nanotubes and graphene: preparations and structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
2.1. Preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
2.2. Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
3. Applications of functionalized carbon nanotubes and graphene for aqueous heavy metal adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
3.1. Adsorption of four most concerned heavy metals (Hg, Pb, Cr, and Cd) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
3.2. Adsorption of aqueous As(III)/(V) and other heavy metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
4. Effects of water environmental chemistry on heavy metal removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
4.1. Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
4.2. pH value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 357
4.3. Ionic strength and coexisting ions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
5. Mechanism of heavy metal removal by functionalized carbon nanotubes and graphene nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
5.1. Adsorption isotherms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
5.2. Adsorption kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
5.3. Adsorption thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
5.4. Other pathways that accompany adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
6. Future research prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
6.1. Functional nanomaterials for treating combined pollution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
6.2. Sustainability of nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
6.3. Computational simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
6.4. Other recommendations for future research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 360
7. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 361

1. Introduction estimated by the World Water Council. As a result of rapid de-

velopments in urbanization, industrialization, and agricultural ac-
Water is the most essential and important component for living tivities, the removal of heavy metals from contaminated waters has
beings on Earth. In the last century, anthropogenic water demand become a major environmental concern. Many metals are essential
has increased sevenfold due to the quadrupled global population nutrients in trace amounts, but become significant threats to
(Pendergast and Hoek, 2011). Approximately 2.6 billion people environmental and human health at high concentrations. Heavy
have gained access to an improved drinking water source since metals are non-biodegradable and can accumulate in the envi-
1990, while 663 million people still lack improved drinking water ronment and living organisms (Hashim et al., 2011; Xu et al., 2017a,
sources in 2015, according to the report of “Progress on Sanitation b). Neurological, mental, and other various adverse effects are
and Drinking Water-2015 Update and MDG Assessment” by the caused by exposure to, transportation of, and accumulation of
World Health Organization (WHO). The number of people living in heavy metals, especially Hg(II), Pb(II), Cr(VI), Cd(II), and As(III)/(V)
water scarce regions will increase to about 3.9 billion by 2030, as (Meng et al., 2014; Sima et al., 2015; Dong et al., 2017; Rehman et al.,
 J. Xu et al. / Chemosphere 195 (2018) 351e364 353

Table 1 silica, titanium dioxide, chitosan, and polymer (George et al., 2016;
Maximum acceptable level of selected heavy metal ions in drinking water in Huang et al., 2016; Lv et al., 2012; Morillo et al., 2015; Vunain et al.,
different countries (mg L1).
2016; Yurekli, 2016). However, pure nanomaterials have some
Heavy metals WHO E.U. U.S. Canada Australia Japan China limitations, and carbon-based nanocomposites or nanohybrids
Hg 6 1 2 1 1 0.5 1 with more and controlled functionalities are attracting attention for
Pb 10 10 15 10 50 50 10 environmental applications (Chang and Wu, 2013; Sun and Xu,
Cr 50 50 100 50 50 50 50 2014). Scientific and technological research face challenges with
Cd 3 5 5 5 2 10 5
the durability, functionality, and performance of advanced nano-
As 10 10 10 25 7 10 10
materials, which are increasingly important in environmental ap-
plications (Chabot et al., 2014).
Over the past decade, nanomaterials with multiple functions
2017). As shown in Table 1, the maximum allowable concentrations
have been rapidly developed through academic pursuit based on
of these five heavy metal ions in drinking water have been strictly
commercial realities. The concepts of functionalization at the
set by the WHO and many countries. The availability of freshwater
nanoscale level have already led to new aqueous heavy metal
is an important issue for human health and social development
treatments with state-of-the-art performance parametersdrapid
(Machell et al., 2015).
removal, high capacity, good selectivity, easy separation, and
Much work has been carried out on the removal of aqueous
satisfactory reusability. Based on the potential advantages of
heavy metals by various methods, including adsorption, filtration,
functionalized CNTs and graphene, we present a brief overview of
precipitation, reduction, ion exchange, and electrochemical
various functionalized CNTs and graphene that are used to adsorb
removal (Xu et al., 2013c, 2016c; Xiao et al., 2016; Huang et al., 2017;
heavy metals from contaminated water, and mainly focus on their
Sounthararajah et al., 2017; Sun et al., 2017; Xu et al., 2017b). The
applications and mechanisms for adsorption of heavy metals.
general advantages and disadvantages of commonly used methods
Meanwhile, the effects of water environmental chemistry on their
for the removal of aqueous heavy metals are given in Fig. 1. Of these
adsorption behaviors are also discussed. In Section 6, we propose
methods, adsorption is more versatile and widely used for the
some interesting research prospects in the field of functionalized
removal of aqueous heavy metals. It has many advantages, such as
nanomaterials.
simple operation, low cost, good pH tolerance, and large industrial
processing capacity. In addition, high efficiency and selectivity can
2. Functionalized carbon nanotubes and graphene:
also be achieved via purposeful functionalization. A simple and
preparations and structures
cheap method that does not require a large investment or energy
inputs is desirable for wastewater treatment.
2.1. Preparations
Nanomaterials are currently on the cutting edge of material
science research and are gradually finding applications in our daily
Due to the non-corrosive property, tunable surface chemistry,
life, including life science, energy, and environmental applications.
high surface area, and presence of surface oxygen-containing
Carbon nanomaterials, with their high specific surface areas and
functional groups, carbon nanotubes and graphene materials
large pore volumes, have remained at the forefront of nanotech-
have been chosen as platforms to build new adsorbents with
nology. Many forms, especially carbon nanotubes (CNTs) and gra-
enhanced or more functions (Perreault et al., 2015). Functionali-
phene, have been widely used to remove aqueous Hg(II), Pb(II),
zation of CNTs and graphene for environmental applications are
Cr(VI), Cd(II), As(III)/(V), Co(II), U(VI), and other metal ions (Mauter
mostly fabricated via chemical methods, including purely chemical
and Elimelech, 2008; Zhao et al., 2011a, b; Tian et al., 2012; Liu et al.,
processes (i.e., chemical oxidation and deposition) and extended
2013b; Perreault et al., 2015; Ihsanullah Abbas et al., 2016). Based
chemical process (i.e., electrochemical, sol-gel, microemulsion, and
on the high surface area, scalable production, tunable surface
hydrothermal methods) (Cho et al., 2010; Khin et al., 2012). These
chemistry, non-corrosive property, and presence of surface oxygen-
methods usually contain a precursor of chemical reductant or
containing functional groups of CNTs and graphene nanomaterials,
photoreductant for nanomaterial generation, and a supportive,
the adsorption performance are generally better than other con-
stabilizer, or additive agent for obtaining the desired function
ventional adsorbents, such as zero valent iron, iron oxide, zeolite,
(Parambhath et al., 2011; Ojani et al., 2014). Chemical reactions are
more selective and straightforward than other processes, and can
integrate functional groups with carbon nanomaterials to obtain
multiple functions (Zhao et al., 2011a, b). Some typical methods for
functionalization of CNTs and graphene are shown in Table 2. After
preparation, characterization is an indispensable procedure to
obtain the micromorphology, chemical composition, surface area,
surface functional groups, and other properties of the nano-
materials, especially focusing on the difference between raw and
functionalized CNTs and graphene. Characterizations provide
important support for understanding the mechanisms involved.

2.2. Structures

Carbon-based nanomaterials have great potential for use in

water treatment, and should be designed to obtain suitable struc-
tures and properties. Therefore, the deliberate design of the
structures and properties of nanomaterials is usually performed
with the intention of obtaining synergistic multi-functionalities or
solving a specific problem. The properties of nanomaterials are not
Fig. 1. Common methods for the removal of aqueous heavy metals. only size dependent, but also structure dependent. Supported,
 354
Table 2
Chemical synthesis methods for various functionalized nanomaterials.

Nanomaterial Method Ref.

Oxidized MWCNTs Simple chemical reaction: (Vukovi

c et al., 2010)
H2 SO4 : HNO3 ð3:1Þ filtered
MWCNTs











!




! oxidized MWCNTs
sonicated;3h;40o C dried

J. Xu et al. / Chemosphere 195 (2018) 351e364

NH2-MWCNTs Simple chemical reaction: (Vukovi
c et al., 2011)
EDA;NHATU filtered

! NH2  MWCNTs
oxidized MWCNTs











!



sonicated;4h;40o C dried

CNTs-FeS Chemical vapor deposition: (Ma et al., 2015)

ethanolþferroceneþthiophene oxidation1h reduction1h sulfur powder filtered










!








!
o
CNTs  Fe2 O3










!










!

! CNTs  FeS
argon flow;pyrolysis air flow;400 C argon flow;900o C argon flow;600o C washed

Bare GO Hummers method: (Hummers and Offeman, 1958)

NaNO3 ;H2 SO4 ;66o C KMn O4 ; < 20o C
Graphite powder























!

















!
vigorous agitation vigorous agitation;ice bath
35±3o C;30min diluted 3% H2 O2 treating









!







!














! GO
vigorous agitation 98o C;15min filtered;washed;dispersed

Sulfur-RGO Green one-step method: (Thakur et al., 2013)

Na2 S2 O3 ;sonicated;1h disproportionation;30min
GO






















!












! S  RGO
Citrus limonjuice;acidic sonicated;washed;dried

PB-GO Modified Hummers method: (Xu et al., 2008)

K2 S2 O8 ;P2 O5 ;H2 SO4 diluted with DI water
Graphite powder





































o

!














!
hotplate;80 C room temperature;overnight
filtered;washed H2 SO4 ;0o C;KMnO4 stirred2h








!






















!



!
dried;overnight stirring;icebath; < 20o C
o 35 C
diluted;stirred2h 30%H2 O2 treating









!















! GO
ice bath; < 50o C filtered;washed;dispersed
 J. Xu et al. / Chemosphere 195 (2018) 351e364 355

coated, grafted, core-shell, and multiple modification types are 2014). MC-N and MC-O were used to remove Cr(VI) through
common structures of functionalized CNTs and graphene nano- reduction and precipitation, and the nanomaterials could be easily
materials for aqueous heavy metal removal. separated by a permanent magnet following the reaction.
The surfaces of carbon nanomaterials always contain some In recent years, many studies have focused on magnetic nano-
functional groups, which play an important role in the adsorption composites, which have some excellent advantages, with their low
process. Thus, many studies have been performed to further in- cost, environmentally friendly composition, mesoporous nano-
crease the abundance of pre-existing functional groups (such as structure with a large surface area for rapid adsorption, and easy
COOH and OH) or graft other functional groups (such as NH2 and magnetic retrieval by an external magnetic field for recycling (Han
SH) onto the surface of carbon nanomaterials as a way to enhance et al., 2009; Xu et al., 2013b; Wang et al., 2010). Generally, magnetic
their adsorptive capacities (Vukovi c et al., 2010; El-Sheikh et al., functionalized nanomaterials are prepared to remove heavy metals
2011; Hadavifar et al., 2014). Additional performance can be ob- and then are retrieved by magnetic separation (Fig. 2a), which is a
tained by coating the carbon nanomaterials with other nano- very effective way to recycle the nanomaterials and avoid envi-
particles (NPs); The carbon-supported nanomaterials are generally ronmental risks that could result from their release (Wang et al.,
porous and stable, with large specific surface area and good 2016). In addition, magnetic carbon materials have also been
adsorptive capacities (Lv et al., 2011; Xu et al., 2012b; Tang et al., developed to capture other functionalized nanomaterials that used
2016). to remove heavy metals. A typical example is presented in Fig. 2b
The core-shell is a novel structure in materials chemistry, and (Shih et al., 2014). Tween 20 functionalized Au NPs were used to
has been attracting increasing attention due to its many applica- remove aqueous Hg(II) from a high-salt matrix (artificial seawater)
tions in biomedicine, catalysis, electronics, pharmaceuticals, and by reducing Hg2þ to Hg0. The Hg0 then deposited onto the surfaces
environmental pollution control. Core-shell carbon-based nano- of the Tween 20-Au NPs. After the reaction, magnetic and reduced
materials usually consist of an inner material (core) and an outer graphite-Fe3O4 NPs were used to collect the Tween 20-Au NPs, and
material (shell). Different combinations of materials have been the mixture was further retrieved by a second magnetic field.
produced and tested, such as Fe3O4@C, RGO@Al2O3, C@Si, and
CNT@C (Cui et al., 2009; Hahm et al., 2013; Du et al., 2014; Yao et al.,
2015; Jastrze˛ bska et al., 2016). However, most of these carbon-
based core-shell nanomaterials are used as high-capacity elec- 3.2. Adsorption of aqueous As(III)/(V) and other heavy metals
trodes, and the applications for aqueous heavy metal removal still
needs to be studied. As a metalloid element, arsenic (As) contamination of ground-
Additionally, more complex nanocomposites have also been water is affecting millions of people globally, and can cause serious
fabricated to remove aqueous heavy metals. CNTs and graphene health problems, such as bladder, lung, and skin cancer (Mishra and
nanomaterials are extensively modified to have multiple proper- Ramaprabhu, 2010). The sources of As, the 12th and 20th element
ties, such as redox ability to change the form of a heavy metal, in order of natural abundance in the human body and the Earth's
magnetic properties for easy separation and recycling of the crust, respectively, are both naturally occurring (in rock and min-
nanomaterials, and enhanced adsorptive capacity. eral erosion, volcanic activity, and forest fires) and anthropogen-
ically produced. As has 4 valence states (3, 0, þ3, and þ5). As(III)
(arsenite) and As(V) (arsenate) are the predominant species of As in
3. Applications of functionalized carbon nanotubes and water, and As(III) is much more soluble, mobile, and toxic than
graphene for aqueous heavy metal adsorption As(V) (Shih, 2005). Hence, an oxidation process of As(III) to As(V) is
usually required.
3.1. Adsorption of four most concerned heavy metals (Hg, Pb, Cr, With the development of nanotechnology, functional nano-
and Cd) materials have been widely synthesized for effective As removal
(Table 3). Iron oxide NPs have commonly been used to remove
Mercury (Hg), Lead (Pb), Chromium (Cr), and cadmium (Cd) are aqueous As, with an adsorptive capacity for mixed Fe3O4 and Fe2O3
regarded as four of the most concerned heavy metals, which are of 5.99 mg g1 (Chowdhury et al., 2010). Because this capacity was a
non-biodegradable, bioaccumulative, and extreme hazardous. bit low, carbon materials with oxygen-containing groups were then
Serious threats to plant, animal, and human health are caused by induced to support the iron oxides and improve their adsorptive
these heavy metals, even at trace levels concentration (Akhavan capacity. The maximum adsorptive capacities of As(III) and As(V) by
et al., 2015; Boening, 2000; Cutting et al., 2010; Gardarin et al., the CNTs-base iron oxides were 24.05 mg g1 and 47.41 mg g1,
2010; Lavoie et al., 2015; Zhu et al., 2012). Table 3 shows various respectively (Chen et al., 2014a).
functionalized CNTs and graphene nanomaterials that have been Since the oxidation rate of As(III) by Mn(IV) complexes was
used for the adsorption of aqueous heavy metals. significantly higher than that by Fe(III) complexes, GO-MnFe2O4
Generally, the interaction between metal ions and the surface nanohybrids were fabricated. The BET surface areas of GO-MnFe2O4
oxygen-containing groups plays an important role in adsorption nanohybrids and bare MnFe2O4 nanohybrids were 196 m2 g1 and
capacity of heavy metals on CNTs and graphene based nano- 91 m2 g1, respectively (Kumar et al., 2014). The adsorptive ca-
materials. As shown in Table 3, the raw CNTs materials usually pacities of As(III) and As(V) by GO-MnFe2O4 nanohybrids were
require acid or oxidation treatments to increase their surface greatly improved, to 146 mg g1 and 207 mg g1, respectively,
oxygen-containing functional groups, while no additional acid or which was much higher than GO NPs in the absence of Mn(IV)
oxidation treatments are required for graphene, because the as- complexes (Mishra and Ramaprabhu, 2011; Paul et al., 2015; Ray
prepared graphene material already possesses a large number of and Shipley, 2015).
oxygen-containing functional groups (Zhao et al., 2011a, b). In addition to the five heavy metals of concern mentioned
Note that the toxicity of Cr(VI) is much higher than that of Cr(III), above, other heavy metals have also been studied due to their wide
and reduction processes have been required before adsorption or industrial use and the threats they pose to humans and ecosystems.
precipitation. For example, functional magnetic carbon-iron nano- Other heavy metals that have been studied for removal by func-
adsorbents were prepared by carbonizing cellulose and reducing tionalized carbon-based nanomaterials include Cu(II), Zn(II), Ni(II),
Fe(NO3)3 or Fe3O4 NPs (MC-N and MC-O, respectively) (Qiu et al., Co(II), and radioactive U(VI) (Table 3).
356 J. Xu et al. / Chemosphere 195 (2018) 351e364

Table 3
Functionalized carbon-based nanomaterials used for aqueous heavy metals removal.

Nanomaterial BET (m2 g1) pH Capacity (mg g1) Ref.

Exp. Cal.

Hg(II)
oxidized MWCNTs N/A 7.0 N/A 3.8 El-Sheikh et al., 2011
MWCNTs-COOH N/A 4.3 81.6 127.6 Chen et al., 2014b
MWCNTs-OH N/A 4.3 89.4 120.1 Chen et al., 2014b
SWCNTs-SH N/A 5.0 74.2 131.6 Bandaru et al., 2013
MWCNTs-iodide 153.0 6.0 100.0 123.5 Gupta et al., 2014
MWCNTs-S 155.3 6.0 100.0 151.5 Gupta et al., 2014
CNTs-MnO2 110.4 6.0 14.3 58.8 Moghaddam and Pakizeh, 2015
KMnO4-DES-CNTs 199.4 5.5 187.0 250.5 AlOmar et al., 2017
CS-MWCNTs-COOH N/A 4.0 183.2 181.8 Shawky et al., 2012
CS-MWCNTs N/A 4.0 167.5 169.4 Shawky et al., 2012
MWCNTs/Fe3O4-SH 97.2 6.5 63.7 65.5 Zhang et al., 2012
Tween 20-Au/graphite-Fe3O4 N/A N/A N/A 47.6 Shih et al., 2014
Pb(II)
MWCNTs N/A 6.0 N/A 15.9 Ren et al., 2011
Acidified MWCNTs 237.3 5.0 85.0 49.7 Wang et al., 2007a
MWCNTs-VP N/A 6.0 N/A 37.0 Ren et al., 2011
MWCNTs-TiO2 N/A 6.0 4.6 137.0 Zhao et al., 2010
CNTs-MnO2 275.0 5.0 N/A 78.7 Wang et al., 2007b
SWCNTs-COOH 400.0 5.0 N/A 94.7 Moradi, 2011
CNTs/Fe3O4-NH2 90.7 5.3 37.6 75.0 Ji et al., 2012
CNTs/Fe3O4-MPTS 97.2 6.5 42.1 65.4 Zhang et al., 2012
GO 430.0 6.8 328.0 367.0 Madadrang et al., 2012
EDTA-GO 623.0 6.8 479.0 525.0 Madadrang et al., 2012
EDTA-RGO 730.0 6.8 204.0 228.0 Madadrang et al., 2012
GO-MnFe2O4 196.0 5.0 N/A 673.0 Kumar et al., 2014
RGO-nZVI N/A 5.0 550.0 585.5 Jabeen et al., 2013
CoFe2O4-GO 212.7 N/A 81.3 82.3 Ma et al., 2015
M-CHAP/GO 106.0 4.5 244.5 246.1 Cui et al., 2015
HMO@GO 383.9 5.0 553.6 512.6 Wan et al., 2016
a
SMG 165.0 6.5 N/A 6.0 Gollavelli et al., 2013
Cr(VI)
IL-oxi-MWCNTs 87.4 3.0 2.6 85.8 Krishna Kumar et al., 2015
CNTs-CeO2 N/A 7.0 30.2 31.6 Di et al., 2006
DBSA-PANI/MWCNTs N/A 2.0 49.5 55.6 Kumar et al., 2013
AC-CNTs 755.8 2.0 9.0 8.6 Atieh, 2011
AA-CNTs 203.0 2.0 142.8 264.5 Sankararamakrishnan et al., 2014
NH2-Fe3O4/GO 43.6 4.5 27.3 32.3 Liu et al., 2013a
MC-N 136.3 1.0 327.5 N/A Qiu et al., 2014
a
SMG 165.0 6.5 N/A 4.9 Gollavelli et al., 2013
Cd(II)
Raw MWCNTs 187.6 8.0 1.29 1.3 Vukovi c et al., 2010
oxidized MWCNTs 78.5 8.0 22.32 22.4 Vukovi c et al., 2010
EDA-MWCNTs 101.2 8.0 21.23 21.7 Vukovi c et al., 2010
Al2O3 MWCNTs 109.8 7.0 0.948 27.2 Liang et al., 2015
SWCNTs 400.0 5.0 N/A 21.2 Moradi, 2011
COOH-SWCNTs 400.0 5.0 N/A 55.4 Moradi, 2011
oxidized CNTs 128.0 5.5 N/A 11.0 Li et al., 2003
AA-CNTs 203.0 7.5 200.0 229.9 Sankararamakrishnan et al., 2014
As(III)
Iron oxide-MWCNTs N/A 8.0 1.8 4.0 Tawabini et al., 2011
Fe3O4-MWCNTs 70.1 N/A N/A 53.2 Mishra and Ramaprabhu, 2010
Fe-MWCNTs N/A 7.0 210.0 200.0 Alijani and Shariatinia, 2017
EDA-MWCNT/Fe2þ 198.5 8.0 0.7 N/A Veli
ckovic et al., 2012
MIO-MWCNTs 209.8 7.0 17.2 20.2 Chen et al., 2014a
GO-MnFe2O4 196.0 6.5 N/A 146.0 Kumar et al., 2014
Fe3O4-RGO 148 7.0 N/A 13.1 Chandra et al., 2010
HA-RGO-Fe3O4 0.9 7.0 7.5 8.7 Paul et al., 2015
HEG-electrodes 442.9 6.1 N/A 138.8 Mishra and Ramaprabhu, 2011
GAC-ZrO2 903.0 7.6 N/A 12.2 Sandoval et al., 2011
b
MWCNTs-ZrO2 152.0 6.0 9.8  102 2.0 Addo Ntim and Mitra, 2012
b
Fe3O4-MWCNTs 153.0 4.0 9.7  102 1.7 Addo Ntim and Mitra, 2011
As(V)
Fe3O4-MWCNTs 70.1 N/A N/A 39.1 Mishra and Ramaprabhu, 2010
MIO-MWCNTs 209.8 7.0 36.3 40.8 Chen et al., 2014a
Fe-MWCNTs N/A 7.0 220.0 200.0 Alijani and Shariatinia, 2017
GO-MnFe2O4 196.0 4.0 N/A 207.0 Kumar et al., 2014
GO-Fe(OH)3 N/A 4.0 23.8 N/A Zhang et al., 2010
Fe3O4-RGO 148 7.0 N/A 5.83 Chandra et al., 2010
HA-RGO-Fe3O4 0.9 7.0 16.0 61.7 Paul et al., 2015
HEG-electrodes 442.9 6.9 N/A 141.9 Mishra and Ramaprabhu, 2011
Mg-Al LDHs/GO 35.4 5.0 183.1 180.3 Wen et al., 2013
b
MWCNTs-ZrO2 152.0 6.0 0.1 5.0 Addo Ntim and Mitra, 2012
 J. Xu et al. / Chemosphere 195 (2018) 351e364 357

Table 3 (continued )

Nanomaterial BET (m2 g1) pH Capacity (mg g1) Ref.

Exp. Cal.
b
EDA-MWCNT/Fe2þ 198.5 4.0 1.0 18.1 Veli
ckovic et al., 2012
b
Fe3O4-MWCNTs 153.0 4.0 0.1 0.2 Addo Ntim and Mitra, 2011
a
SMG 165.0 6.5 N/A 3.3 Gollavelli et al., 2013
Cu(II)
Oxidized CNTs N/A 7.0 50.4 64.9 Tofighy and Mohammadi, 2011
Purified MWCNTs 169.7 5.0 37.5 36.8 Ge et al., 2014
Oxidized MWCNTs N/A 5.0 29 28.5 Li et al., 2003
Sulfonated MWCNTs 28.7 5.0 59.6 43.2 Ge et al., 2014
OH-MWCNTs 111.4 4.9 7.0 10.1 Rosenzweig et al., 2013
COOH-MWCNTs 135.2 4.9 5.5 8.1 Rosenzweig et al., 2013
SWCNTs 400.0 5.0 N/A 22.9 Moradi, 2011
COOH-SWCNTs 400.0 5.0 N/A 72.3 Moradi, 2011
OH-SWCNTs/RGO N/A 6.8 N/A 256.0 Dichiara et al., 2015
COOH-SWCNTs/RGO N/A 6.8 N/A 63.0 Dichiara et al., 2015
MWCNTs/Fe3O4 138.7 5.5 19.0 38.9 Tang et al., 2012
Zn(II)
Oxidized CNTs N/A 7.0 58.0 74.6 Tofighy and Mohammadi, 2011
Purified SWCNTs 423.0 N/A 15.4 41.8 Lu et al., 2006
Oxidized MWCNTs 250.0 6.5 2.0 1.1 Mubarak et al., 2013
Ni(II)
MWCNTs 197.0 5.4 2.9 3.7 Yang et al., 2009
PAA-MWCNTs N/A 5.4 N/A 3.9 Yang et al., 2009
Oxidized MWCNTs 102.0 6.5 12.5 17.9 Mobasherpour et al., 2012
Co(II)
Oxidized CNTs N/A 7.0 69.6 85.7 Tofighy and Mohammadi, 2011
MWCNTs/iron oxide N/A 6.4 2.9 10.6 Wang et al., 2011
U(VI)
CB[6]/GO/Fe3O4 N/A 5.0 N/A 122.5 Shao et al., 2016
Fe3O4/GO N/A 5.5 N/A 69.5 Zong et al., 2013
Amidoximated Fe3O4/GO N/A 5.0 76.88 92.4 Zhao et al., 2013
CMPEI/CMK 1350.0 4.0 N/A 151.5 Jung et al., 2008
a
Trace ions removal of 0.1e5.0 mg L1.
b
Trace ions removal of 100 mg L1.

4. Effects of water environmental chemistry on heavy metal spontaneous and more efficient at higher temperatures (Jin et al.,
removal 2015). The increased temperature not only increases the number
of available active surface sites on the nanomaterials and reduces
4.1. Temperature the thickness and mass transfer resistance of the boundary layer
surrounding the nanomaterials; it also allows the ions to be more
Temperature is a very common parameter affecting physico- readily desolvated for removal from the aqueous phase (Gupta and
chemical reactions and has significant impacts on the adsorption of Rastogi, 2008). However, in a reaction with low activation energy,
heavy metals. The reaction rate increases with increasing temper- diffusion is not the rate limiting step, and the temperature effects
ature for endothermic reactions, and decreases with increasing will be insignificant. In the case of exothermic reactions, negative
temperature for exothermic reactions. DG0 values increase with increasing temperature, while negative
Generally, higher temperature will reduce the mass transfer values of DH0 for Hg(II) adsorption onto MWCNTs-SH indicate that
resistance and accelerate diffusion. Pb(II), As(III), and As(V) the adsorption was more efficient at lower temperatures (Hadavifar
adsorption by MnFe2O4 and GO-MnFe2O4 NPs were enhanced by et al., 2014).
increased temperature (Kumar et al., 2014). The calculated DG0
values were all negative and decreased with increased tempera-
4.2. pH value
ture, which also indicates that the adsorption process was

Since the pH of the solution will affect the ionic forms of heavy
metal ions and functionalized nanomaterials, pH is an important
parameter for aqueous heavy metal removal. For example, K2Cr2O7
can be dissolved in different ionic forms at different pH values.
H2CrO4 is the dominant species at pH < 1.0, while HCrO 4 and
Cr2O2 2
7 are predominant at pH 2.0e6.0, and CrO4 is dominant at
pH > 6.0 (Wang et al., 2015a). Aqueous Pb species usually exist as
Pb2þ, Pb(OH)þ, Pb(OH) 3 , or Pb(OH)2 at different pH values. Spe-
cifically, Pb2þ is the dominant species when pH < 7.0, while
Pb(OH)2 forms and becomes the major species when pH > 8.0
(Vukovi c et al., 2011). Most of the Hg(II) species exist as Hg2þ in
strongly acidic conditions, while HgOHþ and Hg(OH)2 are the main
forms in the pH range of 3.0e8.0, and Hg(OH)2 precipitate is pre-
Fig. 2. Schematic of the (a) retrieval of magnetic nanomaterials and (b) capture of NPs dominant as pH > 8.0 (Wang et al., 2016). As(V) species usually
by magnetic carbon-based nanomaterials. exists in solution as H3AsO4, H2AsO 2
4 , and HAsO4 . The HAsO4
2
358 J. Xu et al. / Chemosphere 195 (2018) 351e364

species is predominant when pH > 7.0, whereas H2AsO 4 is the observed, because the inner-sphere complexation between HMO
major species when pH < 7.0, and H3AsO4 is present at most pH sites and Pb(II) is specific, while the electrostatic interactions be-
conditions (Lin and Wu, 2001). For As(III), the nonionic H3AsO3 and tween Pb(II) species and the oxygen-containing groups on GO is
anionic H2AsO 3 are the dominant forms when pH < 9.0 and nonspecific. Hence, purposeful design of functional nanomaterials
pH > 9.0, respectively (Kwon et al., 2016). would not only enhance the adsorptive capacity of heavy metal
Generally, heavy metals usually exist in the expected forms ions, but also improve the removal selectivity of foreign ions.
under acidic condition, and functionalized carbon-based nano-
materials are synthesized according to these expected forms.
Therefore, acidic conditions usually favor the removal of heavy 5. Mechanism of heavy metal removal by functionalized
metal ions. For example, the removal of Pb(II) by modified MWCNTs carbon nanotubes and graphene nanomaterials
was observed to be significantly affected by pH values. When the
initial pH values increased from 2.0 to 11.0, the removal efficiency 5.1. Adsorption isotherms
rapidly increased at pH 5.0 and 6.0, slowly decreased in the pH
range of 6.0e8.0, and then sharply decreased at pH 8.0e10.0 The adsorptive capacity is the most important indicator and is
(Vukovi c et al., 2011). usually used to evaluate an adsorbent. The theoretical adsorptive
In addition to affecting the speciation of heavy metals, the so- capacity is calculated using adsorption isotherm models. The
lution pH also affects heavy metal removal with different types of adsorption behavior of heavy metals by functionalized carbon-
functional groups and nanomaterials. The ionization of the surface based nanomaterials are described by isotherm models, such as
acidic groups and charges will also be affected by pH values. For the Langmuir, Freundlich, Redlich-Peterson, Temkin, and Dubinin-
example, the pKa values of carboxylic groups are about 3.0e6.0, Radushkevich models. These models are expressed using the
which play an important role in the uptake of heavy metal ions. The following equations (Andersson et al., 2011; Xu et al., 2012b; Zhao
electrostatic interaction between heavy metal ions and nano- et al., 2016):
materials should be considered when making selections for
wastewater treatment (Chandra et al., 2010). Langmuir : qe ¼ kL qm Ce =ð1 þ kL Ce Þ (1)

1=n
Freundlich : qe ¼ kF Ce (2)
4.3. Ionic strength and coexisting ions
. 
The background electrolyte concentration in the solution can be Redlich  Peterson:qe ¼ kR Ce 1 þ aCeb (3)
represented by ionic strength. Ionic strength affects the interface
potential and thickness of the double layer, especially binding Temkin:qe ¼ ðRT=bT ÞlnðkT Ce Þ (4)
during the adsorption process, which plays an important role in the
removal of heavy metal ions by nanomaterials due to their large  
specific surface areas and strong adsorption abilities. The adsorp- Dubinin  Radushkevich:qe ¼ qm exp  kDR ε2 (5)
tion type will be affected by the electrolyte concentrations. The
background electrolyte ions are in the same plane with the outer- where qe and qm (mg g1) signify the equilibrium and maximum
sphere of nanomaterials, which are more susceptible to ionic adsorptive capacities, respectively; Ce (mg L1) is the equilibrium
strength variations than the inner-sphere complexes. For example, aqueous concentration; KL (L mg1) and KF (mg g1 (mg L1)n)
the removal rate of Cr(VI) by MWCNTs-supported nZVI was accel- represent the adsorptive capacity and the affinity between adsor-
erated when the ionic strength was increased from 0 to 0.05 M in bate and adsorbent; kR (L g1), a (L g1), and b (dimensionless) are
our previous study, implying an outer-sphere complexing mecha- constants; kT (L g1) is the equilibrium binding constant; bT (J
nism and b-plane adsorption (Lv et al., 2011). However, an obvious mol1) is related to the heat of adsorption; 1/n (dimensionless)
drop was observed at 0.1 M ionic strength (using NaCl), which represents the heterogeneity of the adsorbent sites and also in-
might be attributed to the obstruction of Cl on Cr(VI) adsorption dicates the affinity between adsorbate and adsorbent; kDR (mol2
by MWCNTs, and the competition of Cl with CrO2 
4 /HCrO4 (Pillay kJ2) is related to the mean free energy (kJ mol1) of adsorption and
et al., 2009). is equal to 1/(2kDR)1/2, and ε ¼ RTln(1 þ 1/Ce).
Coexisting anions and cations are important constituents in the The Langmuir isotherm model is commonly used for monolayer
water environment, and the effects on contaminant removal by adsorption in which most of the adsorption sites have equal affin-
nanomaterials have been widely reported. Gollavelli et al. investi- ities toward the adsorbate, while the Freundlich isotherm model is
gated the effects of common ions on the Cr(VI) adsorption by smart used to describe a heterogeneous chemisorption process in which
magnetic graphene (Gollavelli et al., 2013). A decreased trend of the surface is not energetically uniform. The Redlich-Peterson
Cr(VI) removal was observed with increased SO2 4 , probably due to isotherm model is a combination of the Langmuir and Freundlich
the surface complexation of SO2 4 with Fe2O3 and the resulting models, with values b in the range of 0e1. If the value of aCbe is much
competition with Cr(VI) species for adsorption sites. Compared to larger than 1, the equation can be approximated by the Freundlich
 
SO2
4 , NO3 and Cl had smaller negative charges and did not exhibit equation, while if b ¼ 1, the equation can be approximated by the
obvious effects on the Cr(VI) adsorption. Moreover, coexisting As(V) Langmuir isotherm model. The Temkin isotherm model is applied
and Pb(II) ions in the range of 0.1e5.0 mg L1 also did not affect to study the heat of adsorption (RT/bT) and the interaction between
Cr(VI) removal by magnetic graphene, and the removal efficiencies adsorbates on adsorption isotherms. For example, if the values of
of these three coexisting heavy metals were all 99.0%, which in- RT/bT increase with increasing temperature, the adsorption process
dicates that the magnetic graphene is an effective adsorbent for a is endothermic, and the opposite is exothermic (Andersson et al.,
wide range of heavy metals. In addition, two of the most common 2011). The Dubinin-Radushkevich isotherm model is usually used
cations, Ca(II) and Mg(II), are also usually added to investigate their to investigate the type of adsorption process.
effects on heavy metal ion removal. (Wan et al., 2016). It was found Most of the functionalized CNTs and graphene nanomaterials
that Pb(II) adsorption by HMO@GO was not affected by Ca(II) or mentioned in this review showed better fit with the Langmuir
Mg(II), while a sharp decrease of Pb(II) adsorption by GO was isotherm model, and the adsorptive capacities of the CNTs and
 J. Xu et al. / Chemosphere 195 (2018) 351e364 359

graphene based nanomaterials for removal of various aqueous chemisorption processes are dominant at 20e80 kJ mol1, and
heavy metals are in Table 3. chemisorption processes are dominant at 80e400 kJ mol1
(Andersson et al., 2011).
5.2. Adsorption kinetics
5.4. Other pathways that accompany adsorption
The adsorption kinetics of aqueous heavy metals by carbon-
based nanomaterials are generally well-fitted by the pseudo-first- In addition to the general adsorption mechanism (physical
order, pseudo-second-order, Elovich, and intra-particle diffusion adsorption, electrostatic interaction, and surface interaction be-
models, which are described in the following equations (Mishra tween the heavy metal ions and surface functional groups), other
and Ramaprabhu, 2010; Wan et al., 2016). removal pathways may also occur, depending on the nanomaterial
properties and additional characteristics provided by functionali-
Pseudo first order : logðqe  qt Þ ¼ log qe  k1 t=2:303 (6) zation (Fig. 3).
Oxidation and reduction play significant roles in the interactions
Pseudo second order : qt ¼ k2 q2e t=ðtk2 qe þ 1Þ (7) between heavy metal ions and functionalized carbon-based nano-
materials with redox capacity, especially during the removal of
Cr(VI) and As(III). The reaction mechanism for MWCNTs supported
Elovich kinetics : qt ¼ b1 lnðabÞ þ b1 ln t (8) nZVI nanocomposites prepared to remove Cr(VI) included the
reduction of Cr(VI) to Cr(III) by the oxidization of nZVI to iron ions,
Intra  particle diffusion : qt ¼ ki t 1=2 þ C (9) which would precipitate soluble Cr to form CrxFe1x(OH)3 com-
plexes on the nanomaterial surfaces and enhance the adsorption
where qt and qe are the adsorptive capacities (mg g1) at time t and process (Lv et al., 2011). Since As(III) adsorption is always weaker
at equilibrium, respectively; k1 (min1), k2 (min1), and ki (mg than that of As(V) by MWCNTs and other adsorbents, a pretreat-
g1 min0.5) are the rate constants of the pseudo-first-order, ment for oxidizing As(III) to As(V) is required to achieve satisfactory
pseudo-second-order, intra-particle diffusion models, respec- As(III) removal. The removal pathway of As(III) by GO-MnFe2O4
tively; and C (mg g1) is a constant that approximates the thickness nanohybrids involved oxidation of As(III) to As(V) by the manga-
of the boundary layer. nese oxide, which created more active sites for the adsorption
Detailed adsorption mechanisms can be inferred from the ki- process (Kumar et al., 2014).
netics model. The pseudo-first-order model of Lagergren has long Hydrolysis, flocculation, complexation, precipitation, and ion
been widely applied based on the adsorptive capacity. The pseudo- exchange also may contribute to the removal of heavy metal ions by
first-order model is based on the assumption that the adsorption functionalized carbon-based nanomaterials. For example, non-
rate is controlled by chemical adsorption, which includes the specific ion exchange between GO and Pb(II) was indicated by the
electron transfer and sharing between adsorbate and adsorbent. binding energy peak at 137.8 eV in XPS spectra of Pb-laden GO, and
The Elovich model is an adsorption reaction model that includes inner-sphere complexation between HMO and Pb(II) was implied
chemical reactions. Intra-particle diffusion is usually divided into by the peak forwarded to 137.0 eV in the XPS spectra of Pb-laden
three steps: (i) diffusion through the liquid film to the adsorbent HMO@GO (Wan et al., 2016). Cui et al. modified the surface of GO
surface, (ii) diffusion in the pore liquid (intra-particle diffusion), with CHAP, which had strong ion exchange properties and could
and (iii) adsorption and desorption between the active sites and enhance the Pb(II) removal (Cui et al., 2015).
adsorbate.
6. Future research prospects
5.3. Adsorption thermodynamics
6.1. Functional nanomaterials for treating combined pollution
The adsorption Gibbs free energy (DG0, kJ mol1), enthalpy
change (DH0, kJ mol1), and entropy change (DS0, kJ mol1 K1) can In most cases, water environmental chemistry is very compli-
be determined by the following equations (Xu et al., 2016b): cated. The water contains many kinds of pollutants, which give rise
to more serious environmental damage from their combined tox-
DG0 ¼ RT ln K0 (10) icities and relative mobility. Developing highly effective methods to

DG0 ¼ DH0  T DS0 (11)

. .
ln K0 ¼ DS0 R  DH 0 RT (12)

where T (K) is the system temperature, R (8.314 J mol1 K1) is the

universal gas constant, and K0 is the equilibrium constant. The
value of K0 can be obtained from the intercept of ln(qe/Ce) plotted
versus qe. DG0 is calculated using Eq. (7). DS0 and DH0 are calculated
from the intercept and slope of the regression of ln K0 versus 1/T.
Additional in-depth information of the inherent energetic
changes can be obtained from the adsorption thermodynamic pa-
rameters. Generally, negative DG0 and DH0 values indicate that the
adsorption process is spontaneous and exothermic, respectively,
while positive values indicate the opposite mechanism. Moreover,
the DH0 values are also used to distinguish whether the adsorption
process can be classified as physisorption or chemisorption. Phys-
isorption processes are dominant below 20 kJ mol1, physisorption- Fig. 3. Pathways for aqueous heavy metal removal by functionalized nanomaterials.
360 J. Xu et al. / Chemosphere 195 (2018) 351e364

remove hazardous pollutants from water simultaneously has need to be broadened, which requires to include the impacts of
become a well-researched topic that addresses an urgent demand whole life cycle, rather than prioritizing direct exposure impacts.
for practical applications in water pollution control (Luo et al., 2011; Both the environmental direct-release impacts and production-
Tao et al., 2016; Yan et al., 2016). side impacts of CNT and graphene nanomaterials are required to
Some active substances with good affinity toward a wide range be mitigated. Future development into improving the environ-
of contaminants have been used to modify the NPs and enhance mental sustainability of CNTs and graphene nanomaterials should
their pollutant removal efficiencies (Cai et al., 2010; Khan et al., take a life cycle perspective to balance the commercial-production
2015). Fig. 4 shows some examples that two or more contami- economics, application performance, and environmental
nants were simultaneously removed from water by functionalized implication.
carbon nanomaterials, including GO-zirconium phosphate (GO-Zr-
P) nanomaterials, titanium and lanthanum oxides impregnated on
granular activated carbon (Ti/La-AC), and nitrogen-functionalized 6.3. Computational simulations
magnetic ordered mesoporous carbon (N-Fe/OMC) (Jing et al.,
2012; Pourbeyram, 2016; Yang et al., 2015). Additionally, in our Computational chemistry has been applied to simulate the
previous study, it has been proved that zero valent iron is a strong heterogeneous reactions of heavy metals by nanomaterials func-
reducible agent that can remove not only heavy metal ions (Cr), but tionalized with metals, metal oxides, or carbon (Siddiqui et al.,
also NO3 and chlorinated organics (2,4-dichlorophenol) (Lv et al.,
2013; Hou et al., 2014; Xu et al., 2015). Insight into the removal
2012; Xu et al., 2012a, 2013a, 2016a). Iron-based functionalized reactions at the molecular-electronic level can be gained by
nanomaterials are also expected to treat combined heavy metal and computational simulation via theoretical calculations, including ab
halogenated organic pollution. initio methods, the density functional theory (DFT), and their de-
Research on the removal of combined pollution by carbon-based rivative models (Steckel, 2008; Sun et al., 2011; Wilcox and Okano,
nanomaterials is still lacking, and researchers need to consider 2011). Thermodynamic properties, accurate bond energies, some
potential coexisting pollutants when studying the removal of a experimental kinetic parameters that are difficult to deduce, and a
given pollutant. It is important to synthesize more functional better description of the reaction mechanism can be obtained from
nanomaterials that can remove a wide range of contaminants, the models (Auzmendi-Murua et al., 2014; Wang et al., 2015b). The
maintain good activity for a long time, and meet the requirements results contribute to the design and modification of functional
for the practical treatment of wastewater. nanomaterials to improve their absorptive efficiencies for heavy
metals. However, most of these studies were focused on the gas
phase, especially for mercury oxidization and adsorption from flue
6.2. Sustainability of nanomaterials gas.
Few studies have focused on the optimization of nanomaterial
Although novel and functionalized nanomaterials have good fabrication. Roohi and Khyrkhah investigated the structural and
potential to improve the performance of current and future tech- electronic properties of green chemically functionalized SWCNTs
nologies in many fields, environmental implications (e.g., fate, with IL functional groups via DFT, including the distances and
transport, and ecotoxicity) should be concerned due to the strength of hydrogen bonds in the IL and the length of the C]C
discharge of engineered nanomaterials, in order to reduce (or even bonds in the SWCNTs (Roohi and Khyrkhah, 2015). It was suggested
preclude) the potential of adverse unintended consequences. Since that IL preferred the edge site of pristine SWCNTs rather than other
the application (e.g., adsorption capacity) and implication (e.g., positions, based on the relative energies. However, further studies
toxicity) depend on physicochemical properties (e.g., size, func- on computer simulations of the interaction between heavy metal
tional groups, surface charge, purity and so on), sustainability by ions and nanomaterials in aqueous phase are still needed to save
design is a framework that aims to synthesize engineered nano- valuable time and effort during basic lab experiments.
materials not only to be safe to the environment and humans, but
also to meet the desired performance. The relationships between
the structure design, obtained function, and environmental risk of 6.4. Other recommendations for future research
engineered nanomaterials are desired to be studied and
established. Although the development of functionalized nanomaterials has
Additionally, the production impacts of CNTs were reported to received much attention recently, there is still a long way to go
exceed their direct exposure impacts (Eckelman et al., 2012), and before achieving the ultimate goal of practical application and
the lens of toxicity assessment of CNTs and graphene nanomaterials commercialization.

Fig. 4. Schematic of functionalized nanomaterials for combined pollutant removal.

 J. Xu et al. / Chemosphere 195 (2018) 351e364 361

i. The properties of nanomaterials are mainly dependent on generated by mechanical pulping using activated charcoal and fly ash:
adsorption isotherms and thermodynamics. Ind. Eng. Chem. Res. 50,
the preparation methods and conditions, which play an
7722e7732.
important role in the sizes, structures, compositions, and Atieh, M.A., 2011. Removal of chromium (VI) from polluted water using carbon
reaction activities of functionalized nanomaterials. Few nanotubes supported with activated carbon. Procedia Environ. Sci. 4, 281e293.
Auzmendi-Murua, I., Castillo, A., Bozzelli, J.W., 2014. Mercury oxidation via chlorine,
studies have investigated the effects of preparation condi-
bromine, and iodine under atmospheric conditions: thermochemistry and ki-
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