J Mater Sci (2020) 55:7156–7183

Review
REVIEW

Emerging energy and environmental application

of graphene and their composites: a review
Mohamed I. Fadlalla1, P. Senthil Kumar2, V. Selvam3, and S. Ganesh Babu4,*

1
Centre for Catalysis Research and C*Change (DST-NRF Centre of Excellence in Catalysis), Department of Chemical Engineering,
University of Cape Town, Cape Town 7700, South Africa
2
PG & Research Department of Chemistry, Thiagarajar College, Madurai 625009, Tamilnadu, India
3
Department of Chemistry, The M.D.T. Hindu College, Tirunelveli 627010, Tamilnadu, India
4
Department of Chemistry, School of Advanced Sciences, VIT University, Vellore 632014, Tamilnadu, India

Received: 31 July 2019 ABSTRACT

Accepted: 13 February 2020
Published online:
5 March 2020
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2020
Graphene-based materials receive attention in the field of energy and environ-
mental application. The unique physiochemical assets such as the high surface
area, high thermal stability, chemical flexibility, high electron mobility and
mechanical solidity make it a highly versatile material for different applications.
In this critical review, the application of graphene-based material in energy and
environmental remediation is discussed in detail. More specifically, the role of
graphene in thought-provoking research fields, viz. solar cell, photocatalytic
water splitting, photocatalytic degradation of organic pollutants and heavy
metal removal, is focused. As graphene possesses very good carrier mobility, it
enhances the photocatalytic performance of semiconducting materials. Very
interestingly, graphene is being used in both hole transport layer and electron
transport layer in solar cell. Similarly, high surface area of graphene assists in
heavy metal removal by adsorption. The challenges and recent achievements in
these fields are highlighted in this review.

Introduction can be turned for specific applications which is a note-

Carbon-based materials are highly versatile that can be
used for various applications [1–3]. Interestingly, the
ability of carbon atom to bond with each other allows it
to form linear, planar and tetrahedral arrangement [4].
As a result, there is a significant difference in their
physicochemical properties, namely surface area, pore
size, conductivity, and so on. Hence, the carbon material
worthy advantage of carbon-based materials [5–7].
The carbon materials, viz. carbon nanofibers, activated
carbon, carbon foams, carbon hydrogels, mesoporous
carbon materials/sheets, graphite, graphite materials,
lonsdaleite, carbon nanotubes (CNTs) and fullerene, are
being used in all fields of technologies ranging from
electronic systems to biomedical devices [8–10]. In recent
years, the graphene (a rising-star material) and

Address correspondence to E-mail: ganeshbabu.s@vit.ac.in

https://doi.org/10.1007/s10853-020-04474-0
J Mater Sci (2020) 55:7156–7183
graphene-based materials get spotlight as supports in the
field of heterogeneous catalysis [11–16]. This is mainly
because of the vital properties such as the high surface
area, high thermal stability, chemical flexibility, high
electron mobility and mechanical solidity. The graphene-
based materials provide high flexibility in modifying the
catalyst properties to precise requirements. For instance,
the high surface area assists the well dispersion of
nanomaterials and hence improves the performance
[17–20]. Besides, the high thermal stability under reduc-
ing condition makes it as a favorable support for the
metal nanoparticles [21, 22]. Similarly, the high-speed
electron mobility of graphene extraordinarily increases
the electrocatalytic activity and improves the photocat-
alytic behavior by preventing the electron–hole pair
recombination [23, 24]. On the other hand, the defective
sites in graphene-based materials serve as nucleation
centers for the nanomaterials and thereby arrest the
mobility that avoid sintering of these nanomaterials
during catalysis process [25]. Furthermore, the selective
chemical functionalization of graphene-based materials
allows to alter the acid–base property which in turn can
be used for a specific need.
Owing to the above-said specific properties, gra-
phene and graphene-based materials are widely used
in numerous catalytic reactions, such as oxygen
reduction reaction (ORR) [26, 27] oxidation of SO2 gas
to SO3 [28], oxidative dehydrogenation (ODH) of
ethylbenzene to styrene [29–34], Fischer–Tropsch
synthesis (FTS) [34–37] CO2 reduction [38, 39] water
splitting [40, 41], selective hydrogenation [42–44],
NOx abatement [45–47], catalytic purification of
VOCs [48, 49], hydrogen fuel cell [50], wastewater
treatment [51, 52] and Suzuki–Miyaura coupling
reaction [53]. However, in this review we summa-
rized the recent advances of the graphene-based
materials in solar cell, photocatalytic water splitting,
photocatalytic degradation of organic pollutants and
heavy metal removal in aqueous environment.
Graphene-based material for energy
application
In solar cell
Graphene-based materials for polymer solar cell
Bulk heterojunction (BHJ)-based polymer solar cells
(PSCs) have gained considerable interest owing to its
7157
competitive advantages including solution process-
ability, flexibility, lightweight, low cost and large area
coating [54, 55]. The BHJ consists of mixture of elec-
tron donor and acceptor polymer materials, which
can efficiently absorb solar light, generate exciton and
dissociate into free charge carriers [37, 56, 57].
Poly(3,4-ethylenedioxythiophene) (P3HT) and full-
erene-based acceptors are the most widely used
photoactive blend in PSCs. Recently, several low
bandgap polymers have been developed, which can
absorb a wide range of solar spectra to increase the
efficiency [58–60]. However, poor power conversion
efficiency, chemical instability, fast degradation of
photoactive layers and inefficient charge separation
at the interfaces greatly affect the commercialization
of PSCs [61, 62].
Two-dimensional graphene sheet with unusual
physicochemical properties has gained exceptional
interest for various applications including solar cells,
sensors, fuel cells, photocatalysis, batteries and
supercapacitors [63–68]. Particularly, an outstanding
electrical conductivity, optical transparency, flexibil-
ity and tunable work function turn graphene as an
impressive candidate for PSC applications [69, 70].
Recently, extensive research has been carried out by
utilizing graphene and graphene/nanocomposite as
different components in PSCs [71]. The large reactive
surface area and active edges of graphene offer a
wide range of opportunities to incorporate various
organic, inorganic and polymeric materials to
develop highly efficient PSC [72]. In this section, we
described the multifunctional role of graphene and
graphene-based nanomaterials as a hole-transporting
layer (HTL), electron-transporting layer (ETL), pho-
toactive layer and electrode in PSCs.
Graphene-based hole-transporting layer
Li et al. have successfully employed graphene oxide
(GO) as a hole-transporting layer (HTL) due to its
proper work function with electron donor polymer
and anode [73]. This work further motivated the
researchers to use GO-based buffer layers in PSC.
Figure 1a shows the schematic design of the bulk
heterojunction-based PSC device structure using GO
as a HTL. As displayed in Fig. 1b, the calculated
work function (- 4.7 eV) of GO quite matches with
the work function of poly(3-hexylthiophene) [P3HT],
which further facilitates the hole transportation from
the donor polymer (P3HT) to the respective anode
7158
(ITO). Interestingly, GO as a HTL remarkably
enhances the PCE up to 3.6%, which is favorably
comparable with the PCE of control device made
using PEDOT:PSS as a HTL (Fig. 1c). Thus, the
improved performance was mainly due to the suit-
able work function and effective separation of charge
carriers by GO sheets. Similarly, GO was demon-
strated as a HTL in inverted-type PSC with the device
architecture of ITO/ZnO/C60-SAM/P3HT:PCBM
[74]. It was found that the functional groups of GO
effectively interacted with surface of P3HT and
increased the hole transportation. Furthermore, GO
with optimized thickness (2–3 nm) showed a PCE of
3.61% with an open circuit voltage (Voc) = 0.64 V,
current density (Jsc) = 8.70 mA/cm2 and fill factor
(FF) = 64.5%.
Liu et al. have developed sulfated GO as a HTL for
BHJ-based PSC [75]. The –OSO3H groups from the
fuming sulfuric acid were attached through the
epoxy/hydroxyl groups of GO and improved the
electrical conductivity from 0.004 to 1.3 S m-1. In
addition, the observed suitable work function of
GO-OSO3H facilitated the formation of Ohmic con-
tact with P3HT and considerably boosted the device
performance. Yun et al. have investigated the
Figure 1 a Schematic structure of the PSC device using GO as a
hole-transporting layer, b energy-level diagram of GO-based PSC
device and c current density–voltage (J–V) characteristic curve of
J Mater Sci (2020) 55:7156–7183
solution-processable graphene-based thin film as a
HTL [76]. GO was reduced into reduced graphene
oxide (pr–GO) in the presence of p-toluenesulfonyl
hydrazide as a reducing agent and used as a HTL.
pr–GO-based device showed superior performance
than the device fabricated using GO and rGO. Most
importantly, device with pr–GO manifested better
stability than the solar cell fabricated with most well-
known HTL, i.e., PEDOT:PSS.
In addition to chemical functionalization, GO has
also been modified using thermal treatment. For
example, GO solution was spin-coated on the glass
substrate and thermally annealed at different tem-
peratures in an open atmosphere [77]. Under optimal
thermal treatment, GO exhibited better hole-trans-
porting property, which further enhanced the PCE of
the PSC devices.
Dai and co-workers have prepared GO nanoribbon
and used as a HTL in widely studied BHJ PSC with
the device configuration of ITO/HEL/P3HT:PCBM/
Ca [78]. It was interesting to observe that the GO
nanoribbon possessed an excellent solubility and
film-forming properties than the GO sheets. PSC
device fabricated using GO nanoribbon outper-
formed the conventional HTL materials including
the PSC devices with GO, ITO and PEDOT:PSS as a hole-
transporting layer. Reproduced with permission from reference
[73].
J Mater Sci (2020) 55:7156–7183
PEDOT:PSS and bare GO. Chen and co-workers have
designed GO/oxygen deficient molybdenum oxide
(MoO3-x) bilayer as a HTL in highly efficient PSC
with the device architecture of ITO/GO/MoO3-x/
P3HT or PThBDTP:PC61BM/Ca/Al [79]. The effec-
tive hole collection property of resultant bilayer GO/
MoO3-x thin film was tested with two different
photoactive layers such as P3HT:PC61BM and
PThBDTP:PC71BM. Bilayer GO/MoO3-xthin film
showed an optimized PCE of 4.08% and 8.05% by
using P3HT:PC61BM and PThBDTP:PC71BM as a
photoactive layer. Water-soluble GO-based polymer
composite materials have been demonstrated as an
efficient HTL for high-performance PSC [80]. GO/
(poly[(9,9-bis((60 -(N,N,N-trimethylammo-
nium)hexyl)-2,7-fluorene)-alt-(9,9-bis(2-(2-(2-methox-
yethoxy) ethoxy)ethyl)-9-fluorene))] dibromide
(WPF-6-oxy-F) exhibited a PCE of 6.59%, while GO
alone showed 3.14%. The significant improvement in
PCE of GO/ WPF-6-oxy-F was mainly attributed to
the improved conductivity and doping between GO
and WPF-6-oxy-F polymer. Recently, Kwon et al.
have developed a simple and cost-effective method
for the preparation of rGO using electron beam. The
electron beam-induced reduced GO (ERGO) was
demonstrated as a HTL for PSC [81]. ERGO-em-
ployed PSC showed an average PCE of 3.77% which
was almost threefold higher PCE than the device
fabricated using pristine GO.
Very recently, GO/PEDOT:PSS double-decked
HTL was successfully established as a HTL for
PCDTBT:PC71BM-based PSC device [82]. Figure 2a
and b depicts the PSC device structure and energy-
level diagram of GO/PEDOT:PSS HTL. The PSC
device fabricated using GO/PEDOT:PSS shows a
PCE of 4.28% with Voc = 0.82 V, Jsc = 10.4 mA/cm2
and FF = 50%, whereas the device designed with GO
and PEDOT:PSS alone shows relatively low PCE of
2.77% and 3.57%, respectively (Fig. 2c). Chen and his
research group have recently synthesized fluorine-
functionalized rGO (F–rGO) using 2,3,5,6-tetrafluoro-
4-(trifluoromethyl)phenyl-hydrazine as both reduc-
ing agent and F source [83]. Figure 2d presents the
schematic illustration for the synthesis of F–rGO. As
represented in Fig. 2e, F–rGO as a HTL considerably
enhanced the PCE to 8.6% while the device with GO
and PEDOT:PSS HTLs exhibits a PCE of 7.8% and
7.9%, respectively. Thus, the doping of F with rGO
selectively enhanced the hole mobility which further
increased the device performance.
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Graphene-based electron-transporting layer
GO-based electron-transporting layer (ETL) was
firstly demonstrated by Liu et al. in the year 2012 [84].
The epoxy (–COOH) groups present at the edges of
GO were functionalized with cesium (Cs) metal
through simple charge neutralization process. The as-
prepared GO–Cs was used as an ETL in both normal
and inverted-type PSC. The Cs-functionalized GO
exhibited a very low work function (4.0 eV) com-
pared to the work function of bare GO (4.7 eV). Thus,
the achieved low work function well matched with
the LUMO work function of electron-accepting
polymer to facilitate the photogenerated electrons to
the electrode. The devices fabricated with GO–Cs as
an ETL exhibited much improved performance than
the device using Cs2CO3 as an ETL. Likewise, full-
erene-functionalized reduced graphene oxide (rGO–
fullerene) was used as an ETL in PSC [85]. Fullerene
was non-covalently interacted through pi–pi interac-
tion through the carbon basal plane of GO and pyr-
ene groups of fullerenes. The rGO–fullerene as an
ETL showed a PCE of 3.89% which was almost
threefold higher PCE than the device without ETL.
Yang et al. have developed Cs2CO3-functionalized
graphene quantum dots (GQDs) as an ETL in inverted
architecture-based PSC device [86]. Cs2CO3 as an ETL
exhibited a PCE of 2.72%, whereas GQDs–Cs2CO3-
based PSC device showed an average PCE of 3.23%. The
improvement in the performance was mainly due to
efficient electron extraction property and suitable work
function of GQDs. Recently, Moon et al. have synthe-
sized chemically surface-modified ZnO@graphene
core–shell-type quantum dots (ZGQDs) and employed
as an ETL in inverted PSC [87]. The interfacial charge
transfer between GQDs and ZnO significantly boosted
the efficiency up to 10.3%. Similarly, Liu and his co-
workers have modified graphene quantum dot edges
with tetramethylammonium (GQDs–TMA) using sim-
ple neutralization reaction [88] (Fig. 3a). The resultant
GQDs–TMA showed excellent transparency in both
visible and IR region, which is favorable to use as an
ETL in PSC. Figure 3b shows the device structure of
PSC device using GQD–TMA as an ETL. A device with
GQD–TMA as an ETL exhibits a PCE of 7.0% with Jsc-
= 10.84 mA/cm2, Voc = 0.91 V and FF = 71.11%
(Fig. 3c).
7160
Figure 2 a PSC device structure with GO/PEDOT:PSS as a HTL,
b work function diagram of PSC device with the device structure
of ITO/GO/PEDOT:PSS/PCDTBT:PCBM/Al, c J–V curves of
different HTLs (GO, PEDOT:PSS and GO/PEDOT:PSS)-based
Graphene-based photoactive layer
Fullerene and its derivative are the most widely used
electron acceptor materials in PSC. However, ineffi-
cient charge transport property and excessive cost are
the major issues which greatly limited the usage of
fullerene in PSC. Graphene with excellent charge
transport property, high carrier mobility and unique
two-dimensional structure has been considered as a
potential candidate as an electron acceptor in PSC.
The first solution-processable graphene (SPF gra-
phene)-based electron acceptor material was devel-
oped by Chen et al. in the year 2008 [89]. The
different contents of SPF graphene were mixed with
poly(3-octylthiophene) (P3OT) electron donor and
used as a photoactive layer. The P3OT/SPF graphene
active layer was post-annealed at 160 8C and showed
a maximum PCE of 1.4% with Jsc = 4.2 mA/cm2,
Voc = 0.92 V and FF = 0.37, respectively. Similarly,
same Chen et al. have developed P3HT/solution-
J Mater Sci (2020) 55:7156–7183
PSCs, d schematic illustration for the synthesis of F–rGO and e J–
V characteristics curve of PSC devices using GO, PEDOT:PSS
and F-rGO as HTLs. Reproduced with permission from references
[82, 83].
processable graphene-based photoactive layer in
PSC, which displayed a maximum PCE of 1.1% [90].
Liming Dai and co-workers have chemically graf-
ted P3HT onto the graphene sheet through esterifi-
cation reaction (Fig. 4a) [91]. The resultant G–P3HT
was found to be soluble in various organic solvents.
As depicted in Fig. 4b, the solution-processable G–
P3HT is incorporated as a photoactive layer in bulk
heterojunction-based PSC with the device configura-
tion of ITO/PEDOT:PSS/G–P3HT/C60/Al. Fig-
ure 4c shows the current–voltage characteristics
curves of the PSC device using G–P3HT and P3HT/
C60 as a photoactive layer. It can be clearly seen that
the device fabricated with G–P3HT/C60 exhibits
enhanced Jsc and Voc compared to that of the device
with P3HT/C60. Thus, a maximum efficiency of 0.61
was achieved, which was threefold higher than
P3HT/C60 based device.
Likewise, C60 fullerene was covalently attached on
graphene sheets via simple lithiation reaction [92].
The resultant C60–G composites were used as an
J Mater Sci (2020) 55:7156–7183 7161

Figure 3 a Synthesis
mechanism for the preparation
of GQDs-TMA, b PSC device
structure with GQDs-TMA as
a cathode interlayer and c J–V
curves of PSC devices with
and without GQDs-TMA.
Reproduced with permission
from reference [88].

Figure 4 a Schematic
representation for the synthesis
of fullerene-grafted graphene,
b bulk heterojunction PSC
device structure [ITO (anode)/
PEDOT:PSS (HTL)/G-P3HT
(electron donor): C60 (electron
acceptor)/Al (cathode)] and
c J–V characteristic curves of
P3HT and G-P3HT-based
PSCs. Reproduced with
permission from reference
[91].
7162
Figure 5 a Schematic diagram of rGO/PANI-Ru-used PSC device b J–V curves of PSC devices using PANI-Ru and rGO/PANI-Ru
nanocomposites as an electron donor. Reproduced with permission from reference [72].
electron acceptor along with electron donor (P3HT)
in bulk heterojunction PSC. The devices with C60–
G:P3HT and C60:P3HT as an photoactive layer
exhibited the PCE of 1.22% and 0.47%, respectively.
Such remarkable enhancement in PCE was mainly
due to the unusual electron-transporting nature of
graphene sheets.
In addition to the earlier works, recently graphene
quantum dots (GQDs) have been attracted as a
promising candidate for PSC. The first GQDs-based
PSC device was developed by Li et al. in the year
2011 [93]. The as-synthesized GQDs were utilized as
an electron acceptor in PSC. It was interesting to note
that the GQDs exhibited the low LUMO level work
function of 4.2 eV, which was less than the LUMO
level work function of graphene (4.5 eV). Therefore,
the low work function and the effective transporta-
tion of charge carriers by GQDs significantly
enhanced the PCE to 1.28%. In contrast, the device
without GQDs showed very poor PCE of 0.008%.
Followed by the earlier work, Vinay Gupta has
synthesized aniline-modified luminescent GQDs
(ANI–GQDs) and demonstrated as an electron-
transporting layer in PSC [94]. A maximum PCE of
1.14% was achieved with 1 wt% ANI–GQD in P3HT.
In addition to electron acceptor, GQDs was also used
as an additive for the photoactive layer [95]. The
GQDs were incorporated onto the photoactive layer,
which considerably improved the performance of the
device compared to that of device without GQDs.
Very recently, Neppolian and co-workers have
designed a metallopolymer-grafted reduced gra-
phene oxide sheets (rGO) photoactive layer for bulk
heterojunction PSC [72]. In this work, pyridyl benz-
imdazole-based Ru complex-decorated polyaniline
J Mater Sci (2020) 55:7156–7183
(PANI–Ru) was covalently linked onto rGO via sim-
ple chemical approach. As illustrated in Fig. 5a, the
resultant rGO/PANI–Ru composite is used as an
electron donor along with fullerene as an electron
acceptor. Figure 5b shows the current–voltage char-
acteristics curve of PSC device constructed with
PANI–Ru and rGO/PANI–Ru as an electron donor.
The rGO/PANI–Ru used device displays sixfold and
twofold higher Voc and Jsc than the device made with
PANI–Ru alone. The significant enhancement in the
Voc was owing to the excellent charge carrier sepa-
ration and ultrafast transportation of electrons by
graphene sheets.
Graphene-based electrode
The flexible and transparent nature of single- or few-
layered graphene sheets has been widely used as an
electrode in PSC [96]. The CVD-grown graphene was
used as an anode in PSC with the device structure of
CVD-grown graphene/PEDOT:PSS/CuPc/C60/Al
[97]. The resultant CVD-grown graphene electrode
displayed a maximum PCE, which was comparable
with the PCE of ITO-based PSC devices. Followed by
earlier work, CVD-grown graphene was demon-
strated as a top electrode in inverted-type PSC device
[98]. Interestingly, CVD-grown graphene not only
increased the PCE but also exhibited better mechan-
ical stability compared to that of most widely used
ITO anode.
On the other hand, chemically reduced graphene
(rGO) was also constructed as the bottom electrode in
P3HT:PCBM-based PSC. The rGO sheets were spin-
coated on the flexible polyethylene terephthalate
(PET) substrate. The highest PCE of 0.78% was
J Mater Sci (2020) 55:7156–7183
achieved under optimized rGO film thickness. Park
et al. have designed graphene as both anode and
cathode electrodes for flexible PSC [99]. Graphene
anode and graphene cathode-based PSC devices
significantly enhanced PCE of 6.1% and 7.1%,
respectively. Recently, Zhang et al. have reported
solution-processable rGO/silver nanowires
(AgNWs)/rGO-based transparent electrode for PSC
[100]. The resultant rGO/AgNWs/rGO hybrid elec-
trode showed an excellent transparency of 90% at
550 nm. Moreover, the rGO/AgNWs/rGO electrode
demonstrated an improved photovoltaic perfor-
mance and better mechanical flexibility than the
control devices fabricated with ITO electrode.
The current progress and recent developments of
graphene-based materials in PSCs have been widely
investigated. The excellent electronic properties, bet-
ter optical transparency and tunable work function
offered a wide range of opportunities to utilize gra-
phene as a hole-transporting layer, electron-trans-
porting layer, electron donor, electron acceptor and
transparent electrode in PSC applications. In addition
to 2D graphene sheets, 0D GQDs has shown
improved properties than graphene sheets and
demonstrated as a potential candidate in PSC, espe-
cially as an electron acceptor owing to its desired
work function with enhanced charge transportation
properties. Therefore, the development of graphene
and graphene-based derivatives could open a wide
range of prospects for the fabrication of highly effi-
cient PSC devices in a large scale.
In photocatalytic water splitting
The increasing demand for the development of
renewable source of energy can meet the growing
energy demand with environment impact on mind.
The most promising energy source is hydrogen due
to it high burning energy [101]. Currently, the major
source of H2 is from fossil fuel (* 95%); the
remainder comes from water electrolysis [101–103];
therefore, a lot of research is focused on the use of
H2O as H2 source. The production of H2 from H2O
can be carried out by photochemical or photocatalysis
process; the difference between the two processes is
that the former begins with the reactants in an excited
state, while in the latter the reactants start in the
ground state. Some of the main advantages of visible-
light photocatalysis for H2 production are the cheap
endless supply of sunlight and environmentally
7163
friendly process with no disadvantages to earth.
Some of the challenges associated with photochem-
istry are the fact that most organic compounds do not
absorb in the visible-light wavelength. Therefore, an
expensive and energy demanding source of high
energy ultraviolet source (i.e., photoreactor) is
required and that introduces obstacles for industrial
use. This review is only focused on the H2 production
through the photocatalysis process for water splitting
and will not discuss the photochemical process any
further. Three modes of operation are considered to
take part in photocatalysis; firstly, a radical photo-
catalyst is formed by exciting atom or a group. Sec-
ondly, a radical anion or cation is formed by electron
transformation between the photocatalyst and sub-
strate. Thirdly, metal center carries out the reaction
[104].
Graphene is discovered in 2004 by Novoselov et al.
which was described in an atomic level to consist of
hexagonally bound carbon atoms arranged in a two-
dimensional monolayer sheet [105]. Graphene is
shown to have great electronic, mechanical, thermal
and surface area properties [106, 107]. The properties
of graphene can be tailored by modifying the syn-
thesis method and functionalization groups on the
graphene surface [104]. Due to these great properties,
graphene and doped graphene are used in different
areas of catalysis, which was reviewed elsewhere
[106–110], for example, in the oxygen reduction
[104, 111, 112], hydrogen evolution reaction [113–115]
and metal-free catalysis over doped graphene [116].
The focus of this review is to highlight the use of
graphene in a composite to produce H2 from water
through the water splitting reaction. The review
focuses on the effect of graphene loading on H2
production, the mechanism of action of the graphene,
the type and effect of the sacrificial agent, the stability
of the graphene containing composite under reaction
condition. The reader is referred to other reviews
focusing on several aspects of photocatalysis which
are extensively reviewed, for example, photocatalysis
over TiO2 [117], heterojunction photocatalyst [118],
materials for heterogeneous photocatalyst [119],
hydrogen production through water splitting
[120, 121], the use of semiconductor in photocatalysis
[122].
Li et al. reported the use of CdS cluster decorated
on graphene nanosheet for H2 production in water
spilling through photocatalysis with visible-light
irradiation, where Pt was the co-catalyst and lactic
7164
acid the sacrificial agent [123]. The role of Pt was to
limit the overpotential during water splitting reaction
and the reverse reaction (i.e., formation of water from
hydrogen and oxygen), while the lactic acid provides
electrons to consume the photogenerated holes. The
rapid recombination of the conductive bad (CB) and
the valence band (VB) in the CdS (GC0—no gra-
phene) is the reason for low H2 production. The
introduction of graphene sheets improved the activ-
ity, where with 1 wt% of graphene addition, the H2
production increased 4.87 folds in comparison with
no graphene addition (Fig. 6). The increase in the
activity is due to two reasons: firstly, the increase in
the catalyst specific surface area, which leads to more
active adsorption sites, and secondly, graphene plays
the role of electron acceptor for the electrons gener-
ated at the CdS site, therefore reducing the recombi-
nation of the photoexcited electron–hole pairs.
However, the further increase in the graphene con-
tent leads to the decrease in the H2 production due to
shielding of the active site by decreasing the intensity
and penetration of the light radiation. Based on these
results, the authors proposed a reaction mechanism,
where the electrons are excited in the CdS cluster
from the VB to CB by visible-light irradiation. The
generated electrons then transferred by one of three
pathways, which are to the graphene sheet, to the Pt
located on the graphene sheet or to the Pt on CdS
cluster. The electron then reacts with H? for H2. The
graphene sheets in this system act as an electron
collector and transport carrier, thus increasing the
lifetime of the catalyst by limiting photogenerated
electron–hole pairs.
Figure 6 Effect of the graphene content in the visible-light
catalytic hydrogen production with CdS cluster, 0.5 wt% Pt as co-
catalyst and 10 vol% lactic acid as a sacrificial agent. Sample
GCx (x = wt% content of graphene). Reproduced with permission
from reference [123].
J Mater Sci (2020) 55:7156–7183
Mukherji et al. studied the photocatalytic H2 pro-
duction over nitrogen-doped Sr2Ta2O7 coupled with
graphene sheet, for all catalyst 0.5 wt% Pt was used
as a co-catalyst. The authors prepared graphene
oxide from commercial graphite powder using
modified Hummer’s method. The Pt nanoparticles
with 4–6 nm size loaded onto the GO surface are
confirmed by TEM analysis. Besides, the doping of
Sr2Ta2O7 with nitrogen leads to an increase in the H2
production [124]. This can be explained by the fact
that N-doping reduces the overall energy gap and
forms intermediate steps (higher than the VB)
because of N2p and O2p orbitals mixing. Figure 7a
demonstrates the activity of the different composites
with respect to time; the results indicate the steady
increase in H2 production with time, without appar-
ent change in activity. Figure 7b shows the activity
(H2 production) of the different composites, with and
without graphene layer, with methanol as a scav-
enger. The highest activity of 293 lM/h was obtained
with the 5 wt% graphene contents, and the increase
in graphene content to 10 wt% reduced the photo-
catalyst activity, due to the limited light penetration
into the reaction mixture. The electron is generated at
the Sr2Ta2O7Nx and transported on the graphene
layer (high charge carrier mobility) to the Pt site
which is responsible for H2 production.
Babu et al. reported the effect of rGO on the
enhancement of Cu2O–TiO2 composite in the photo-
catalytic water splitting reaction (as shown in Fig. 8)
[125]. The loading of Cu2O–TiO2 composite on rGO
surface was done using low-frequency ultrasonicator
under pulse mode. Under this preparation protocol, a
folded graphene sheet with the well-dispersed Cu2O–
TiO2 composite was achieved. Besides, simultaneous
loading of Cu2O–TiO2 composite and reduction of
GO was occurred during the low-frequency ultra-
sonication. Furthermore, no free Cu2O–TiO2 com-
posite was observed at the background of the TEM
images which confirmed the complete loading of
these composites on the rGO layer. The introduction
of rGO improved the photocatalytic water spilling
from 16656 to 1110968 lmol h-1 gcat-1 over Cu2O–
TiO2 and Cu2O–TiO2/rGO, respectively. The authors
attributed this enhancement to rGO creating a carrier
mobility layer at the heterojunction of Cu2O, TiO2
and rGO preventing electron–hole repair recombi-
nation; this was highlighted by the photoelectro-
chemical and photoluminescence analyses,
respectively. Furthermore, the effect of the rGO
J Mater Sci (2020) 55:7156–7183
Figure 7 Effect of graphene on Sr2Ta2O7-xNx on H2 production
in water splitting photocatalysis, as a function of a reaction time
and b graphene content. Reproduced with permission from
reference [124].
Figure 8 Water splitting over different Cu2O-, TiO2- and rGO-
based catalysts as a function of time. Reproduced with permission
from reference [125].
loading was also investigated and the results
obtained showed the rGO loading goes through a
maximum (at 3%) and then the activity decreased.
7165
The decrease in H2 production with the increase in
the rGO loading ([ 3%) is due to the rGO effect on
light absorption. The authors proposed a mechanism
for the photocatalytic water splitting over Cu2O–
TiO2/rGO based on the CB and VB energies for both
TiO2 and Cu2O. TiO2 acts as a sink for the photo-
generated electrons illuminated from Cu2O since the
former CB energy is lower than the latter. Therefore,
the holes remain within the Cu2O, which is ideal for
charge separation. The role of the rGO surface comes
into play for the electron transfer to the TiO2 CB level;
these electrons are responsible for the reduction of
H? to H2. Glycerol was used as a scavenger or sac-
rificial agent for the removal of h? from the Cu2O
surface. The recyclability study of the Cu2O–TiO2/
rGO catalyst shows that the catalyst maintains the
initial activity for at least four cycles.
Xiang et al. investigated the photocatalyst water
splitting over graphene/C3N4 composite [126]. In this
study, the graphene content and proposed mecha-
nism was highlighted. The H2 production over g–
C3N4 was reported to be 147 lmol h-1; this is
attributed to the unique electronic structure of the
material and moderate energy gap. However, the
introduction of a graphene (0.25 wt%) sheet
increased the H2 production to 202 lmol h-1 and a
further increase in graphene content to 0.5 and 1 wt%
increased the H2 production to 290 and 451 lmol h-1,
respectively. Further increase in the graphene content
leads to a decrease in the photocatalytic activity of the
catalyst. This is due to the increase in light scattering
and opacity which results in less light available for
the reaction. The proposed mechanism for this sys-
tem is illustrated in Fig. 9 in which the electrons
generated in the g–C3N4 by the visible-light irradia-
tion excite the electrons from the N2p orbital (i.e., VB)
to the C2P orbital (i.e., CB) creating a hole in the VB.
Usually small amount of these electrons will be
injected to the Pt particle due to electron–hole
recombination through Schottky barrier [127, 128].
The electrons on Pt reduce H2O to H2, and the holes
on the g–C3N4 react with the sacrificial agent (i.e.,
methanol). However, the introduction of a graphene
sheet provides a new pathway for the electrons
generated on CB to accumulate on the Pt particle (via
percolation mechanism) [129], due to the great elec-
tronic conductivity of the graphene layer. This leads
to hole–electron separation, resulting in a reduction
of the recombination of charge carriers. The steps of
this reactions are shown in Eqs. 1–4.
7166
Figure 9 Proposed mechanism for photocatalytic H2 production
in water splitting over graphene/g–C3N4. Reproduced with
permission from reference [126].
Graphene=g  C3 N4 ! graphene ðe Þ=g  C3 N4 hþ
Graphene ðe Þ þ Pt ! graphene þ Pt ðe Þ
Pt ðe Þ þ 2Hþ ! Pt þ H2


g  C3 N4 hþ þ CH3 OH þ 6OH
! g  C3 N4 þ CO2 þ 5H2 O
The recyclability study of the catalyst showed that
the system is stable for at least four runs without loss
of photocatalytic activity.
Fan et al. highlighted the effect of RGO on P25 in
photocatalysis. The authors investigated the RGO–
P25 composite synthesis method (i.e., UV-assisted
photoreduction, hydrazine reduction and
hydrothermal method) and the optimal sacrificial
alcohol agent (i.e., methanol, ethanol and i-propanol)
on the H2 production from water splitting [130]. The
H2 production as a function of composite synthesis
method increased in the sequence hydrazine reduc-
tion \ photoreduction \ hydrothermal method as
demonstrated in Fig. 10. This is due to the high
electrical conductivity of the graphene layer in com-
parison with pure P25. The best sacrificial is deter-
mined to be MeOH was in good agreement with
previously reported results [131–133].
Table 1 summarizes the current state of the art in
hydrogen production using graphene containing
composites. The different experimental parameters
that are key to catalyst performance and stability,
such as light source, sacrificial agent and graphene
loading, are shown in Table 1. The highest H2 evo-
lution was reported by Babu et al. using Cu2O–TiO2
and reduced graphene oxide [125].
From these literature examples, it is very clear that
the introduction of graphene into the photocatalyst
J Mater Sci (2020) 55:7156–7183

Figure 10 Effect of graphene reduction method on H2 evolution
during water splitting reaction. Reproduced with permission from
ð1Þ reference [130].
ð2Þ
for the water splitting reaction improved the catalyst
ð3Þ activity which is mainly because of the electronic and
surface properties of graphene. Graphene enhanced
ð4Þ the H2 production by preventing charge–hole
recombination and providing a pathway for elec-
trons, since graphene has good electronic property.
However, the reports in the literature highlight
clearly the importance of graphene weight % in the
composite or catalyst. The graphene loading goes
through a maximum after which the H2 production
decreases due to the optical property of graphene
limiting light penetration into the reaction mixture.
Another challenge or a drawback is the need for co-
catalyst, which is usually Pt. The disadvantage of
using Pt is the economic impact of Pt price. The use of
visible light is key in photocatalysis, since it is infi-
nitely available and no need for complex
photoreactor.
Graphene-based material
for environmental remediation
In photocatalytic degradation
In the modern world, the global industrialization has
played the vital role in growing the economy and
urbanization of the current environment [138–140].
The growth of substantial number of industries
caused the pollution mainly water pollution since the
wastages from industries were released in the aquatic
environment [141–144]. Hence, the severe problems
were risen to the aquatic living hoods due to the
J Mater Sci (2020) 55:7156–7183 7167

Table 1 Comparison of H2 evolution over graphene containing photocatalyst, with key experimental parameters

Entry Photocatalyst Light source Sacrificial Mass fraction H2 evolution Enhancement factor References
agent of graphene rate (lmol over the reference
(wt%) h-1 g-1) photocatalyst

1 Sr2Ta2O7-xNxG; Solar light Methanol 5.0 2930 1.50 [124]

co-catalyst: Pt
2 TiO2-G UV light Methanol 6.5 160 2.30 [134]
3 P25-G UV light Methanol 20 740 10.80 [130]
4 TiO2-G UV light NaS ? Na2SO3 2.5 80 1.20 [135]
5 TiO2-G UV light NaS ? Na2SO3 5.0 86 1.90 [136]
6 CdS-G Visible light Lactic acid 1.0 56,000 4.87 [123]
co-catalyst: Pt
7 g-C3N4/G Visible light Methanol 1.0 451 3.07 [126]
co-catalyst: Pt
8 CdS/N-doped G Visible light NaS ? Na2SO3 2.0 1050 5.25 [137]
9 P25-GR 300 W Xe lamp Methanol 0.5 6680 1.68 [131]
Co-catalyst: Pt
10 Cu2O-TiO2/rGO Hg lamp Glycerol 3 110,968 6.66 [125]

wastewater released from the industries. The pre-
vention of mixing of wastewater from the industries
is a challenging task, and it is better to minimize/
degrade the wastewater before mixing into the
aquatic environment. Several methods are available
for the degradation of pollutants which is released
from the industries [145–150]. Among them, photo-
catalysis is a potential way for the degradation/de-
composition of wastewater-contaminated water,
mostly organic pollutants [151–155]. Since the emer-
gence of photocatalysis using semiconductor nano-
materials, a variety of metal, metal oxide, polymeric,
porous, carbon-based materials have been used
[156–163].
However, the focus has been fallen on the carbon-
based semiconductor nanomaterials, especially gra-
phene-based materials, for the photocatalytic degra-
dation of organic contaminants because of its
influence of electron transport assets, potential effi-
cacy, layer structure, large surface area and multi-
functional performance. The valence and conduction
bands of graphene, consisting of bonding p and anti-
bonding p (p*) orbitals, respectively, touch at the
Brillouin zone corners, which makes a single sheet of
graphene a zero bandgap semiconductor [164, 165].
The distance between the close carbon–carbon might
lead to intensive overlapping of electronic bands, and
the electrons and holes in graphene behave similarly
to mass-free charges [166]. Tuning the electronic
properties of graphene by introducing heteroatoms
or functionalities extends the applications of gra-
phene to photocatalysis processes [167]. The property
of electron transport was occurred, while the gra-
phene/graphene oxide (GO)/reduced graphene
oxide (rGO) is supported to other semiconductor
nanomaterials. Hence, in this section the photocat-
alytic behavior of graphene-based nanomaterials is
discussed.
The photocatalytic degradation of methyl orange
(MO) dye solution was performed by Babu et al.
using rGO-supported CuO–TiO2 nanocomposite
[168]. The graphitic oxide was prepared from gra-
phite powder by following modified Hummer’s
method. Sono-chemical methods were used for the
exfoliation of graphitic oxide to form GO and also for
the reduction of GO to produce rGO. Likewise, the
CuO–TiO2 nanocomposite was loaded onto the sur-
face of rGO under ultrasonication. Besides, the
irregular edges were observed for the rGO layers
under TEM investigation. The authors provided the
detail discussion of role of rGO in the photocatalytic
process (Fig. 11). The energy gap of the CuO–TiO2
nanocomposite was not altered/affected even after
the doping of rGO, and it suggested that the rGO be
only as a solid support. The PL analysis of the CuO–
TiO2 and rGO-loaded clearly provided an idea that
the rGO not only acts as a solid support and facili-
tates fast transport of electrons but also hinders the
rate of charge carrier recombination. Moreover, the
role of rGO was strongly evidenced by the
7168
photoelectrical response which could clearly explain
the electron transferring performance. Hence, it was a
solid evidence for the rGO-loaded nanocomposite
might exhibit the higher photocatalytic activity.
The authors evaluated the diffused sunlight-as-
sisted photocatalytic mineralization of MO dye
solution in the presence of different photocatalysts,
viz. CuO-, TiO2-, CuO–TiO2- and rGO-loaded CuO–
TiO2 nanocomposites. The results suggested that the
rGO-loaded CuO–TiO2 nanocomposites exhibited an
enhanced photocatalytic efficiency compared to that
of other photocatalysts since the characterization
results are unique. Moreover, they also performed
the photocatalytic reaction under different condi-
tions, viz. dark, light alone, ultrasound, diffused
sunlight and use of both ultrasound and diffused
sunlight at the same reaction. The results observed
suggested that the combined ultrasound and diffused
sunlight provided a higher efficiency. The TOC
analysis suggested that the complete mineralization
of the MO dye solution in the presence of rGO-loaded
CuO–TiO2 nanocomposites and the photocatalyst
possesses significant stability even after its third run.
The electron transfer property and the possible
mechanism for the photocatalytic degradation of MO
dye solution using rGO-loaded CuO–TiO2
Figure 11 Plausible mechanism for the ultrasound-assisted photocatalytic degradation of MO under diffused sunlight. Reproduced with
permission from reference [168].
J Mater Sci (2020) 55:7156–7183
nanocomposites are given in Fig. 12. The mechanism
and the reactive oxidative species involved in the
photocatalytic reaction were also evidenced. The
authors also performed the sono-photocatalytic
degradation of organic pollutants, viz. methylene
blue (MB) dye solution and 4-chlorophenol.
The simple approach for the synthesis of silver-
loaded rGO (rGO–Ag) nanocomposites was done by
Bhunia et al., and it was utilized as a visible-light
active photocatalyst against the colorless endocrine
disruptors (phenol, bisphenol A and atrazine) [169].
The XPS and XRD analyses strongly evidenced the
formation of pure rGO–Ag and poses higher crys-
tallinity. Besides, the authors confirmed the com-
posite nature of rGO–Ag using TEM analysis which
evidenced the homogeneous decoration of Ag
nanoparticles over rGO surface. Furthermore, the
average particle size of Ag nanoparticles was esti-
mated to be around 5 nm. The authors varied the
loading of Ag nanoparticles on rGO support and
prepared a different loading ratio of 1:0.5, 1:0.25 and
1:0.12. The optical properties suggested that the rGO–
Ag possessing both the p – p* transition of rGO at
265 nm and the surface plasmon resonance (SPR)
peak of Ag at 420 nm was appeared, and the SPR
J Mater Sci (2020) 55:7156–7183
Figure 12 Synthetic route for the fabrication of reduced graphene oxide–silver nanoparticle (rGO–Ag) composite and photocatalytic
degradation strategy for endocrine disruptors. Reproduced with permission from reference [169].
peak of Ag gradually increased while increasing the
Ag content.
The photocatalytic degradation of well-known
endocrine disruptor compounds, viz. phenol,
bisphenol A and atrazine, was performed by the
rGO–Ag nanocomposites under visible-light irradia-
tion. The electrostatic interaction between anionic
graphene oxide and cationic Ag nanoparticle leads to
the strong interaction between two components, and
the presence of the Ag component inhibits the
extensive rGO–rGO interaction. Thus, rGO surface is
accessible for organic pollutants. In addition, a thin
silica coating (*1–5 nm) offers a shorter distance
between rGO and silver so that tunneling of photo
excited electron is possible. The results suggested
that the rGO–Ag (0.25) showed excellent photocat-
alytic efficiency compared to that of other ratios of
Ag-loaded rGO nanocomposites. Moreover, the
authors performed the reusability test and with the
help of photoluminescence spectroscopy they have
found out the hydroxyl radical as an active reactive
oxygen species (ROS) and provided the tentative
mechanism for the photocatalytic degradation
reaction.
Graphene-wrapped titanium dioxide nanoflower
composites (G–TiO2) were synthesized using two-
step solvo/hydrothermal process. The authors
obtained the nanoflower morphology with the parti-
cle size of 10 nm observed in the TEM images and the
TiO2 deposited on the layered GO was clearly visible.
Electrochemical impedance spectroscopy (EIS) was
7169
performed, and the results suggested the improved
charge transfer and decreased ionic diffusion resis-
tance of the TiO2 nanoflowers over commercial P25.
The schematic representation discussed by the author
is given in Fig. 13.
The energy gap value observed for P25, the TiO2
nanoflowers and G–TiO2 from the Kubelka–Munk
function was 3.0 eV, 2.9 eV and 2.6 eV, respectively.
The absorption clearly suggested the increased
charge generation efficiency and subsequently
increased potential radical generation and target
degradation. The photocatalytic degradation of MB
dye solution was performed under UV light illumi-
nation in the presence of different photocatalysts like
P25, the TiO2 nanoflowers and G–TiO2. The results
observed from the photocatalytic degradation of MB
dye solution suggested that almost 90% of the dye
solution was degraded within 30 min of irradiation.
This enhanced performance might be due to the
ability of graphene to increase the conductivity, slow
down the recombination and provide adsorption
sites for MB dye solution [170].
Likewise, Malekshoar et al. reported the graphene-
based titanium dioxide and zinc oxide composites
(TiO2–G and ZnO–G) for the photocatalytic degra-
dation of phenol [171]. The successful loading of TiO2
or ZnO nanoparticles over GO surface was analyzed
by using SEM and TEM. In addition, the size of these
nanoparticles was also estimated from TEM images.
The authors mentioned that the oxygen functional
groups (–COOH and –OH) existing on the GO
7170
Figure 13 Proposed diagram of the photocatalytic mechanism for
graphene-wrapped TiO2 nanoflowers. The main photodegradation
pathways include (1) the reduction and oxidation of adsorbed
water species by a photogenerated electron–hole pair and (2)
oxidation of MB by donating an electron to graphene (or the
photocatalyst). Reproduced with permission from reference [170].
surface are responsible for the effective loading of the
nanoparticles. The rate was enormously increased up
to 30% compared to that of pure TiO2 and ZnO
nanoparticles. This demonstrated that the graphene
conduct the electrons and suppress the recombina-
tion rate, while coupling of the two composites pro-
duced more efficient charge separation and longer
life time of charge carriers which eventually
enhanced the photocatalytic efficiency. The opti-
mization of the various operational parameters like
catalyst loading, phenol concentration, pH and light
intensity was evaluated. The complete degradation of
40 ppm phenol solution was occurred within 60 min
in the presence of coupled ZnO–G/TiO2–G photo-
catalysts at the optimum conditions. It is well evi-
denced from these literature examples that loading of
graphene effectively increases the photocatalytic
performance of semiconductors.
In heavy metal removal
Heavy metal contamination in environment and
aquatic systems is one of the critical problems of the
universe. The discharge of heavy metals into aquatic
system, soil and atmosphere creates the extreme
pollution to the environment. Most of the heavy
J Mater Sci (2020) 55:7156–7183
metal ions are highly soluble in the aquatic environ-
ment; it also tends to bind with essential cellular
components such as proteins, enzymes and nucleic
acids and restricts their functioning of living organ-
ism and human body [172, 173]. The important
sources of heavy metals are mining industry, metal
plating, sewage irrigation, electronic industry, fertil-
izer production, pesticides and variety of plastic
synthesis [174–179]. Recently, the amount of release
of heavy metals increase in ecosystem is due to the
increases of heavy metals used in industries [180].
The most common heavy metals which present in
environment are arsenic, cadmium, chromium, cop-
per, lead, mercury, nickel and zinc. Even at low
concentration these heavy metal ions may cause
serious health risk toward human beings such as
kidney damage, emphysema, hypertension, neuro-
logical effects and even cancer [181–184].
The heavy metals should be removed as even a
trace amount of in aquatic system caused serious
health hazards (Fig. 14). Various methods such as
chemical precipitation, ion-exchange, coagulation,
reverse osmosis, electrochemical processes, adsorp-
tion and solvent extraction are being used for the
removal of heavy metals [185–189]. Among these, the
technique called adsorption is the best that is
employed for the removal of heavy metal ions from
aquatic system.
Nowadays, large numbers of adsorbents are
available in the market such as activated carbon [190],
polymeric adsorbents, clay [191] and palm shell [192].
However, the low performance against the metal ion
removal makes it more challenging task. On the other
hand, graphene oxide (GO) and its oxide derivatives
have been successfully used as an adsorbent due to
the large surface area, lamellar structure, good
mechanical and electrical properties [193, 194]. In this
part of the review, the application of GO and its
composites in the adsorption of various heavy metal
ion removal from aquatic system is discussed in
detail.
Removal of heavy metal ion by GO
The GO is considered as a potential adsorbent for the
removal of heavy metal ions such as Au(III) and
Pt(IV) [195], Pb(II) [196], Cu(II) [197], Zn(II) [198],
Cd(II) [199], Co(II) [200], etc., with the corresponding
adsorption capacities of which were much higher
than those of other adsorbents under similar
J Mater Sci (2020) 55:7156–7183
Figure 14 Effect of heavy
metal ions to human health.
conditions. Pristine GO has large surface area due to
aggregation which cannot produce performance
against the removal of heavy metal ions. As a result,
surface of the GO required chemical modification for
the removal of heavy metal ion [201].
Removal of chromium
Generally, chromium occurs in two main oxidation
states: Cr3? and Cr6?. Among these, the trivalent
chromium [Cr3?] is essential in the functioning of
insulin hormone. However, Cr6? is highly dangerous
and it’s poisonous nearly 500 times more than that of
the Cr3?. Similarly, based on the pH of the medium
Cr ion can exist in the form of chromate or dichro-
mate ions. These ions are highly soluble in water as
well as highly toxic in nature. As per the statement of
U.S. Environmental Protection Agency (EPA), Cr6? is
most hazardous pollutant to environment. Hence, the
removal of Cr ion is necessary from aquatic system
[202]. Generally, adsorption behavior of GO toward
Cr removal is greater than that of other adsorbents
which might be due to the higher electronegativity of
7171
Cr ion that exhibits stronger attraction toward the
surface of negatively charged GO.
Seongpil et al. proposed a mechanism for the
removal of ions from water through graphene and
GO composites as shown in Fig. 15 [203]. Surface
modification was done to make the graphene surface
as hydrophilic. This surface-modified graphene gen-
erally possesses low range of water contact angles
(WCA). Another researcher observed that nearly 90%
of K2CrO7 was reduced by SnS2/rGO composites,
whereas the pure SnS2 reduced only 36% of K2CrO7
under similar conditions. Besides, the change in pH is
one of the key factors in the adsorption of Cr ion from
aqueous solution which greatly influences the per-
centage of heavy metal removal. This might be
because Cr6? ion present as HCrO4- and CrO42- at
pH less than and greater than 6.8, respectively. Chen
et al. noticed that ion exchange is higher at the low
pH level; however, OH- ion concentration is more at
higher pH values which develop the competition
between the OH- ion and Cr anion for the adsorption
over GO sites [204, 205]. Consequently, the adsorp-
tion of Cr ion decreases with increases of pH values
in their studies.
7172 J Mater Sci (2020) 55:7156–7183

The surface area of the GO is not only a key factor
for the removal of Cr ion. Reduced GO/polypyrrole/
Fe3O4 composites (Ppy–Fe3O4–rGO) removed more
amount of Cr ion as compared to Fe3O4–rGO. The
calculated surface area of Fe3O4–rGO and Ppy–
Fe3O4–rGO is 126.4 m2 g-1 and 80.5 m2 g-1, respec-
tively. Though the surface area of Ppy–Fe3O4–rGO is
low, the Cr ion removal efficacy is relatively higher
than that of the Fe3O4–rGO which is mainly due to
the electrostatic attraction [206]. In addition, GO
membranes were used for the filtration process to
remove the heavy metals as illustrated in Fig. 15. The
selectivity can be achieved by size exclusion and/or
electrostatic repulsion between charged species and
the pores [207]. The authors used roll-to-roll pro-
duction technique for the large-scale production of
high mechanically stable graphene. Besides, this
methodology resulted in the formation of nanopor-
ous GO stacking and hence improved the filtration
capability. These nanoporous graphene membranes
rejected the salts because of its larger size and also
due to the electrostatic interactions.
Removal of arsenic
Arsenic ion interferes with a numerous of important
physiological actions. It can easily attach with
proteins and enzymes which in turn produce slow
metabolic disorders. In general, the arsenic ions exist
in two oxidation states such as arsenite (As3?) in the
form of arsenious (H3AsO3) acid and arsenate (As5?)
in the form of (H3AsO4). However, it is observed that
As3? ions are more toxic than As5? [208–210].
Sima et al. prepared graphene oxide–zirconium
nanocomposites (GO–Zr) for the removal of arsenic
ions (both (As3?) and (As5?)). They observed that
As5? ions can be absorbed rapidly for first 5 min after
that slowly increased to attain equilibrium after
10 min [211]. Under similar conditions, the removal
of As3? ions takes more time compared to As5? ions.
But the removal capacity of As5? is higher than that
of the As3? and they achieved nearly 100% removal
in the presence of 100 mg GO–Zr nanocomposites
(2 mg mL-1) later than 20 min at room temperature.
Zhang et al. used (GO) cross-linked with ferric
hydroxide series of composites for the removal of
arsenic ions both As3? and As5? [212]. They revealed
that the efficiency of removal of arsenic ion was
increased by as-prepared composites. The removal of
arsenate effectively occurred in the pH range
between 4 and 8. However, the efficiency of arsenate
removal is decreased at higher pH values.

Figure 15 Schematic
representation of the two types
of graphene-based
membranes: a nanoporous
graphene membranes consist
of a single layer of graphene
with nanopores of defined pore
size. Selectivity is achieved by
size exclusion and electrostatic
repulsion between charged
species and the pores.
b Membranes composed of
stacked GO sheets. In stacked
GO membranes, the size of the
pores is determined by the
interlayer distance between the
sheets. Reproduced with
permission from reference
[207].
J Mater Sci (2020) 55:7156–7183
Removal of Cu (II), Pb(II) and Cd(II) ions
Li et al. prepared diethylenetriaminepentaacetic acid
(DTPA)-modified magnetic graphene oxide (MGO)
composites (DTPA/MGO) for the removal of Cu(II),
Pb(II) and Cd(II) ions in low pH levels. Interestingly,
the DTPA/MGO composites were able to remove
higher amount of Cu(II), Pb(II) and Cd(II) ions as
compared to that of as-prepared MGO. Also, it is
faintly dependent of pH values [213].
Likewise, Hao et al. prepared a various metal ion
solution of Cu(II), Pb(II), Ni(II), Co(II), Cd(II) and
Cr(III) for competitive adsorption [214]. They sug-
gested that the removal of Pb(II) ion was high on the
SiO2/graphene composites due to the electrostatic
interaction between Pb(II) cations and negative sur-
face charge and/or p-electrons of SiO2/graphene
composites. However, the removing ability decreases
for other ions; it represents that this composite is
highly selective for the removal of Pb(II) ions.
In addition, Gu et al. found that the order attraction
of heavy metal ions to GO was Pb(II) [ Cu(II) [ [
Cd(II) & Ni(II) & Zn(II) [ Sr(II) & Ca(II), whereas
the order of ionic radius was Pb(II) [ Sr(II) [
Ca(II) [ Cd(II) [ Zn(II) [ Cu(II) [ Ni(II) [215]. It
showed that the removal of heavy metal ions was not
based on the ionic radius and, however, more asso-
ciated with the electronegativity of metal ions.
Table 2 summarizes the recent reports involved in the
removal of heavy metals from wastewater using GO
and GO-based materials.
Table 2 Maximum removing capacities (Q, mg/g) of several heavy metal ions on GO
Adsorbents Removal of heavy metal ions Amount of removal (mg/g)
GO Cu(II) 294
Zn(II) 345
Cd(II) 530
Pb(II) 1119
GO Cu(II) 117.5
GO Ni(II) 38.61
DTPA/ MGO Cu(II) 131.4
Pb(II) 387.6
Cd(II) 286.5
7173
Adsorption time and temperature
The adsorption time plays a significant role in the
removal of heavy metal ions by GO [219]. In general,
at the beginning, the rate of heavy metal removal is
faster and then gets slower after it reaches the max-
imum equilibrium as the absorption time is extended.
Initially, the adsorption sites are more on the GO
surfaces that is enough for heavy metal ions. How-
ever, as the adsorption time increases, both adsorp-
tion sites and thrust of heavy metal ion decreased.
Then the absorption attains the saturation [220].
Temperature also affects the adsorption rates
which causes the molecular interaction and solubility
[221]. When the temperature increases, it leads to an
increase in the adsorption sites on the surface of the
GO and increase in the diffusion rate of heavy metal
ions. Further, the adsorption rate increases with the
increases in temperature which corresponds to that
adsorption process is endothermic and spontaneous
process.
Conclusions and future directions
Graphene, a rising-star material, gained more atten-
tion after it was first reported by Novoselov and co-
workers in 2004. Certainly, graphene-based materials
are highly potential support materials in energy and
environmental remediation. The given examples
strongly support this claim. As graphene surface
provides excellent electron mobility, it can be highly
useful in photovoltaics, photocatalytic water splitting
and photocatalytic organic pollutant degradation/
pH Temperature (K) References
5.0 298 [216]
5.3 RT [217]
6.0 RT [218]
3.0 RT [213]
7174
mineralization from the wastewater. Similarly, ther-
mal and chemical stability of graphene makes it
suitable as a support material for nanocatalysts for a
wider range of applications. Furthermore, high sur-
face area and outstanding adsorbing capability assist
in the removal of heavy metals and other pollutants
from wastewater as an adsorbent. However, the
value of these graphene-based materials in catalyst
market denotes only a modest segment. The potential
growth of the graphene-based material in the cat-
alytic industries largely depends on (a) better
understanding of the surface chemistry of graphene-
based materials, (b) fine tuning of the microstructure
of these materials to exploit as a unique catalyst for a
specific application and (c) significant development
in quality control and manufacturing approaches.
The rapid development of graphene-based materials
in fuel cells, solar cells, hydrogen production, energy
carrier and wastewater treatment evidenced the sig-
nificant possibility to increase the market value of the
graphene-based catalysts in the near future.
Compliance with ethical standards
Conflict of interest The authors declare that there is
no conflict of interest regarding the publication of this
paper.
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