Environmental Technology Reviews

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A review on graphene–TiO2 and doped

graphene–TiO2 nanocomposite photocatalyst for
water and wastewater treatment

B. A. Bhanvase, T. P. Shende & S. H. Sonawane

To cite this article: B. A. Bhanvase, T. P. Shende & S. H. Sonawane (2017) A review

on graphene–TiO2 and doped graphene–TiO2 nanocomposite photocatalyst for
water and wastewater treatment, Environmental Technology Reviews, 6:1, 1-14, DOI:
10.1080/21622515.2016.1264489

To link to this article: http://dx.doi.org/10.1080/21622515.2016.1264489

Published online: 13 Dec 2016.

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ENVIRONMENTAL TECHNOLOGY REVIEWS, 2016
VOL. 6, NO. 1, 1–14
http://dx.doi.org/10.1080/21622515.2016.1264489

A review on graphene–TiO2 and doped graphene–TiO2 nanocomposite

photocatalyst for water and wastewater treatment
B. A. Bhanvasea, T. P. Shendea and S. H. Sonawaneb
a
Department of Chemical Engineering, Laxminarayan Institute of Technology, Rashtrasant Tukadoji Maharaj Nagpur University, Nagpur, MS,
India; bDepartment of Chemical Engineering, National Institute of Technology, Warangal, Telangana, India

ABSTRACT ARTICLE HISTORY

TiO2 is a more effective photocatalyst for the photocatalytic degradation of organic pollutants. Received 8 July 2016
However it shows more reactivity under UV light and around 5% of solar spectrum contains UV Accepted 20 November 2016
radiations. A new approach for the degradation of pollutants present in wastewater is suggested
KEYWORDS
by making use of nanocomposite photocatalysts. The technique has potential for the treatment Graphene; TiO2;
of wastewater because of the use of doped graphene-based nanocomposite photocatalysts. nanocomposite;
Graphene is a one-atom-thick planar sheet of sp 2-bonded carbon atoms that are densely packed photocatalyst; doping
in a honeycomb crystal lattice. Furthermore, graphene has high electron mobility and therefore
it will supress the recombination of the electron-hole pair formed which in turn improves the
effectiveness of the graphene-TiO2 photocatalyst. In addition, development of doped graphene-
TiO2 photocatalyst will be useful as it can be effective for the degradation of pollutants in the
visible sunlight. Recently, there has been an increase in interest in the preparation of high
performance graphene-based TiO2 photocatalyst with doping of it using metal and non-metal
ions. In this review, the preparation method and application of TiO2, graphene-TiO2 and doped
raphene-TiO2 photocatalyst are presented.

Introduction
Organic pollutants play a very important role in the
water pollution, it mostly takes up more than 50% of
water pollutants. Water contamination majorly comes
from human activities, which produces a large
number of industrial, agricultural and domestic
wastes that are directly discharged into the water.
The major path of this kind of organic pollutants are
concerned with the industry of plastics, synthetic
fibres, synthetic rubber, detergents, pigment, solvents
synthesis, paints, pesticides, food additives, pharma-
ceuticals and other organic compounds. These hazar-
dous pollutants in water and wastewater are very
dangerous for human and aquatic life. Also they are
well thought-out as toxics or a contributor diseases to
human that includes the human hepatic dysfunction,
carcinogenics, hindering the development of human
body and endangering body endocrine system [1–3].
In the late 1960s, photocatalysis technology was
utilized for the application of water and wastewater
treatment. Studies have paid more attention to
photochemical-assisted techniques for water and
wastewater treatment. Photocatalysis is an important
technique which is useful for the decomposition of
various organic toxins into carbon dioxide and water
using very less energy and it is totally environmentally
friendly. Numerous studies have been reported on the
use of TiO2 as a photocatalyst for various applications
such as degradation of organic pollutants, hydrogen
generation from water splitting and air purification
[4–6]. However, photocatalysts have drawbacks such
as high cost, low efficiency, high electron–hole pair
combination speed and UV-radiation response. TiO2
is a broadly used photocatalyst for the treatment of
wastewater; the possible reasons are (1) high stability,
(2) low cost and toxicity and (3) enhanced photocata-
lytic activity compared to other semiconductor
materials. However, TiO2 has photocatalytic activity
in the UV region and the earth’s solar spectrum con-
tains around 5% UV radiations. Therefore, it has
limited photocatalytic activity in the visible range of
the solar spectrum. Also the recombination rate of
electron and hole is higher in TiO2. These problems

CONTACT B. A. Bhanvase bharatbhanvase@gmail.com Department of Chemical Engineering, Laxminarayan Institute of Technology, Rashtrasant Tukadoji
Maharaj Nagpur University, Nagpur, MS 440033, India
© 2016 Informa UK Limited, trading as Taylor & Francis Group
2 B. A. BHANVASE ET AL.
can be overcome by the preparation of graphene–
TiO2 composite photocatalyst as the electron mobility
of graphene is higher, which enhances the transport
of the electron and recombination of the electron
and hole gets suppressed. Furthermore, it is possible
that with the use of graphene–TiO2 composite
agglomeration of TiO2 can be avoided so that higher
surface area can be maintained and there will be
more active sites for the degradation of pollutants
and this improves the degradation rate of the pollu-
tants with the use of lesser amount of graphene–
TiO2 composite-based photocatalyst. Furthermore,
graphene has excellent thermal conductivity, larger
specific area, better charge carrier mobility and good
mechanical strength [7]. These electronic and photo-
nic properties of graphene make it an ultimate candi-
date material for enhancement of TiO2 photo-
reactivity. Also graphene–TiO2 nanocomposites have
enhanced photoactivity resulting from increased
extended visible light absorption and strong affinity
for other organic materials. Also TiO2 combined with
graphene acts as an electron trap, which promotes
electron–hole separation and facilitates interfacial
electron transfer.
Further, to have the applicability of the graphene–
TiO2 composite photocatalyst in the visible range of
the solar spectrum, the modification of graphene–
TiO2 composite photocatalyst can be carried out
with the use of metal and non-metal ions. Therefore,
the review of this type of work is included in this
manuscript to study the various parameters and use
of a doped graphene–TiO2 composite photocatalyst
in the degradation of pollutants in the presence of
UV and visible sunlight. In view of this, the present
review aims to present a logical story of TiO2, gra-
phene–TiO2 and doped graphene–TiO2 composites,
their preparation methods and applications as a
photocatalyst. Furthermore, in this review, photo-
assisted applications such as hydrogen generation
from water splitting are presented.
TiO2 photocatalyst
TiO2 has been considered and studied widely since it
has been considered as one of the most effective
photocatalysts for the degradation of organic pollu-
tants [8]. It is due to its long-term thermodynamic
stability and relative nontoxicity. Today, many
research groups have managed an enhancement in
the photocatalytic properties and optimized it to
degrade various organic and inorganic pollutants [9].
The energy from solar radiation that reaches the
earth’s surface will stimulate TiO2 particles at less
than 5% of all radiation energy (λ < 385 nm) [10]. A
novel type of titanium oxide photocatalyst could
degrade pollutants effectively under this kind of
irradiation. TiO2 has a narrow band-gap energy (Ebg
= 3.2 eV for anatase type TiO2) and can be used as a
photocatalyst for oxidation or reduction. The oxidation
reaction of various organic pollutants in water and air
is generally initiated by the very active radicals such as
OH• and O•2 or holes generated during UV irradiation.
This oxidation reaction of organic species in water
and air leads to partial or total oxidation and CO2
and mineral acids’ formation takes place [11–13].
Fujishima was the first to investigate photoelectrolysis
[14]. In this study the rutile n-type TiO2 electrode have
been selected as an oxidant which has an adequately
positive valence band to cause oxidation of water to
oxygen. The formation of electron–hole pair takes
place, when the TiO2 photocatalyst is irradiated with
UV light. This mechanism is widely accepted. The
charge carriers may stay inside the crystal or at the
surface so that they can react with the pollutants avail-
able. The holes in the valance band are highly oxi-
dative, which not only straightly react organic
molecules that are adsorbed on the TiO2 but also
oxidize the organic pollutants indirectly through the
generation of •OH radicals. These formed •OH radicals
are highly reactive and are responsible for the
initiation of the degradation process of organic pollu-
tants during photocatalysis [15]. There is high oxi-
dation electrode potential between conduction band
electrons and valence band holes. In redox chemistry
reactions which include organic pollutant decompo-
sition in water, the light energy can be very efficiently
used. The water organic pollutants discharged from
textile, paper and plastic industries are always danger-
ous to humans. Phenol, dye stuff and aromatic like
compounds [4–6] are the main organic water pollu-
tants with high toxicity. All these industries usually
contaminate the environment by releasing toxic, can-
cerogenic and coloured wastewater [1–3]. After a
thorough study, TiO2 has been considered to have a
wide-energy band gap which is a constraint to extract-
ing more radiation energy under the visible light
wavelength. Most light-sensitive semiconductor
materials have the drawbacks of low quantum yields

and the lack of visible light utilization [4]. Photocataly-
sis has not been widely applied to treat wastewater in
industry, as its reaction speed is not high enough [16].
Photocatalytic decomposition of a variety of organic
species present in wastewater has been broadly exam-
ined and numerous nanometer-sized photocatalysts
have been established for photocatalysis technology
[17]. Photocatalytic water treatment causes photo-
degradation of organic matter such as alkanes, lipids,
organic acids, aromatics, etc. These molecules are reg-
ularly oxidized to low molecular weight intermediates
and eventually into CO2, H2O and other anions with
radiation [16]. Heterogeneous nano photocatalysts
are nanometer-sized particles (20–200 nm) with
photo sensitivity and high-surface area. Since the
particles have ultra-small size and higher surface
area, the electronic property of the particle is totally
different from a bulk arrangement. The activation of
the catalyst surface is much superior to that of the
normal semiconductor. The quantum size of particles
leads to separation of energy levels [18,19] therefore
the potential of conduction band becomes more
negative, and the energy gap becomes wider. There-
fore, nano-semiconductor particles have a stronger
oxidizing or reducing potential which leads to a
much easier contribution to photo-electronic reaction.
The catalysts with wide band-gap energy get stimu-
lated under ultraviolet light [20]. Thus, the develop-
ment of semiconductor based photocatalyst for the
degradation of pollutants in the visible light attracts
more interest of the researchers.
When light was irradiated on the surface of TiO2 at a
wavelength shorter than that of the TiO2 band gap,
that is, (3.1 eV), water could be decomposed using
ultraviolet irradiation according to the following reac-
tions:
TiO2 + hv  e− + h+ , (1)
2H2 O + 4h+  O2 + 4H+ , (2)
2H+ + 2e−  H2 , (3)
The overall reaction is:
2H2 O + 4hv  O2 + 2H2 . (4)
TiO2 is used as a semiconductor due to its beneficial
properties. TiO2 particles with nano-size have high
photocatalytic activity, low cost and nontoxicity. Kim
et al. [21] employed TiO2 with anatase crystal for
ENVIRONMENTAL TECHNOLOGY REVIEWS 3
sterilization of food-borne pathogenic bacteria. Zinc
oxide is also a photocatalyst similar to TiO2 because
of its strong oxidizing power, nontoxicity and low
cost. ZnO is a wide band-gap semiconductor
(3.37 eV) with a conduction band edge located at
about the same level as that of TiO2.
The most photoactive form of TiO2 is thought to be
anatase due to its high adsorption of organic com-
pounds and high hole trapping rate, though the
rutile and brookite phases have also been shown to
be photoactive [22]. In fact, TiO2 containing multiple
phases has been shown to improve photocatalytic
activity and reduce recombination of charge carriers.
The anatase and rutile TiO2 phases are the most rel-
evant and widely studied in the degradation studies.
The most thermally stable crystal phase of TiO2 is
anatase (101) [23]. Both anatase and rutile have tetra-
gonal crystal structures, and the transformation of
anatase into rutile is possible by annealing anatase
at temperatures greater than 400°C [20]. At neutral
pH, the conduction band of anatase has a potential
of −0.5 eV. The valence band is also sufficiently posi-
tive to oxidize H2O and other hydroxide species to
form their respective radicals. When placed relative
to the redox potential of organic functional groups
such as aromatics, phenols, amines and sulphur
bands, TiO2 is highly capable of inducing redox reac-
tions. Apart from photocatalytic applications, TiO2 is
used extensively as a pigment in paints and coatings,
as a UV-blocker in sunscreens and as a food additive
[24]. TiO2 is useful as a white pigment due to its
high refractive index and high brightness [14]. Its
high refractive index means that light is easily bent
and redirected off of the surface – even for very thin
layers of TiO2. With the addition of strong UV absorp-
tion, this also makes TiO2 a useful additive in sunsc-
reens. In foodstuff, TiO2 is commonly used as both a
whitening agent and as an anti-bacterial additive for
increasing product shelf-life. Now it is well known
that TiO2 or other semiconductors and their modified
particles can be adapted for various applications. Kim
et al. [21] employed TiO2 with anatase crystals for ster-
ilization of food-borne pathogenic bacteria. TiO2 with
in close proximity to ultraviolet radiation (UV-A) can
produce electronic holes (h+) in valence band and is
responsible for the generations of hydroxyl radical
(OH•) through the oxidation of water which can be
capable of decomposing the bio-cell efficiently and
remove bacteria. Thus photocatalysts play a significant
4 B. A. BHANVASE ET AL.
role in a heterogeneous system identical to UV
radiation.
Doped TiO2 photocatalyst
One of the effective ways to extend light absorption in
the visible region of the photocatalyst includes het-
eroatom doping technology, which also modifies the
property of a photocatalyst. This reduces the recombi-
nation rate of photo-induced electrons/holes. At the
same time the doping ion can inflict structural
defects to confine the electronic carrier and extend
its lifespan. The heteroatom in the crystal lattice will
lead to structure distortion and different ion size,
breaking the symmetry of the crystal. This phenom-
enon is advantageous in improving the photo-
induced electron and hole separation. Though TiO2
is capable of degrading the organic pollutants into
CO2 and H2O under UV-irradiation, it cannot absorb
visible light by means of wavelengths longer than
387 nm and because of a greater band gap of
3.2 eV. Therefore, TiO2 can only utilize 3–5% of the
total solar energy reaching the earth’s surface. The
general technique for prolonging the activity of TiO2
in the visible light region is doping [6,25–28].
The modification of TiO2 photocatalyst is being
considered and widely studied because the general
effectiveness of photon exploitation by TiO2 is less
due to the recombination of electron and hole
which basically transforms radiation into thermal
energy. Indeed, photon scattering and the intrinsic
physical properties of TiO2 limit the absorption of
photons to those with UV or greater wavelength
energy lights [29]. Because of this reason, photocata-
lyst modification of TiO2 has been considered as one
of the key technologies in future photo-chemistry.
The properties of TiO2 relevant to photocatalysis
have been widely studied [30]. The doping method
is generally used to modify the TiO2 or other photoca-
talysts. One of the effective ways to extend light
absorption in the visible region of the photocatalyst
involves heteroatom doping to enhance the property
of the photocatalyst. It involves the reduction in the
recombination rate of the photo-induced electrons/
holes. The doping ion can cause structural defects in
the prepared photocatalyst which suppress the
recombination of electron hole pair. The heteroatom
present in the crystal lattice will lead to structural dis-
tortion and different ion size, breaking the symmetry
of the crystal. This phenomenon is beneficial in
improving the photo-induced electron and hole separ-
ation. Zou et al. [20] reported a encouraging result for
TiO2 with heteroatom doping technology. They have
developed nickel–indium–tantalum-oxide with nickel
and doping. During the experiment the catalyst
samples remained quite stable under visible light
irradiation. The band gap was between 2.3 and
2.6 eV. The band structure of NiO at Ni 3d orbits can
absorb ultraviolet visible irradiation even more at
420–520 nm. Fe3+ has been found to be the most
acceptable dopant for TiO2 modification because of
its unique 3d atomic orbitals with half-filled electron
and moderate molecular energy [31]. Zhu et al. [31]
have claimed that Fe3+ can be successfully doped
into the TiO2 lattice by the sol–gel method under
different calcination conditions. DRS spectra and
Raman diffraction indicate that the Fe3+-doped TiO2
particle can have a narrow band gap. The crystal struc-
ture of TiO2 plays a very important role and anatase
TiO2 is much more efficient than rutile lattice in
organic pollutant degradation. Non-metal dopants
are considered to be more beneficial to catalyst modi-
fication because electronic energy level in non-metal
atoms is discrete, which will narrow the semiconduc-
tor band gap. Compared with metal dopants, the
non-metal element increases the surface area and
adjusts the pH value of the surface for enhancing
the pollutant adsorption process [24]. Yang et al. [23]
introduced carbon and nitrogen into the TiO2 lattice
and concluded that the visible light sensitivity was
enhanced by narrowing the band gap due to mixing
N 2p and O 2p states. Also carbon dopant played a sig-
nificant role in the enhancement in the separation of
the photo-excited phase [23] and weaken recombina-
tion. The N–C-doped TiO2 photocatalyst has superior
performance in degradation of dyes under visible
irradiation. Zou et al. [20] presented a good result
about TiO2 with heteroatom doping technology. Zou
et al. [20] said that Fe can be successfully doped into
the TiO2 lattice the by sol–gel method considering
different calcination conditions. The crystal structure
of TiO2 plays a very important role and anatase TiO2
is much more efficient than rutile lattice in organic pol-
lutant degradation. In Raman diffraction the Fe-doped
TiO2 particle results in narrowing the band gap energy.
Non-metal dopants are considered to be more ben-
eficial for catalyst modification. When compared
with metal dopants, non-metal dopants increase the

surface area and adjust the pH value of the surface for
enhancement in the pollutant adsorption process [24].
In 1967, Fujishima and Honda [14] first reported a
photocatalytic reaction which has been found to be
of interest in the application of photo-semiconductor,
water treatment, novel energy and photo electric
property. In their report, they mentioned that water
may be hydrolysed on the surface of a titania single
crystal electrode with the introduction of wavelength
radiation, which reveals the phenomena with the
possibility of production of hydrogen gas from solar
radiation energy, and thus it was recognized as the
Honda–Fujishima Effect [14].
Abe et al. [32] synthesized platinum, tantalum,
tungsten, iodine, oxygen and nitrogen multiple
element complex photocatalyst for water splitting
and hydrogen production. This novel system has a cat-
alytic response under visible light and high efficiency
for hydrogen production from water. The Pt-TaON par-
ticle has a band gap of about 2.5 eV; the conduction
band and valence band edges are −0.3 and +2.2 V,
respectively. This system has enough negative
normal hydrogen electrode (NHE) to reduce H2O to
hydrogen gas. In contrast, the Pt-WO3 system is
good at oxidation, the NHE of valence band of
which is much higher than H2O to oxidize water [32].
The dye-sensitized TiO2 method established the
ability to decompose pollutants with the application
of visible light; the photoreaction efficiency was very
low due to slow interfacial electron transfer between
substrates and the back electron transfer to the oxi-
dized sensitizer. Photoactive sensitization compounds
are chemicals with a high photo stimulating factor and
easy adsorption onto the surface of the photocatalyst.
Bae et al. [33] investigated a RuII + L3 sensitizer with
Pt-TiO2 particles. They found carbon tetrachloride
(CCl4) could be decomposed to Cl− under visible
light irradiating but the fast initial dechlorination on
Pt /TiO2/RuII + L3 stopped after 30-minute irradiation.
Thuy et al. [34] have used the hydrothermal method
with various solvents for the preparation of
vanadium-doped TiO2 nanoparticles. The concen-
tration of vanadium was in a range from 0.1% to
0.9%. All the prepared photocatalysts have an
anatase phase with particle size in the range from 10
to 20 nm. The prepared photocatalyst, that is,
vanadium-doped TiO2, has been reported to cause
long-tailed absorption in the visible light above
380 nm. This is attributed to the transfer of the
ENVIRONMENTAL TECHNOLOGY REVIEWS 5
charge for D orbital of vanadium to the conduction
band of TiO2. It has been further reported that with
0.5% vanadium doping, the obtained photocatalyst
shows better photocatalytic activity. Luo et al. [35] syn-
thesized pure and Sb-doped TiO2 photocatalysts by a
co-precipitation method using TiCl4 and SbCl3 as pre-
cursor. Sb ions can be isomorphously substituted into
the TiO2 lattice to generate a new doping energy level
and change the electron transition way of TiO2 from a
valence band to a conduction band. In this case, it
extends the scope of the TiO2 absorption spectrum
to the visible light region and improves the photoca-
talytic activity of catalysts. The reported result shows
that the photocatalytic activity of 0.1–1% Sb-doped
TiO2 is higher than pure TiO2, and 0.1% Sb-doped
TiO2 presents the best photocatalytic activity, which
is much better than Degussa P25. Furthermore, combi-
nation of various types of carbon with TiO2 has been
suggested as a favourable technique for an improved
photocatalytic performance [36,37]. As a result, gra-
phene/TiO2 nanocomposite with better interfacial
contact with graphene nanosheets (GNS) without
aggregation would be required for an improvement
in the photocatalytic performance. This exclusive
assembly will enable charge separation and facilitate
electron transfer from TiO2 to graphene when it is
exposed to irradiation. [38]. Banerjee et al. [39] have
used a Ga-doped TiO2 photocatalyst, which is prepared
via the sol–gel deposition process by using titanium iso-
propoxide and gallium oxide as precursors, for the
photocatalytic degradation of organic dye solution
(Rhodamine B). It has been reported that size-strain
analysis of the doped materials showed slight stress
due to the presence of Ga ions within the TiO2 matrix
as substitutional and/or interstitial dopants. XPS analysis
proved the presence of Ti+3 and surface titanol groups,
which are responsible for enhancement of the photoac-
tivity of the nanoparticles. Recently, Bethi et al. [40] used
ultrasound-assisted preparation of TiO2 and cerium- and
Fe-doped TiO2 nanophotocatalysts. The prepared
photocatalysts were used for the decolourization of
crystal violet dye in the presence of hydrodynamic cavi-
tation. It was concluded that 0.8% of Fe-doped TiO2
yielded maximum photocatalytic activity in the deco-
lourization study of crystal violet dye.
Overall, doping of the TiO2 photocatalyst by metal or
non-metal results in a decrease in the recombination
rate of the electron–hole pair and leads to enhance-
ment in the degradation rate of the pollutants.
6 B. A. BHANVASE ET AL.
Graphene–TiO2 composite-based
photocatalysts
Graphene is said to be a new carbon-based nanoma-
terial and has gained more attraction because of its
excellent chemical, electrical and structural properties.
Graphene is a single sheet of graphite with a hexago-
nal honeycomb network structure. The sp2-bonded
carbon lattice have many excellent electronic and
delocalized π-bonds that improve its structural stab-
ility and also enhance the current conductivity
capacity [41]. Yeh et al. [42] have studied graphene
oxide as a semiconductor showing photocatalytic
activity. The electronic property of GO has been
widely studied by researchers. Wang et al. [43] have
stated that corrugation and scrolling are part of the
intrinsic nature of GNS, because the 2D membrane
structure becomes thermodynamically stable via
bending. Son et al. [44] predicted that external electric
fields cause half-metality in zigzag graphene nanorib-
bons. This type of magnetic behaviour may be attrib-
uted to itinerant electron magnetism to a certain
extent than super replace magnetic coupling inter-
action between spins like molecule-based magnets
[44]. This property makes carbon nanomaterials prom-
ising for transport of spin-polarized currents and for
spin-based quantum information processing [44].
Numerous efforts in the use of GO or RGO for the
modification of TiO2 for photocatalytic degradation
of organic pollutants have been reported [45,46]. Gra-
phene has a theoretical surface area of 2600 m2/g [47],
making it highly attractive. It has high mechanical
strength (1060 GPa) and high thermal conductivity
(∼3000 Wm−1K−1) [48–51]. TiO2 particles are well
known to be one of the highest effective photocata-
lysts in degradation of dye pollutants and other
organic pollutants; however, their high trigger photo
energy and high recombination ratio impede their
utilization [8]. So, visible light-responsive modification
to TiO2 through GO/graphene is an attractive route to
treat water pollution [10]. Many researchers specified
that graphene, graphene oxide or reduced graphene
oxide (RGO) can be adopted as coupling or doping
compounds with photo-sensitive semiconductors
such as TiO2, ZnO, etc. for degradation of various pol-
lutants present in water [5,52–67]. Lui et al. [68] syn-
thesized hierarchical TiO2 nanoflowers using a
solvothermal reaction. The graphene-wrapped hier-
archical TiO2 nanoflowers have been reported to
show improved performance of degradation of
methylene blue (MB) under UV irradiation. This
enhanced photodegradation is attributed to the excel-
lent ability of transport of the charge, that is, electron
as graphene has excellent conductivity which in turn
suppresses the recombination of the electron–hole
pair and that provides more, preferential adsorption
sites for MB which in turn enhances the degradation
of MB. Muthirulan et al. [69] used a one-step effective
route and applied cost-effective strategy for synthesis
of the graphene–TiO2 nanocomposite. The reported
microscopic results showed proper incorporation of
TiO2 nanoparticles on the GNS. There was an excellent
assembly and interfacial bonding between graphene
and TiO2 nanoparticles which is revealed by spectro-
scopic studies. Furthermore, Muthirulan et al. [69]
have studied the photooxidation of AO7 under UV
irradiation and it has been reported that the degra-
dation of AO7 follows the pseudo-first-order kinetics
as professed by the Langmuir-Hinshelwood model. It
has been further reported that the degradation effi-
ciency of the graphene–TiO2 nanocomposite is higher
compared to TiO2 alone and this is attributed to the
presence of graphene which inhibits the recombination
of the electron–hole pair and in turn there is a drastic
enhancement in the photocatalytic performance. It
can be said that the graphene–TiO2 nanocomposite is
an efficient multifunctional photocatalyst for the degra-
dation of hazardous compounds in wastewater.
Out of various synthesized graphene-based compo-
sites, graphene–TiO2 composites have been exten-
sively investigated for diverse applications. The
graphene–TiO2 composite is reported to yield
improved performance in photocatalysis. Various
methods have been used for the preparation of gra-
phene–TiO2 nanocomposite so far, such as (1) hydro-
thermal method, (2) molecular grafting, (3)
solvothermal method and (4) heterogeneous coagu-
lation. Conversely, many of the graphene–TiO2 nano-
composites have been reported to be fabricated by
somewhat difficult methods such as (1) hydrothermal
treatments, (2) graphene–TiO2 assembly by multistep
methods or (3) the reduction of the TiO2–graphene
oxide composite into TiO2–graphene composite. For
photocatalysis uses, the morphology of TiO2 is
expected to be one-dimensional when it is compared
with the spherical TiO2 nanoparticles, as one-dimen-
sional morphology has outstanding mobility of
charge carriers, high surface areas, scatters more

light at the red part of the solar spectrum and the
existence of straight pores. These properties improve
the accessibility of electrodes to the hole-transporting
materials and hence improve charge collection and
transport. In a photochemical reaction process, con-
duction band electrons (e−) and valence band holes
(h+) are generated when aqueous TiO2 suspension is
irradiated with light energy bigger than its band-gap
energy (Eg = 3.2 eV). Graphene is a 0 eV band-gap
semiconductor in which the filled valence band
touches the empty conduction band, thus giving rise
to a new band for radical production. Zhang et al.
[52] indicate that high adsorption material will
support a higher composition of reactants near the
TiO2. Leary et al. [22] indicate that the graphene
sheets are perfect electron sinks or electron transfer
bridges. Exfoliated graphene sheets have a theoretical
surface area of 2600 m2/g, making graphene highly
attractive as a high surface area 2D photocatalyst
support. The application of graphene in amalgamation
with TiO2 consequently offers the prospect of concur-
rently covering all three mechanisms of photocatalytic
reaction. Jeong et al. [70] synthesized GOs, which were
analysed using various characterization techniques
such as TEM, FTIR, Raman spectroscopy, 13C NMR
and XPS. The most important and interesting feature
of graphene oxide is its layered structure which is
nicely maintained with a clear AB stacking order and
a hexagonal structure in the plane with various func-
tional groups randomly distributed. The basal planes
close to each other have hydroxyl and epoxide func-
tional groups located. The carboxyl and alkyl groups
will probably be located at the edges of the GO
flakes. With longer oxidation times, hydroxyl groups
were converted into more epoxide groups in the
basal plane. Morales et al. [71] have reported the inter-
esting role of graphene and its derivatives in gra-
phene–TiO2 nanocomposites. These are generally
related with: (i) the capture of generated electrons
due to light irradiation of TiO2 particles which gives
active oxygen radicals and suppresses the electron–
hole recombination; (ii) the improved adsorption
capacity of organic pollutants and (iii) the light absorp-
tion to extended wavelengths. Kim et al. [72] have pre-
pared a graphene–SnO2 composite with large capacity
for Lithium storage in Lithium rechargeable batteries.
They have developed a simple fabrication route for
the SnO2/graphene hybrid composite. Nanosized
SnO2 particles were synthesized, which leads to the
ENVIRONMENTAL TECHNOLOGY REVIEWS 7
formation of a uniformly distributed SnO2–GNS com-
posite. The prepared SnO2/graphene electrode has a
high reversible capacity, as high as 634 mA h g–1 at
the end of 50 cycles.
Alberto et al. [73] have mixed the GO and rGO with
quantum dots and various other semiconductors,
which leads to the formation of a graphene-based
nanocomposite. Also neat graphene was mixed with
fine-tuned quantum dots to enable a decent photode-
tector, which uses inherent physical properties from
defect-free/less-defect graphene. Jin et al. [74] have
studied the effect of expansion temperature on
expanded graphite by thermal blow of graphite
oxide. It has been reported that an increase in the
expansion temperature enhances the expansion
ratio of graphite oxide. They have proposed the scal-
able method to prepare aqueous solution of graphene
sheets from low-temperature-expanded graphite with
strong interaction of solvent with expanded graphite
flakes. Zahra et al. [75] have used graphene sheets’
support for the preparation of graphene–TiO2 compo-
site by in situ sol–gel synthesis of TiO2 nanoparticles
on graphene sheets. The novel composite has excel-
lent photocatalytic activity for degradation of pharma-
ceuticals which is ascribed to a thin 2D graphene sheet
support with higher surface area which increases the
adsorption capacity. Also graphene sheets act as
excellent electron acceptors which transfer the
photo-generated electrons from the conduction
band of TiO2 to the graphene sheet. The higher degra-
dation rates of in-situ synthesized RGO/TiO2 to RGO/
TiO2 mixture can be attributed to attachment of TiO2
on the graphene basal plane which facilitates electron
transfer to produce radicals. In summary, adsorption,
transparency, conductivity and very large planar struc-
ture of graphene are the key enhancing factors of
photodegradation of the pollutants over reduced gra-
phene/TiO2 composites. This new composite shows
promising applications in the field of environmental
photocatalysis, especially water purification. Xuan
et al. [76] prepared a graphene–TiO2 nanowire
(GNW) composite using the hydrothermal method.
It has been reported that the GNW shows highly
uniform and fine distribution of TiO2 nanowires over
the graphene sheet compared to that of TiO2 nanopar-
ticles and graphene–TiO2 nanoparticle composite
structures. It has been further reported that the nano-
composites have better adsorptivity of pollutants and
have a higher rate of pollutant degradation compared
8 B. A. BHANVASE ET AL.
to TiO2 nanowires and nanoparticles. Furthermore, a
substantial enhancement in the photocatalytic degra-
dation of pollutants has been observed in the case of
graphene–TiO2 nanowire composite compared to
other prepared materials under solar light, which is
ascribed to the improved charge separation and trans-
portation by inducing graphene. Zhang et al. [77] have
prepared stable and high-concentration graphene dis-
persions by chemical reduction of GO in the presence
of ultrasonic irradiation. The aggregates of graphene
sheets observed in the case of a mechanical stirred
system were successfully removed using the ultra-
sound-assisted method. Oh et al. [78] have reported
that thinner graphene oxide layers were produced
using thermal and ultrasonic treatments. It has been
reported from the FTIR spectroscopic analysis that
the ultrasonic treatment did not change the functional
groups of GO; however, all oxygen-containing func-
tional groups in the TTG layers were nearly completely
removed during the thermal treatment. The visible D
peak, the clear G peak and the characterized 2D
band witnessed the existence of defect-free mono-
layer graphene and few-layer graphene in the
sample of TTG. Monolayer graphene and few-layer
graphene were clearly observed in the TEM image of
TTG. The minimum height of the obtained layers
(AFM) was 309 nm. Deosarkar et al. [79] have used
an ultrasound-assisted, solution-based chemical syn-
thesis method for the preparation of graphene–SnO2
nanocomposites. The reported TEM image (Figure 1)
shows the particle size of 3 to 5 nm which is attributed
to the extreme environment generated by ultrasonic
irradiations. This extreme environment is responsible
for the fine and uniform distribution of smaller nano-
sized SnO2 nanoparticles on GNS.
Deosarkar et al. [80] have used the ultrasound-
assisted method for the preparation of the gra-
phene–Fe3O4 nanocomposite with fine dispersion of
Fe3O4 on GNS. Min et al. [81] have carried out the reac-
tion between graphene oxide and titanium alkoxide in
the presence of ultrasound. As per their report, they
modified the graphene oxide with poly-acrylic acid
and this increased the number of carboxylic groups
on the graphene surface and then hydrolysis of
titanium alkoxide was reported on the modified gra-
phene oxide in the presence of ultrasonic irradiations.
The prepared graphene–TiO2 nanocomposite was
used as a photocatalyst for the degradation of Rh.B
and is reported to be much higher than that of
commercial P25. Min et al. [82] reported a simple
method for the preparation of the graphene–TiO2
nanocomposite which has application as a photocata-
lyst in visible light for the degradation of methylene
blue. Significant enhancement in photocatalytic
activity has been reported with fine dispersion of
TiO2 nanoparticles on graphene sheets. Wang et al.
[83] reported a simple one-step solvothermal
method for the synthesis of GNs–CdS and GNs–ZnS
composites with the use of GO. This preparation is
very simple and can produce GNs–metal sulphide
composite materials. It has been reported that GNs–
CdS show interesting photovoltaic properties. Zhang
et al. [84] reported that the graphene combined with
various semiconductors to form graphene-semicon-
ductor nanocomposites with a large surface area,
high conductivity, carrier mobility, easy functionaliza-
tion and low cost. These exclusive properties of gra-
phene have shown new ways for the preparation of
high-performance photocatalysts. Ojha et al. [85]
reported the synthesis and unique properties of gra-
phene and graphene-based composites with particu-
lar importance given to the environmentally benign
(green) synthetic methods and their wide applications,
particularly in energy conversion, energy storage, elec-
tronics, biomedical and biosensing applications. Divya
et al. [86] have reported the preparation and charac-
terization of graphene. They have also offered insights
into the different preparation methods for a gra-
phene-based semiconductor photocatalyst and its
uses like photodegradation of organic pollutants,
photocatalytic hydrogen generation, photocatalytic
conversion, etc. The coupling of graphene with a semi-
conductor leads to enhancement in the properties
such as high dye adsorption capacity, prolonged
light absorption range, improved charge separation
and transportation properties, which will improve
the photocatalytic activity. Lee et al. [87] reported
two types of photocatalytic nanocomposites, particu-
late and continuous nanofibre systems, which were
successfully synthesized for the photodegradation of
organic toxins. For the particulate system, anatase or
rutile nanocoating on functionalized multi-walled
carbon nanotubes was achieved via a sol–gel
process. The photodegradation of azo dye molecules
was also performed under visible light irradiation.
Almost 50% dye degradation by the anatase nano-
coated carbon nanotubes in the post UV-A experiment
have been reported. Liang et al. [88] have prepared

Figure 1. TEM image of the SnO2–graphene nanocomposite prepared using the sonochemical method at (a) 10 nm and (b) 5 nm mag-
nification. Reprinted with permission from Ref. [79].
graphene/Fe3O4 hybrid papers using a simple water
solution process. It has been established that the pre-
pared multifunctional hybrid papers have various
properties such as good flexibility, electrical conduc-
tivity, mechanical strength and better superparamag-
netism. It has been further reported that these
properties of the paper can be altered easily by con-
trolling the loading of Fe3O4 nanoparticles in the
hybrid system. Zhang et al. [89] have used a simple
chemical deposition technique for the preparation of
graphene oxide–Fe3O4 hybrid material. The reported
size of Fe3O4 nanoparticles on graphene oxide dis-
persed was between 2 and 4 nm. This hybrid material
demonstrates more improved optical limiting per-
formance compared with graphene oxide. For photo-
catalytic degradation of dyes, various studies have
been reported using semiconductor particles as
photocatalysts [56,90]. To effectively utilize the inex-
haustible energy of solar radiation reaching the
surface of the earth, which is inexpensive, low cost
and nontoxic, photocatalysts with more efficient
photocatalytic activity and high stability are sought.
However, no such material or system currently satisfies
all these requirements [22]. Jiang et al. [54] investi-
gated azo dye degradation on a TiO2–graphene com-
posite. Graphene has low solubility in water and polar
organic solvents and the strong van der Waals force
makes graphene aggregating. The hydrophobic/
hydrophilic incompatibility between graphene and
inorganic compounds makes it difficult to directly
deposit metal oxides on graphene [91,92]. Calcination
temperature affects the photocatalytic activity of gra-
phene-loading TiO2 composites. When the calcination
ENVIRONMENTAL TECHNOLOGY REVIEWS 9
temperature is increased from 100°C to 200°C there is
a weak tendency of degradation ability whereas the
activity is higher at 250°C. Generally, the calcination
temperature is much higher [54]. It is believed that a
high temperature will result in partial combustion of
graphene oxide, causing partial destruction of the
composite structure which is unsuitable for photode-
gradation [54]. Graphene-doped ZnO nanoparticles
are useful to extend the light absorption or suppress
the electron–hole recombination [52]. Li et al. [93] syn-
thesized flower-like ZnO nanoparticles anchoring on
GO sheets and applied for the photocatalytic degra-
dation of organic dyes in aqueous system in the
visible light. In a typical process, ZnCl with exfoliated
GO suspension was mixed in ethanol and sodium
hydroxide solution, and then the particles were
annealed at 400°C. The UV spectrum study shows
that the ZnO/GO composite has absorption in the
whole visible region.
Overall, it can be concluded that the graphene base
can be effectively used for the degradation of pollu-
tants presents in water and wastewater with improved
efficiency. It is also possible that with the use of gra-
phene electron–hole separation efficiency is signifi-
cantly enhanced which results in enhancement in
the degradation of pollutants.
Doped graphene–TiO2 composite
photocatalysts
The doping of graphene–TiO2 composite photocata-
lyst will shift the optical response of TiO2 to the
visible spectral range, which is an important issue
10 B. A. BHANVASE ET AL.
and area of study in the current scenario [94,95]. The
thermal stability of the prepared photocatalyst is an
important drawback for the doped materials with tran-
sition metal. Graphene, a two-dimensional carbon-
aceous material, has garnered attention in the field
of photocatalysis [96]. The excellent electron mobility
and rapid change separation capabilities of the gra-
phene made researchers to use it in the photocatalyst
preparation. The above-mentioned properties of
doped materials and graphene motivated researchers
to prepare the doped graphene–TiO2 composite
photocatalyst by various methods, which can be
further used for the photocatalytic degradation of
various pollutants present in water and wastewater.
This combination is expected to enhance the photoca-
talytic degradation of various pollutants in the pres-
ence of UV and visible sunlight. Huang et al. [97]
reported the preparation of carbon nitride/TiO2/
reduced graphene hybrid with the use of a simple
one-step solvothermal method. The application of
the prepared hybrid photocatalyst was reported for
the degradation of Methyl Orange, Rhodamine B
and phenol under visible light irradiation. It has been
also reported that this hybrid photocatalyst shows
enhanced photocatalytic activity which is attributed
to the larger specific surface area and enhanced
visible light absorption capability of the prepared
hybrid photocatalyst. Min et al. [98] have reported
enhanced photocatalytic activity of the graphene-
hybridized TiO2 composite by nitrogen anion under
visible light. As per the reported method, the prep-
aration of nitrogen-doped graphene/TiO2 was carried
out using the hydrothermal method in a solution con-
taining urea. This hybrid graphene-based photocata-
lyst consisting of TiO2, nitrogen anion and graphene
sheets showed excellent solar light-induced photoac-
tivity. Yue et al. [99] reported decomposition of
crude oil absorbed into expanded graphite/TiO2/NiO
composites. In their study, TiO2 loaded on NiO photo-
catalyst was supported on graphite which is con-
sidered to have high adsorption capability for heavy
oils in water. FTIR spectra indicate that most of
organic functional groups such as C–H, C–S and C–C
decreased because of photo-decomposition with
solar energy. Ali et al. [100] prepared Ce-TiO2/gra-
phene photocatalysts via the hydrothermal method.
It has been reported that the enhanced photocatalytic
activity of cerium-doped TiO2/graphene composites is
due to synergy effects which includes improved
visible light absorption, enhanced charge carrier sep-
aration and formation of π−π conjugation structure
of graphene sheets. It has been further reported that
both cerium doping and graphene modification
provide better ways to get low cost and efficient
photocatalysts for visible light activation. Yue et al.
[101] prepared a ternary hybrid nanocomposite
which includes TiO2 and Fe3O4 nanoparticles which
are dispersed on GNS. As per their report, this photo-
catalyst nanocomposite showed an enhanced photo-
catalytic degradation of RhB as compared to the
unsupported TiO2–Fe3O4 composite and pure TiO2
nanoparticles. The photodissolution of Fe3O4 in the
prepared nanocomposite is reported to be suppressed
to a relatively low level by the presence of graphene,
which insures the stability of the prepared nanocom-
posite in photocatalytic reactions. They have also
confirmed the reusability of the prepared photocata-
lyst. As per their finding, the electron transfer from
the TiO2 nanoparticles to RGO is an important
aspect in obtaining high durability of the prepared
nanocomposite.
Recently, Zhou et al. [102] prepared CeO2-TiO2-RGO
for the degradation of Tetrabromobisphenol A under
visible light. It has been further reported that the Tet-
rabromobisphenol A degradation rate was higher and
the degradation rate constant was 0.0191 min−1. It has
also been concluded that the photo-generated holes
have an important role in the degradation reaction
for repeated runs. Prabhakarrao et al. [103] have
attempted the synthesis of Zr-doped TiO2/RGO nano-
composites’ photocatalyst by an in-situ process by a
modified sol–gel method at low temperature. It has
been reported and concluded that the generation of
radical •OH is responsible for the degradation of dye
molecules during irradiation. Overall, it can be con-
cluded that the doping of graphene–TiO2 nanocom-
posite plays an important role in the degradation of
various reported pollutants in the presence of visible
light with a higher degree of degradation. This will
be a promising photocatalyst in the future for degra-
dation of various pollutants present in water and
wastewater.
Critical comments
With the review of the mentioned articles in this
article, TiO2 is a broadly used photocatalyst for the
treatment of wastewater due to high stability, low

cost and toxicity and enhanced photocatalytic activity
compared to other semiconductor materials. Also,
doping of TiO2 extends its application in visible light
with improved degradation rate of pollutants. Gra-
phene has excellent electron mobility which can be
useful in applications of charge separation and it sup-
presses the recombination of an electron–hole pair.
This can enhance the utilization of the formed holes
for a more effective formation of radicals which in
turn enhances the degradation rate of the pollutants.
Also, the use of the graphene extends light absorption
and its application in degradation in visible light. In
addition, doping of various metal, metal oxides or
non-metals in the graphene–TiO2 nanocomposite
photocatalyst further extends its application in
visible light with a higher rate of the degradation of
pollutants.
Summary
Organic pollutants are a threat to human beings due
to their adverse effects. To solve this problem,
photo-degradation technology plays an important
role, by introducing the application of photo-sensitive
semiconductors and solar energy, which could
decompose organic compounds into CO2 and H2O.
But many photocatalysts possess high band-gap
energy and low efficiency which lead to low surface
area, low absorption etc. Various researchers have
attempted different strategies for the modification of
the photocatalyst in order to increase its light absorp-
tion capacity, stabilization and photoreaction effi-
ciency by ion doping, dye sensitization, noble metal
doping and electron scavenger. This will extend its
application in visible light. In addition, graphene is a
new carbonaceous nanomaterial with one carbon
layer structure, and with special photo and electric
property. Because of special properties, high surface
area, excellent electron mobility and super stability,
graphene-doped photocatalysts are found to be
good in visible light absorption, higher charge separ-
ation capability, suppression of recombination of elec-
tron–hole pair and adsorption of a pollutant. This
drastically enhances the photocatalytic degradation
of various pollutants in the presence of visible light.
Moreover, doped graphene–TiO2 composite photoca-
talyst extends the application of these photocatalysts
in the visible light range. Thus, graphene-doped
photocatalysts can be used in water purification as
ENVIRONMENTAL TECHNOLOGY REVIEWS 11
well as for the degradation of dyes in the presence
of visible light.
Disclosure statement
No potential conflict of interest was reported by the authors.
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