Catalysis Today 285 (2017) 1328

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Environmental applications of titania-graphene photocatalysts

Marisol Faraldos , Ana Bahamonde
Instituto de Catlisis y Petroleoqumica, ICP-CSIC, C/Marie Curie, 2, 28049 Madrid, Spain

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

Article history: Nowadays, graphene is considered one important achievement as a consequence of its high potential in
Received 5 October 2016 nanotechnologyand in the development of new environmental and energy processes. Reciently, graphene
Received in revised form is receiving great attention in the area of photocatalysis, where is emerging in the next generation of
26 December 2016
photocatalysts, as a tool for enhancing photocatalytic performance and solar photoefciency. Titanium
Accepted 17 January 2017
dioxide hybridization with graphene has an effect on band gap energy decrease, shifting its absorption
Available online 26 January 2017
threshold to the visible light region and allowing to harness solar energy. So, the conjugation of graphene
with semiconductor solid particles such as TiO2 , results in photocatalysts with improved charge separa-
Keywords:
Graphene
tion, reduced recombination of the photogenerated electron-hole pairs, increased specic surface area,
Titania and introduces an adequate quantity and quality of adsorption sites, given that enhances their electronic,
Water treatment optoelectronic, electrocatalytic and photocatalytic properties.
Air pollution This critical review sumarizes the recent progress in the design and synthesis of graphene-based tita-
Dye nia semiconductor photocatalysts. Moreover, their applications in wastewater treatments, disinfection
Heterogeneous photocatalysis and air pollution control have been also discussed. Finally, some perspectives and challenges consid-
ered essential to extend the photoefciency of these new photocatalysts in the visible region, to harvest
directly solar light, have been suggested to introduce and elucidate new improvements in environmental
photocatalytic processes.
2017 Elsevier B.V. All rights reserved.

1. Introduction materials sience and condensed-matter physic elds, aiming for a

In 2003, two researchers at The University of Manchester, Prof.
Andre Geim and Prof. Kostya Novoselov, were managed to isolate
from graphite a magnicent new wonder material that is a million
times thinner than paper, stronger than diamond and more conductive
than copper. This strictly two-dimensional material that exhib-
ited exceptionally high crystal and electronic properties was called
graphene, and has revolutionized the physics community when the
rst paper appeared published in Science in 2004 [1]. Six years later,
they were awarded the 2010 Nobel Prize in physics for this work.
Graphene is the name given to a single layer of carbon atoms
densely packed into a benzene-ring structure, and is widely used
to describe properties of many carbon-based materials, including
graphite, large fullerenes, nanotubes, etc. (e.g., carbon nanotubes
are usually thought of as graphene sheets rolled up into nanometer-
sized cylinders) [24]. Fascination with this material stems from its
remarkable physical properties and the potential applications these
properties offer for the future. Nowadays, graphene is emerging on
Corresponding author.
E-mail address: mfaraldos@icp.csic.es (M. Faraldos).
wide range of technological applicacions [59],. Its high potential in
nanotechnology applications converts to graphene in an important
achievement which could change our lifes with the development
of new processes in environmental and energy disciplines. Various
methods, including thermal expansion [1] micromechanical exfo-
liation [10], epitaxial growth [11], chemical vapor deposition [12],
chemical and electro-chemical reduction of graphite oxide [13,14]
and bottom-up organic synthesis have been developed [15,16]
from the rst report on graphene isolated by manual mechanical
cleavage of graphite with a Scoth tape [1]. Reduction of exfoliated
graphene oxide (GO) has proven to be an effective and reliable
way to obtain graphene nanosheets at low cost and great stabil-
ity. Besides, via chemical modication can be well adjusted surface
properties of graphene, which offers excellent chances for the
progress of functionalized graphene-based materials [17,18]. They
are very attractive for many potential applications, such as energy
storage [19], catalysis [20], biosensors [21], molecular imaging [22],
drug delivery [23], nanomedicine and more concretely stem cell-
based tissue engineering [24], and recently nanomotors [25]. All of
them are posible, fundamentally, because graphene shows distinc-
tive electronic and optical properties with good biocompatibility.
Concretely, this material is receiving great attention in the area of

http://dx.doi.org/10.1016/j.cattod.2017.01.029
0920-5861/ 2017 Elsevier B.V. All rights reserved.
14 M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328
Fig. 1. Proposed mechanisms of phenol degradation in oxygen by TiO2 -graphene composites: A) Without e transfer from TiO2 conduction band (CB) to graphene. B) With
e transfer. (from [48]).
nanotechnology and photocatalysis due to its outstanding prop-
erties, especially those which exploit its high electron mobility
and chemical stability [26,27], and its high adsorption capacity
[28,29]. In photocatalysis area, semiconductor materials have been
the focus of numerous investigations due to its application to the
quantitative destruction of undesirable chemical contaminants in
water and air [30,31], and to solar energy conversion [32].
Although several oxide semiconductors have photocatalytic
properties, the polycrystalline powders of titanium dioxides
present unique properties since it is a stable material, high rel-
ative photoactivity, high chemical inertness, nontoxicity and low
cost [33,34]. However, many problems need to be solved in the
TiO2 photocatalyst system for practical applications, such as nar-
row UV spectrum response range because of a large band gap
energy (3.0 eV for rutile and 3.2 eV for anatase) and relatively
fast recombination of the photo-generated e /h+ pairs [32]. Hole-
electron recombination is a serious problem for the development
of photo-catalytically based technologies since it severely limits
the quantum yields achievable [35]. Therefore, various methods
have been developed to extend the absorption range of titania into
the visible region and to improve its photocatalytic activity, and
there are strategies to reduce electron-hole recombination rates
and increase photocatalyst efciency. For instance, via suitable tex-
tural design, doping with noble metals, such as Pt, Ag, Au, Pd, etc,
transition metal cations, non-metallic doping or immobilization
on adsorbent surface and forming semiconductor composites have
been employed [3644]. In this line, also carbon nanomaterials such
as fullerenes, carbon nanotubes and graphene are recently receiv-
ing a great attention in photocatalityc process, predominantly
graphene, because of its unique properties, including large specic
surface area, exible structure, excellent mobility of charge carriers
at room temperature and good electrical and thermal conductivi-
ties [45,46]. So, graphene is emerging as one of the most promising
materials in the next generation of photocatalysts [47], given that
has been embraced in the design of new photodegradation cata-
lysts as a tool for enhancing their photocatalytic performance [48].
The excellent properties of graphene are important features when
dealing with the preparation and use of graphene-based materi-
als, thus graphene-based TiO2 composites are being developed and
successfully applied as photocatalysts for the abatement of pol-
lutants, hydrogen production and others applications [44,4951].
Where the most widely used synthesis procedures with semicon-
ductors such are TiO2 are in situ growth, solution mixing, sol-gel,
hydrothermal and/or solvothermal methodologies [44]. Titanium
dioxide hybridization with graphene has an effect on band gap
energy decrease, thus shifting the absorption threshold to the vis-
ible light region and allowing utilization of solar energy [30]. The
excited electrons could be transfered from the conduction band of
TiO2 to the surface of graphene, hence improving the separation of
the electron-hole pairs and preventing their recombination [52,53],
because it has been already proven that the electron accepting and
transport properties of graphene provide a convenient way to direct
the ow of photo-generated charge carriers, which thus increases
the lifetime of e /h+ pairs generated by TiO2 upon light irradiation
[54,55].
Therefore, graphene is a suitable alternative to noble metals
because it has a high conductivity, high surface area, and the abil-
ity to favor the electron transfer from the conduction band of
TiO2 to delocalized aromatic structure of graphene [56]. So, the
conjugation of graphene with semiconductor solid particles, such
as TiO2 , results in a photocatalyst with improved charge separa-
tion, reduced recombination of the photogenerated electron-hole
pairs, increased specic surface area, and introduces an adequate
quantity and quality of adsorption sites, that lead to enhance their
electronic [57], optoelectronic [58], electrocatalytic [59] and pho-
tocatalytic properties [60].
2. Mechanistic aspects of titania-graphene photocatalysts
It is known carbonaceous materials play an important role in
photocatalytic processes given that usually present exceptional
adsorption ability to many type of pollutants. In this line, TiO2 -
graphene based catalysts can in turn, if photo-generated charges
are transferred toward graphene, improve the nal efciency of
the process [30,31]. However, there is not a complete agreement
on the real role of the presence of graphene on these types of
composites along photocatalytic process. Often, different opera-
tional parameters and some of the most relevant properties of
TiO2 -graphene composites can even affect their nal photocatalytic
efciency, such as type of substrates, irradiation light (UVvis or
Vis), etc. In the work of Minella et al. [61] a complete summary of
the operational mechanism alternatives acting on TiO2 -rGO com-
posites is presented. They discuss three types of photo-mechanism,
concluding as follow:
1) When substrates are not absorbing light, and are hardly being
adsorbed on the catalyst surface, a typical UV-based photo-
catalytic process can happen, supported by UV-activated e
transition from valence band (VB) to conduction band (CB),
which originates e /h+ pairs (Fig. 1A). In this case, no electron
is transferred between TiO2 and rGO, and rGO can act only as
competitive light absorber. The extension of light absorption
to visible range could happen due to the presence of graphene
which can even create states between the VB and CB of TiO2 .
 M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328
Fig. 2. FT-IR spectra of as-prepared Brodie-GO (black) and Hummers-GO (red).
(from [73]). (For interpretation of the references to colour in this gure legend,
the reader is referred to the web version of this article.)
2) Two possible mechanisms can operate when substrates are not
absorbing light and movement of photogenerated charges from
TiO2 and rGO are possible.
a. Electron transfer from TiO2 to rGO (Fig. 1B). The e photogen-
erated in the TiO2 jump into the CB and are immediately injected to
the graphene aromatic structure avoiding their recombination with
the photogenerated h+ that remains in the VB of TiO2 . The transi-
tions are favored by graphene redox potential that is less negative
than the conduction band edge of titanium dioxide.
b. Electron transfer from rGO to TiO2 . This less probable and
more specic mechanism describes the transference of e from
photoexcited rGO to TiO2 structure with further dissipation of
energy excess. In this case, rGO would be a merely sensitizer.
3) When dyes are involved in the photocatalytic process, a visible-
activated dye-sensitized pathway can be found, with the single
or multi-electron injection from the photo-excited dye to the
delocalized empty states of rGO or TiO2 to form the oxidized
dye molecules, and following photodegradation.
3. Methods for preparation of titania-graphene
photocatalysts
In general, the route to obtain graphene oxide starts from
graphite that is oxidized to graphite oxide, then delaminated to
render graphene oxide and further reduced to form graphene as it
can be illustrated in Fig. 2 [62].
Graphite oxide chemistry is quite old and was rst studied
by Brodie in 1859 [63]. Afterwards, several authors such as Stau-
denmaier [64], Hofmann and Frenzels [65], Hamdi and Hummers
[66], among others, have reported synthesis of graphite oxide from
graphite, under very strong oxidizing agents presence, with slight
modications in reaction conditions [67].
An important property of GO, brought about by the hydrophilic
nature of the oxygenated graphene layers, is its easy exfoliation
in aqueous media. As a result, GO readily forms stable colloidal
suspensions of thin sheets in water. After a suitable ultrasonic treat-
ment, such exfoliation can produce stable dispersions of very thin
graphene oxide sheets in water. These sheets are, however, differ-
ent from graphitic nanoplatelets or pristine graphene sheets due to
their low electrical conductivity [68].
Brodie was the rst to describe a graphite oxidation method
[61], which drives through the mixture of graphite with potassium
chlorate (3:1 proportion), with the addition of the strongest fum-
ing nitric acid. This reaction evolves at a temperature of 60 C in
a water-bath during 3-4 days. The obtained material was through
15
into water, washed, and re-oxidized under the same conditions,
until no further change in C:H:O ratio was observed, usually up
to four repetitions. Finally a light yellow solid was obtained upon
drying in vacuum and then at 100 C. Variations with shorter reac-
tion times and higher temperature of nal calcination have been
described [69]. Staudenmaier [62] and later Hofmann [63] slightly
modied Brodies oxidation method by progressively dosage of
potassium chlorate and further acidication with concentrated sul-
phuric acid or using non-fuming nitric acid, respectively. The result
was a material with similar C/O ratio in shorter time.
Graphite oxidation by Hummers method [64] is based on the
reaction of commercial graphite powder with H2 SO4 /NaNO3 and
KMnO4 (safer method than preceding since nitric acid is generated
in situ), followed by the addition of H2 O2 to neutralize the excess of
MnO4 that remains unreacted. The brownish solid was ltered and
washed repeatedly with HCl and water, then dried under vacuum
at room temperature. The graphite oxide was heavily oxygenated,
as such; it has been frequently adopted by many researchers for
subsequent preparation of photocatalytic composites. Recently,
in situ production of nitric acid was replaced by phosphoric acid,
trying to reduce risks, provide more oxidized forms of graphite
oxide and keep unaltered 2D graphitic structure [70]. Successive
improvements on synthesis methods of graphite oxide pursue safer
procedures that led to materials with high C/O ratio, but able to
maintain the crystallinity upon reduction and exfoliation steps [71].
As mentioned above, Hummers method approaches are the pre-
ferred for graphite oxidation specially for further photocatalytic
applications. This is mostly due to the smaller amount of oxygen
introduced by Brodies method compared to Hummers, and the
difculty to recover the Csp2 structure of the carbon lattice after
treatment at moderate temperatures; however residual oxygen
remains even after treatment at 2000 C. In contrast, the presence
of less conjugated oxygen groups in Hummers graphite oxide facil-
itates their thermal removal resulting in a better restoration of
the pristine graphite 2D structure [72]; and added reason for the
preference of Hummers-GO in photocatalysis applications, essen-
tially those where water or high relative humidity environments
are involved.
The ability of GO to disperse in aqueous media on separate
graphene oxide sheets has recently attracted strong attention to
these materials. It is known that GO sheets undergo swelling
when immersed into water (or other liquid solvent) provoked
by solvent molecules intercalation (solvation) between GO layers
which results in an increase of the distance. The different func-
tionalities of Brodie and Hummers GO samples originate different
hydration/solvation behavior. In particular, the presence of higher
number of C O groups in Hummers-based GO materials (see Fig. 3)
could be responsible for higher separation of graphene oxide sheets,
thus achieving higher degree of hydration/solvation. In contrast,
C OH groups, more abundant in Brodie-based GO samples, leads
to better ordering of graphene oxide sheets in the stacks and conse-
quently, better crystallinity of the solvated GO structure. The better
crystallinity of the Brodie-based GO sample makes it difcult to dis-
perse Brodie-based GO on single sheets in water solution even after
intense sonication. Indeed, experiments with samples prepared by
both methods showed that Hummers-based GO samples are very
easily dispersed in water after mild sonication, while Brodie-based
GO does not delaminate well even when sonicated for tens of hours
[73].
The reduction of graphene oxide to graphene is visually recog-
nized by a color change of the suspension from brown (graphene
oxide) to black (graphene), and an increase of hydrophobic-
ity/aggregation of the material due to loss of oxygenated functional
groups.
The efciency of a reduction method can be evaluated by
increase of C/O ratio (to quantify the decrease of oxygen content)
16 M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328

Fig. 3. Schematic route of GO reduction and in situ growth of TiO2 nanoparticles on RGO sheets via hydrothermal process. (Adapted from [62] and [110]).

Fig. 4. Routes for the synthesis of graphene oxide-TiO2 composites.

and enhancement of current conductivity (to evaluate the crys-
tallinity of graphitic basal plane) [69].
The reduction of graphite oxide could be afforded by physical
procedures, traditional redox reactants or green chemical agents.
i) Among physical processes, temperature treatment in vacuum or
inert atmosphere is a simple way [43,7476], microwave [7782],
sonication [8386] or irradiation [49,8789]; last three could be
carried out directly on the suspension and permit to afford reduc-
tion and partial exfoliation simultaneously. ii) The traditional
redox chemicals are frequently toxic; however, use to follow
well-known reduction routes, which permit to control the reduc-
tion degree and tune the properties of nal compounds. A wide
range of agents with different nature and chemical behavior have
been reported, although collateral processes could happen like
adsorption or doping of resulting graphene. The chemical agents
most used are [69]: a) Borohydrides (commonly NaBH4 ) soluble
in aqueous but limited efciency with some types of carbonyl
groups [90,91]; b) Aluminum hydrides, strongest reducing agents
than borohydride salts; c) Sulphur-containing reducing agents
(Thiourea dioxide in alkaline conditions); d) Nitrogen-containing
reducing agents (Hydrazine, Hydroxylamine, Pyrrole, Benzy-
lamine, p-Phenylene diamine, Ethylenediamine, Urea, Dimethyl
ketoxime, Hexamethylenetetramine, Polyelectrolyte, Poly(amido
amine)) [59,88,92]; e) Oxygen-containing reducing agents (Alcohol,
Hydroquinone, L-Ascorbic acid, Saccharides, Gallic acid) [88,93];
f) Sulphur-containing reducing agents (namely Na2 SO3 , Na2 S2 O3 ,
 M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328
Thiourea, Thiophene); g) Metalacid (Al, Fe, Zn, Mg, Sn); h)
Metalalkaline (Zn, Al, Na); etc. iii) The last years, growing efforts
to achieve safer and greener synthesis have arisen the use of
natural or biocompatible reduction agents like: a) Amino acid
(L-Cysteine, Glycine, L-Lysine, L-Glutathione) [94]; b) Plant extracts
(green tea, reach in polyphenols) [95]; c) Microorganisms; d) Pro-
teins; e) Hormones; etc.
Usually, the combination of chemical and physical processes is
convenient to minimize the synthesis time. In a typical procedure,
GO is suspended in water and sonicated to yield a homogeneous
yellow brown dispersion. The reduction chemical agent in ade-
quate proportion was added to the solution and heat treated
(or microwave, sonication, UV) for determined time (from min in
some cases to hours, correspondingly). Reduced GO was gradually
produced as a black solid. The product was ltered and washed
copiously with water (and/or any other solvent). The product could
be additionally calcined under vacuum (or inert atmosphere) to
complete the desired reduction grade [96].
Once known how to oxidize, exfoliate and reduce the graphite,
the strategy to prepare the photocatalytic composite with titanium
dioxide or the selected semiconductor could be afforded. Two gen-
eral cases are generally found, as it has been graphically described
in Fig. 4: i) synthesis route based on commercial or synthetized
crystalline TiO2 or ii) synthesis procedure using titanium dioxide
precursors. In both cases the role of pH is important to favor the
optimal dispersion of solids in the reaction media and the interac-
tion among graphene oxide and titania particles in suspension.
A simple route consists on physical mixing of crystalline
TiO2 (anatase or anatase/rutile phases) with previously exfoliated
graphene oxide, but weak interactions arise and any evidence of
photocatalytic efciency enhancement takes place [9799]. Sev-
eral other synthesis of graphene oxide-titanium dioxide describe
that crystalline TiO2 and exfoliated graphene oxide are suspended
in an adequate media (water, alcohol o mixture or both, gener-
ally), stirred, heat treated and dried, accomplishing the reduction
of GO to rGO and the interaction between rGO and TiO2 at the
same time. This heat treatment could be carried out at vacuum or
inert atmosphere in an oven [76] or hydro/solvo-thermal reaction
[100103]. In other cases the reduction could be carried out by UV
irradiation, then a strictly control of time is recommended [104] to
avoid composite photodegradation. Prolonged times of UV irradi-
ation on TiO2 -GO composites can result in excessive GO reduction
degree and further photodegradation of rGO sheets [105], what
could be a drawback in long-driven photocatalytic applications.
This characteristic has been used for production of a novel structure
of graphene called graphene nanomesh [106].
In general, the initially higher oxygen-containing functional
groups and surface properties of graphene oxide obtained by Hum-
mers method leads to more stable TiO2 -GO composites with better
performance in photocatalytic applications. Therefore, when an
intimate link between reduced graphene oxide sheets and tita-
nium dioxide is pursued, most of the researchers follow a sol-gel
route where the formation of TiO2 nanoparticles and deposition on
Hummers-GO layers happens simultaneously, where a further cal-
cination step is needed [107112]. However some authors tried
hydro/solvo-thermal approaches to crystalize TiO2 , deposit the
nanoparticles and reduce GO in one-pot [78], or combination of
two stages: sol-gel followed by hydro/solvo-thermal procedures
[113115].
The synthesis of doped TiO2 or GO (out of the focus of this short
review) uses the same described routes with the incorporation of
the dopant (metal, non-metal, anion) in the initial steps, followed
by sol-gel and/or hydro/solvo-thermal reaction to complete the
formation of the doped graphene oxide-titania composite.
Most of the authors are conscious that one of the main factors
for having a good graphene-titania composite is the formation of
17
Fig. 5. PL signals for G0-TiO2 , Mixing, and G2.5-TiO2 under excitation at 325 nm.
(The lowest PL intensity indicates the lowest recombination rate of photoinduced
electronhole pairs. PL results demonstrate that only the TiO2 /graphene composite
with the chemically bonding interface can effectively facilitate charge transporta-
tion and separation. From [119]).
Ti C and/or Ti O C between TiO2 and graphene. In the aim to
improve this interaction, new developments have been designed
in the recent years employing different molecules to functionalize
rGO and facilitate the anchorage of TiO2 nanoparticles, leading to
more efcient and durable photocatalyst composites [94,116118].
4. Characterization of titania-graphene photocatalysts
The photocatalytic behavior of graphene oxide-titanium dioxide
photocatalysts becomes directly related to their physico-chemical
properties. The knowledge of these specic features is desirable
to optimize the design of photoefcient composites, where the
modication of synthesis parameters could be associated to some
characteristic variation and nally to photocatalytic activity.
An exhaustively use of many different characterization tech-
niques are usually employed trying to control the oxidation and
reduction degree obtained during graphite to graphene route
(Raman spectroscopy), crystallinity of components (X-ray diffrac-
tion), understand the nature of GO and TiO2 interaction (X-ray
Photoelectronic Spectroscopy, XPS; Fourier Transform Infra-red
spectroscopy, FTIR; Ultraviolet-Visible spectroscopy, UVvis), etc.
All of them facilitate the complementary information required
to argue the improvement on photocatalytic efciency when
graphene oxide is incorporated to the photocatalyst composition
by chemical bonding. While loosely interactions have no effect
on photocatalytic activity; even the photoluminescence (PL) sig-
nal decrease due to recombination inhibition, usually detected for
GO-TiO2 composites (Fig. 5), was not observed in a simple mixing
of materials [91,119125].
Another useful techniques are the determination of photocur-
rent induced when a GO-TiO2 lm deposited over a conductive
substrate, acting as working electrode, is irradiated; or electric
impedance spectroscopy (EIS) to detect the limiting interfaces in
the electronic transfer [109], [126129].
On the other hand, the information obtained by scanning (SEM)
and transmission (TEM) electron microscopy are valuable tools
for morphological, structural and composition (when associated to
EDX) properties of GO-TiO2 composites [46,130,131].
As key values when chemical bonding between GO and TiO2
takes place, could be mentioned: reduction of band gap, UVvis
continuous absorption, appearance of Ti O C signal in FTIR par-
 18
Table 1
Summary of photocatalytic applications of graphene-titania composites in wastewaters.

Fraction of Preparation method Initial Operating Lamp Photocatalytic efciency Reference

Graphene/TiO2 Conditions

Phenol
Solvothermal Phenol Visible and UV Vis: Composite (TGC3-3) [73]
light Xphenol = 62% <> P25,
Xphenol = 20%
UV: Composite (TGC3-3),
Xphenol = 81% <> P25,
Xphenol = 48%
Different TiO2 Sol-gel followed by [phenol] = 10 mg L1 Medium Hg Degree of phenol [74]
concentrations calcination in air or [catalyst] = 100 mg L1 150-W decomposition: Composite
treatment under = 200600 nm (T-G15 V), 0.92 <> P25, 0.58
vacuum max = 366 nm

M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328

Few, one (1), two (2) Hydrothermal [phenol] = 10 mg L1 Halogen Lamp P25 < Police < Composite [152]
graphene layers [catalyst] = 100 mg L1 (400900 nm) (1-RGO-T)
max = 650 nm Best Composite: (single-layer
1-RGO-TiO2 )
0.25-0.5-1.0 wt.% One-pot [phenol] = 50 mg L1 400-W Heraeus (TiO2 -0.25 wt.% TGO), [46]
graphene oxide synthesis + Heat [catalyst] = 147 mg L1 Lamp Xphenol = 96%
treatment
N2 /300 C/1 h
05 wt.% graphene Sol-gel and heat [phenol] = 1 mM UV and Vis Poor phenol photodegradation [59]
oxide treatment 100 C/1 h [catalyst] = 0.5 g dm3 radiation under UV and scare under Vis
light
110 wt.% graphene Heterocoagulation [phenol] = 1 mM High pressure Worse conversion than P25. [96]
oxide from aqueous [catalyst] = 1 g L1 Hg-Lamp Study cycles photodegradation
dispersions = 240580 nm

Phenolic compounds
0.2/0.5/1.5/3 wt.% Hydrothermal [TCP] = 60 mg L1 400-W Composite (GR-1.5 TiO2 ), 90% [122]
graphene oxide [catalyst] = 1000 mg L1 high-pressure TCE and 77% TOC
Na-Lamp. UV
cut-off lter
max > 420 nm
Electrostatic [BPA] = 100 mg L1 Hg-Lamp UV Composite photodegradation [156]
self-assembly [catalyst] = 200 mg L1 Cut-off lter increases:
method + hydrothermal max = 400 nm (GR/TiO2 ) nanoparticle
process < (GR/TiO2 ) nanorod
< (GR/TiO2 ) nanowire (80%)
Hydrothermal [BPA] = 100 mg L1 500-W pH 8, Composite, 84% UV, 71% [121]
[catalyst] = 200 mg L1 Hg-Lamp Vis
UV- pH 11, Composite, 100% UV,
max = 365 nm 85% Vis
Vis-
max = 400 nm
1/2/3/4/5 wt.% Electrospun + Heat [4-CP] = 5.33105 M 500-W Bare Titania, Xphenol = 23% [155]
graphene oxide Treatment [catalyst] = 222.22 mg L1 Xenon-Lamp P25, Xphenol = 41%
Air/500 C/2h < 420 nm Composite (TiO2 /4%GO),
Xphenol = 88%
 Solvothermal [2,4-DCP] = 10 mg L1 High pressure TiO2 nanosheets/grapheme [153]
[catalyst] = 0.04 g Hg-Lamp best performance Cycles
max = 365 nm photodegradation
GO/TiO2 weight ratio: Hydrothermal [Na-PCP] = 50 mg L1 High pressure Best Composite (GO/TiO2 ) [155]
(1:10, 1:100) [catalyst] = 100 mg Hg-Lamp XNa-PCP > 97% <> P25,
XNa-PCP = 31.1%

Trichloroethylene (TCE)
wt. ratio GO-WTiO2 Chemical [TCE] = 500 mg L1 Solar Simulator Best Composite [80]
(0-0.01: 1) Reduction+ [catalyst] = 80 mg L1 Vis-cut-off (WTiO2 -d-graphene-20), 75%
Thermal lter TCE
Treatment > 440 nm
0.520 wt.% graphene Hydrothermal [TCE] = 500 mg L1 Xe solar Best Composite (FTS-G-1), 80% [157]

M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328

oxide [catalyst] = 200 mg L1 simulator + TCE
AM 1.5G lter

Pharmaceutical compounds
Hydrothermal [ATL] = 525 mg L1 1000-W Xe arc Best Composite, 72% ATL and [162]
[catalyst] = 0.5- Lamp + 100% TOC
2 mg L1 AM 15G lter
GO: TiO2 ratio (1:10) Hydrothermal [RS] = 2 mg L1 1500-W Xe arc Higher photocatalytic activity [163]
[catalyst] = 100 mg L1 Lamp of TiO2 -rGO composites
Vis compared to TiO2 -P25
= 430 nm Inuence of water matrix:
photocatalytic efciency
decreases: distilled water < tap
water < river water < lake
water
GO: 0.110 wt.% Hydrothermal [pharmaceuticals] = 5 High-Hg-Lamp Best Composite (TiO2 -2.7% [164]
deposition mg L1 rGO), 54% carbamazepine, 81%
method 10 cm max > 365 nm Ibuprofen, 92%
photocatalyst-coated Low-Hg Lamp sulfamethoxazole
SOFs were placed in a
glass petri max > 254 nm
Vis uorescent
Lamp
(simulated
natural
sunlight)
0.11-11.45 wt.% Solvothermal [noroxacin] = 20 mg L1 Xe Lamp UV- Best Composite: [165]
graphene oxide [catalyst] = 1000 mg L1 > 320 nm (G-TiO2 -0.86 wt.%)
Vis-cut-off XTOC = 86%
lter
> 400 nm
120 wt.% graphene Hydrothermal [acetaminophen] = 5 UV lamp Study of operating conditions: [161]
oxide mg L1 = 254 nm [pollutant], pH Cycles of
[catalyst] = 0.1 g L-1 photodegradation.

19
 20
Table 1 (Continued)

Fraction of Preparation Initial Operating Lamp Photocatalytic efciency Reference

Graphene/TiO2 method Conditions

4 wt.% graphene oxide Immobilized in [Diphenylhydramine] = 3.4105 M Medium- Best performance composite [91,112,158160]
membrane pressure (M-GOT) under vis light
Hg-Lamp
cut-off ltered
>350 nm

Pesticides
0.11-11.45 wt.% Solvothermal [aldicarb] = 10 mg L1 Xe Lamp UV- Best Composite [165]
graphene oxide method [catalyst] = 1000 mg L1 > 320 nm (G-TiO2-0.86 wt.%)
Vis-cut lter XTOC = 36.8%
> 400 nm
4 wt.% graphene oxide Liquid phase [isoproturon] = [alachlor] = 12.5 mg L1 , Fluorescent- Best performance: Composite [151]

M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328

deposition [diuron] = 7.5 mg L1 , Lamp (GO-TiO2 )
[atrazine] = 6.25 mg L1 UV: 6BBL + 4DL, Vis: Composite (GO-TiO2 )
[catalyst] = 500 mg L1 max > 365 nm higher photodegradation than
Vis 10 DL TiO2 -P25
> 400 nm
80 mgL1 graphene TNA by in situ [alachlor] = 210 mg L1 Xe Lamp Best photodegradation: [146]
oxide anodization. Composite (GR/TNA)
GR-TNA by Xalachlor > 99.5% after 15 cycles
electro-
deposition

Photodegradation of others pollutants

One-pot [DCA] = 10090 M 450-W Xe arc Best (Layered-titanate-RGO)
= [102]
synthesis Lamp XDCA = 72%
sol-gel method cut-off lter
> 330 nm
0.510 wt.% graphene Solvothermal [Naftenic 12-W Composite (P25-GR), [148]
oxide acid] = 0.1 g L1 UV-Lamp, XNA > 90% <> P25,
[catalyst] = 0.1 g L1 = 254 nm XNA = 80%
420% wt. graphene Liquid phase [Microcystin- Xe Lamp Vis Better performance under [166]
oxide deposition LA] = 0.2 M simulated and solar light:
[catalyst] = 0.5 g L1 Composite (TiO2 -GO-4)
0.56.4 wt.% graphene Solvothermal [Fulvic High pressure Best Composite (T-3.2% G) [167]
oxide acid] = 100 mg L1 Hg-Lamp
[catalyst] = 0.5 g L1 = 254 nm

Photo-reduction of metals
Deposition [Cr(VI)] = 0.2 mM at pH 20-W UV Lamp Best Composite. (Heat [168]
TiO2 2 max = 253.7 nm Treated GO-TiO2 ): 5.4 times
nanoparticles [catalyst] = 0.5 g L1 more photo-reduction than
on GO P25
nanosheets
20% TiO2 -rGH [Cr(VI)]o = 510 mg L1 250-W Under Continuous ow [171]
[catalyst] = 1000 mg L1 Hg-Lamp conditions- Best performance
max = 365 nm composite (TiO2 -rGH), 100%
photo-reduction
 Hydrothermal [Zn2+ ] = 21 mg L1 1000-W Xe arc Best Composite (TiO2 -G), [172]
method [FA] = 250 mgL1 Lamp + AM 99.99% removal at pH 7.1
[catalyst] = 2 g L1 1.5G lter under solar light
0.510 wt.% Hydrothermal [BrO3 ] = 10 mg L1 24-W Low Best Composite (P25-GR 1%), [173]
graphene oxide method [catalyst] = 0.1 g L1 Pressure-Hg- 99% removal at pH 6.8
Lamp (8 lamps)

M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328

max = 254 nm
30 mg GO One-pot [Cr (VI)] = 10 mg L1 UV 230-W Best photo-reduction, [170]
Solvothermal [catalyst] = 500 mg L1 Hg-Lamp composite (G-TiO2 )
method
Sol-Gel + heat [Cr (VI)] = 12 mg L1 125-W Improved Cr (VI) reduction [169]
treatment [catalyst] = 0.2 g L1 Hg-Lamp (86.5%) composite (TiO2 -RGO)
under vacuum Vis > 450 nm compared to bare TiO2 (54.2%)

Photo-disinfection
Deposition on Antibacterial Test Solar light Best graphene oxide/TiO2 lm [130]
TiO2 thin lms (E. coli, ATCC 25922) by a factor about 6 (7.5)
of GO platelets relative to bare TiO2
TiO2 Standard E. coli test UV-UVP Best disinfection activity: [174]
solvothermal Pen-Ray Composite (GO-TiO2 ) under
GO- Hg-Lamp solar light
TiO2 = Mixing = 254 nm
Vis-Xe Arc
Lamp
1.4, 4.2, 7 wt.% Redox reaction Standard E. coli test Indoor natural Best Composite (TiO2 /4.2 wt% [175]
graphene light GSs)
irradiation,
= 400700 nm
5% w/v GO Mixing + Photoreduction Antibacterial test E. coli Real Natural Vis: E. Coli disinfection: [176]
respect to TiO2 K-12 (ATCC 23631) Solar light Composite TiO2 -RGO better
Fusarium solani (CECT UVA-ltered than P25
20232) solar radiation Vis: E. solani spores similar for
composite and P25

21
22 M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328
tially overlapped to Ti O Ti, wider XPS signal in the region of C1s
and Ti2p due to Ti O C and Ti C contribution, shift of signal due
to weight loss in ATR by stabilization of species when GO-TiO2
are strongly interacting, and attenuation of Ti OH signal in Raman
assigned to Ti O C formation [132135].
5. Photocatalytic applications
It is a long concern that semiconductor-mediated photocatal-
ysis are attracting a lot of attention among scientic community
for its potential applications in environmental remediation [30];
where the presence of materials such as graphene in new titania-
based composites is undoubtedly improving their photocatalytic
performances. The relatively high rate of photocatalytic degrada-
tion ability of graphene-titania nanocomposites is attributed to
efcient charge separation and transfer of photo-induced electrons,
decreasing h+ and e recombination rates, increased light absorp-
tion ranges, ordered crystalline size, and the high oxidizing capacity
of photo-generated h+ [121]. In this section, in turn subdivided in
two parts (water and air pollution processes), a brief summary of
the main applications of graphene-titania catalysts of the last ten
years is reviewed.
5.1. Photocatalytic water treatment
5.1.1. Photocatalytic water decontamination
Great deals of effort are being dedicated to address the
widespread pollution of efuents from urban environment, agri-
cultural and industries with very different bio-recalcitrant organic
pollutants by means of photocatalytic processes. Concerning TiO2 -
graphene composites applied to hazardous waste remediation and
water purication, Chen et al. [136], presented a possible way to
fabricate graphene oxide/semiconductor composites (GOT) with
different properties by using a tunable semiconductor conductiv-
ity type of graphene oxide (GO), where the concentration of GO
in starting solution played an important role in photoelectronic
and photocatalytic performance of composites on methyl orange
photodegradation, and semiconductors formed by GO on the sur-
face of GOT could act as a sensitizer and enhance the visible-light
photocatalytic performance of GOT. However, since the creative
work of Zhang et al. [98], chemically bonded TiO2 (P25)-graphene
composite photocatalysts were prepared by using a hydrother-
mal method; many efforts have been made to utilize the unique
properties of graphene in order to increase the efciency of photo-
catalytic processes. But until now, most of the studied substrates
have been mainly dyes, such as Methylene Blue (MB) [66,137139],
Rhodamine B (RhB) [140142], Methyl Orange (MO) [143], Acridine
Orange Brilliant Red X3B [144], Congo Red [145], Acid Orange 7
(AO7) [146148], Reactive Yellow 145 [149], and Disperse Red 1
(DR1) [150], under both UVvis and Vis light irradiation. When
dyes degradation is involved, the photocatalytic activity of GO-TiO2
composites is most of the times followed by UVvis spectroscopy,
where contributions of other organic molecules (e.g. original com-
pound and intermediates) could happen, disturbing the evaluation
of nal photocatalytic conversion.
Nevertheless, it is essential to extent these studies to differ-
ent types of pollutants, to try to solve the widespread pollution
of efuents where photocatalytic processes will be competitive,
with the aim to reach new developments where this new gen-
eration of photocatalysts based on titania-graphene composites,
can be applied. In this section the main environmental applica-
tions of graphene-titania composites without any metal doping,
concerning treatment of pollutants different of dyes, are briey
summarized in Table 1, where proportion of graphene/TiO2 , prepa-
ration method, initial operating conditions, type of used lamps and
photocatalytic efciency are included, and commented following.
The evolution of these pollutants along irradiation time have
been generally followed by chromatographic system, comple-
mented by determination of total organic carbon (TOC) to evaluate
the effectiveness of mineralization or biodegradability of resultant
efuents [59,151156].
Phenol photodegradation is a frequently studied pollutant, used
as target compound because of its presence in many residual indus-
trial efuents.
One of the rst papers about TiO2 -graphene composites (TGC)
with visible and UV light photocatalytic performance in phenol
degradation was that presented by Jiang et al. [73], where the
thermally treated composites, prepared by solvothermal process,
exhibited higher photocatalytic efciency than Evonik P25, under
both visible and UV lights. Whereas, Aleksandrzak et al. rst studied
the inuence of TiO2 loading and calcination treatment on TiO2 -
reduced graphene oxide nanocomposites in [74]; where higher
TiO2 concentrations resulted in higher photo-catalytic activity; in
[157], the inuence of graphene thickness on its photoactivity was
also explored by these authors, concluding that the highest photo-
catalytic activity was arisen by TiO2 supported on single-layered
graphene (1-RGO-T), where an important decrease in photocat-
alytic activity was observed when the number of graphene layers
was increased. Lastly, Adamu et al. [46] prepared, by a simple
one-pot synthesis, TiO2 -graphene oxide (GO)/thermally reduced
graphene oxide (TGO) composites, where the best performance
was arisen with 0.25 wt% loadings of GO and TGO, which could
be explained by hybridized adsorption-carrier charge separation
cooperation. In contrast, Szab et al. [96] and Minella et al. [59]
reported worse phenol conversion when graphene oxide was incor-
porated to the photocatalyst composition. In the case of [96] GO
was prepared by Brodies method with different ratios to TiO2 (P25)
in the composite; besides photoactivity, a sedimentation study for
catalyst recovery and reuse during four cycles was carried out with-
out photoactivity loss. The GO-TiO2 composites prepared by [59]
showed poorer conversion with increasing GO proportion under
UV light, while scarce photoefciency was observed when Vis light
was employed.
Other chlorophenolic compounds have been also studied as tar-
get pollutants in their photo-oxidation; graphene modied TiO2
composites prepared by Hu et al. [122] was used for the photo-
catalytic degradation of 2,4,6-trichlorophenol (TCP) under visible
light, where a percentage of 1.5 wt% of graphene in a modied TiO2
nanocomposite showed the highest electron-hole separation rate,
the highest photocatalytic activity (90%) and good stability after
three cycles of photodegradation. Sun et al. [158] described the
photodegradation of 2,4-dichlorophenol (2,4-DCP) with different
TiO2 morphologies (nanosheets and nanorods) bonded to graphene
oxide, achieving the maximum conversion with a loading of 0.5%
GO. They studied the mechanism using scavengers and durability
along ve consecutive cycles. Continuing with studies of chlorophe-
nols, Zhang et al. [159] photodegraded sodium pentachlorophenol
(Na-PCP); both found improvement with the incorporation of
graphene oxide by simple solvo/hydro-thermal routes. Finally,
Zhang et al. [160] has recently reported the preparation of well-
dened and structurally stable TiO2 nanobers aggregated by GO
with different contents (05 wt.%) by means of electrospinning
technology. Their photocatalytic activity indicated that TiO2 /GO
composite nanobers possessed higher photocatalytic ability than
TiO2 -P25 and the bare titania nanobers for degradation of 4-
CP molecules under visible-light due to the enhanced separation
efciency of photogenerated electron-hole pairs showing higher
mobility of charge carriers.
The photodegradation of bisphenol-A (BPA) in water was
studied by Hua et al. [161] who analyzed different graphene (GR)-
 M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328
modied morphologies of TiO2 , including nanoparticles, nanorods
and nanowires, and Bai et al. [121] prepared graphene (GR)/TiO2
nanocomposites that presented signicantly higher photocatalytic
activity than TiO2 -P25, mostly attributed to effective charge trans-
fer from TiO2 nanoparticles to GR, exhibiting good performance
after ve cycles of photodegradation.
The photocatalytic performance of some graphene-titania
composites were evaluated through the photodegradation of
trichloroethylene (TCE) in aqueous suspensions, by Lee at al. [81],
who improved the photocatalytic properties of TiO2 (P25) by
using water-mediated titania decorated with graphene (WTiO2 -
d-graphene) composites, and Kim et al. [162] who synthesized
novel ower-like TiO2 spheres (FTS)/reduced graphene oxide (rGO)
composites (FTS-G) which also presented a good photocatalytic
performance in TCE photodegradation.
The destruction of emerging contaminants is one of the most
suitable applications of photocatalysis technology; usually, rela-
tively dilute multi-component solutions and xed volumes are
involved, that can be recirculated to achieve complete miner-
alization of organic carbon in the existing environment. In this
context, the most recent papers focused on the photo-oxidation
of antibiotics, pharmaceutical compounds, drugs, pesticides, etc.
over titania-graphene composites can be considered very rele-
vant in wastewater applications by heterogeneous photocatalysis.
Pastrana-Martnez, Morales-Torres et al. [91,112,163165] carried
out a complete study about diphenilhydramine photodegrada-
tion utilizing the GOT composite immobilized in membranes, they
found relevant the photoactivity employing Vis light. The pho-
tooxidation of acetaminophen [166] was aborded analyzing the
effect of initial concentration of contaminant and catalyst load-
ing, pH, scavengers and cycles, although using 254 nm UV light.
Bathia et al. [167] synthesized, by a simple hydrothermal method, a
graphene oxide-TiO2 (P25), evaluating its photoactivity in atenolol
(ATL) photo-degradation, as model pharmaceutical pollutant under
UVvis light and simulated Sun irradiation conditions. One of the
most novelty and complete papers has been presented by Calza
et al. [168] where some graphene-based composites were syn-
thesized through a hydrothermal method using graphene oxide
and the commercial TiO2 -P25 as starting materials. Their photo-
catalytic activities were assessed through the photodegradation of
risperidone (RS, an antipsychotic drug), under a variety of experi-
mental conditions, such as, different aqueous matrices (distilled,
tap, river and lake water) under articial solar light and visible
light. Concluding that the use of a TiO2 -rGO10 composite revealed
the effectiveness and benets, in terms of faster drug disappear-
ance, earlier abatement of toxicity and easier photodegradation of
the transformation products and mineralization; at the same time
both reduction of toxicity and mineralization were faster achieved
than with bare TiO2 -P25. The photocatalytic performance of a series
of TiO2 -reduced graphene oxide (rGO) coated side-glowing optical
bers (SOFs), synthesized by polymer assisted hydrothermal depo-
sition method (PAHD), in the degradation of three pharmaceuticals,
including carbamazepine, ibuprofen, and sulfamethoxazole, under
UV and visible light irradiation, was analyzed by Lin et al. [169].
Their photocatalytic activity increased with the concentration of
rGO (02.7%) in composites, but the degradation was inhibited
when the rGO concentration was larger than 2.7%. A pesticide,
aldicarb, and an antibiotic, noroxacin, were used as the model
compounds to determine the photocatalytic performance in sim-
ulated sunlight and visible light irradiation [170] under a series of
graphene/TiO2 composites using a single-step nonionic surfactant
strategy combined with the solvothermal treatment technique.
Cruz et al. [151] analyzed the photodegradation of a mixture of
four pesticides: diuron, alachlor, isoproturon and atrazine with
a GO-TiO2 composite under both UVvis and visible light. Their
photo-efciencies were always better than bare TiO2 , with very
23
Fig. 6. Effect of water matrix on pesticides photodegradation: relation of initial
reaction rates (r0,natural /r0,ultrapure ) for degradation of pesticides with bare TiO2 and
GO-TiO2 catalysts. Operating conditions: [TOC]0 = 22.8 mgL1 , irradiance: EUV-A = 40
Wm2 and catalyst loading = 500 mgL1 . (From [156]).
good initial pesticide photodegradation rates under both natu-
ral and ultrapure water matrices as it can be seen in Fig. 6. The
photocatalytic activity found for GO-TiO2 composite under visi-
ble light was remarkably higher than TiO2 -P25. Zheng et al. [146]
developed a titanium dioxide nanotubes electrodes where was
electrodeposited graphene oxide to demonstrate the improvement
in alachlor photodegradation, maintaining a conversion higher
than 99.5% after 15 cycles.
Finally, others compounds such as e. g. dichloroacetic acid
(DCA) was also studied as model pollutant in the photocatalytic
degradation (Kim et al. [102]), under coupled nanocomposites of
layered titanate and reduced graphene oxide (RGO), where the
layered-titanate-RGO nanocomposite was much more active than
uncomposited layered titanate under visible-light as a consequence
of fairly strong electronic coupling. Liu et al. [148] prepared P25-
GR composites by solvothermal method, that achieved more than
90% of naftenic acids removal, much higher than P25 (XNAs < 80%).
The effect of pH and graphene content was optimized and radi-
cals trapping experiments pointed to OH and holes as the crucial
reactive species. Sampaio et al. [171] described the behavior of GO-
TiO2 with variable GO loading (420%) during photodegradation
of microcystin-LA under Xe or Vis lamps, obtaining the best per-
forming with 4% GO. However, Zhou et al. [172] found a slight
improvement in the photodegradation of fulvic acids with T-G com-
posites prepared by solvothermal procedure.
Compared to other chemical methods, the photocatalytic
method displays many advantages in removing toxic heavy metal
ions, including high efciency, low energy consumption, and mild
reaction conditions, which are the key points for removing Cr (VI)
pollution from water. Jiang [173], Zhao et al. [174], Wang et al.
[175] and Li [176] studied the photocatalytic reduction of Cr (VI)
with graphene-titania based composites. Whereas the synthesized
graphite oxide/TiO2 composites [168] not only exhibited excel-
lent photocatalytic ability for the oxidative degradation of organic
pollutants, but also showed strong photocatalytic activity for the
reductive conversion of inorganic pollutants such as Cr (VI). TiO2 -
graphene hydrogel with three-dimensional (3D) network structure
[171] also presented an excellent adsorption-photocatalysis per-
formance, removing 100% Cr (VI) under UV irradiation. The same
optimal behavior was obtained for the sol-gel prepared TiO2 -RGO
photocatalyst [169] followed by heat treatment at 600 C for 1 h,
able to reduce 86.5% of Cr(VI) compared to 54.2% of bare TiO2 .
Kumordzi et al. [177], synthesized a composite catalyst of TiO2
and graphene by a hydrothermal treatment method to photo-
reduce Zn2+ , the most abundant heavy metal found in combined
 24
Table 2
Summary of graphene-titania composites in photocatalytic applications in air pollution control.

Fraction of Preparation method Initial Operating Conditions Lamp Photocatalytic efciency Reference
Graphene/TiO2

0.230 wt.% graphene Solvothermal [benzene] = 250 ppm UV lamp, = 254 nm Best Composite (TiO2 -P25-0.5% [48]
oxide GR), XBenzene = 76.2% <>
P25, XBenzene = 5.8%

M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328

0-0.2 wt.% graphene Hydrothermal [acetone] = 300 20 ppm UV 15-W Lamp, = 365 nm Best Composite (TiO2 -0.05 wt.% [177]
oxide [catalyst] = 0.3 g (dish-coated) GO) enhanced photoactivity
1.7 and 1.6 times more
TiO2 -bare and TiO2 -P25
0.01-0.15 wt.% Colloidal blending 55% RH Vis: 8-W daylight lamp Best photodegradation [178]
graphene oxide process [BTEX] = 0.11 ppm = 400700 nm Composite (TiO2 GO-0.10)
UV: 8-W black light
= 352 nm
510 wt.% graphene Impregnation 96 vol.% ethanol/benzene 1000 W high-pressure Best performance: Composite [179]
oxide [catalyst] = 0.05 g Hg-Lamp cut-ltered, (TiO2 -P25/H-GO)
= 310390 nm
Nanostructured Hydrothermal [Methanol] UV radiation Total photodegradation of [180]
Membrane: rGO/TiO2 methanol composite
ratio 1:10 (Graphene + TiO2 ) Type B
graphene 0.04cm2
0.53.0 wt.% graphene Solvothermal [HCHO] = 200 ppm UV LED, = 365 nm Composite (G2.5-TiO2 ), 2.6 [181]
oxide [catalyst] = 0.05 g times more photodegradation
than pure TiO2
GO-TiO2 ratio: 0.033 Chemical mixing Study of [catalyst], [2E1H] and Fluorescent lamp Best composite (GO-TiO2), [149]
percentage of humidity = 400720 nm X2E1H = 99.3%, mineralization
55.1%
0.52.0% Solvothermal [NO] = 1000 ppb 20 W m2 Iron Halogenide Best composite GO-TiO2 [182]
[catalyst] = 50 mg Lamp, = 315400 nm XNOx = 100%
RH: 50%
0.01/0.1/1.0 wt.% Solvothermal NOx Standard ISO/DIS-22197-1 UV-A 15-W Lamps Best composite (TiO2 /rGO-2) [183]
graphene oxide procedure Vis 8-W Lamps UV XNOx = 41.51%
[NO] = 1 ppm Vis XNOx = 22.34%
Relative Humidity 50%
 M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328
sewer overows (CSOs). This TiO2 -Graphene composite showed
high performance in the photo-reduction of Zn2+ under solar light
compared to un-doped titania. The photodegradation of bromate
(BrO3 ) has attracted much attention as bromate is a carcino-
genic and genotoxic contaminant in drinking water. Huang et al.
[178], studied TiO2 -graphene composite (P25-GR) photocatalyst
for BrO3 reduction, prepared by a facile one-step hydrothermal
method, where the composite of P25 with 1% GR loaded exhibited
higher (BrO3 ) removal efciency. The physical characterization
revealed that the photo-reduction instead of adsorption was pre-
dominantly responsible for the bromate removal.
5.1.2. Photocatalytic water disinfection
It is widely known that the addition of a catalyst enhances the
efciency of solar disinfection. Heterogeneous photocatalysis uti-
lizes light along with a semiconductor to produce reactive oxygen
species (ROS) which can inactivate bacteria and degrade a wide
range of chemical contaminants in water. One of the rst appli-
cations reported of titania-graphene composites was the work of
Akhavan et al. [179] who utilized graphene oxide/TiO2 thin lms
reduced at different irradiation times as nanocomposite photocat-
alysts for degradation of E. coli bacteria in an aqueous solution
under solar light irradiation. The photocatalytic reduction of these
graphene oxide platelets for four hours caused an improvement of
the antibacterial activity of the TiO2 thin lm by a factor of about
7.5.
Gao et al. [180] successfully synthesized various TiO2 nanos-
tructures including one-dimensional (1D) TiO2 nanotube, 1D TiO2
nanowire, three-dimensional (3D) TiO2 sphere assembled by
nanoparticles (TiO2 sphere-P) and 3D TiO2 sphere assembled by
nanosheets (TiO2 sphere-S). The combination of TiO2 sphere-S with
graphene oxide (GO) sheets can further enhance the photodegrada-
tion efciency of AO7 and disinfection activity of Escherichia coli (E.
coli) under solar light, which is more energy efcient. Cao et al. [181]
obtained composites of ultrane TiO2 nanoparticles and graphene
sheets (GSs) for the photodegradation of E. coli bacteria. With opti-
mization of the content of GSs in the composite, the TiO2 /4.2 wt%
GSs sample exhibited the best photocatalytic antibacterial activity
under ambient visible light illumination.
TiO2 (P25)-RGO composites have been applied in the disinfec-
tion of water contaminated with E. coli and Fusarium solani (F.
solani) spores under real sunlight by Fernandez-Ibanez et al. [182].
An enhancement in the rate of inactivation of E. coli was observed
with the TiO2 -RGO composite compared to P25 alone. The rate of
inactivation of F. solani spores was similar for both TiO2 -RGO and
P25. When the major part of the solar UVA was cut-off (k > 380 nm)
using a methacrylate screen, there was a marked increase in the
time required for inactivation of E. coli with P25 but no change in the
inactivation rate for TiO2 -RGO was found. There is evidence of sin-
glet oxygen production with visible light excitation of the TiO2 -RGO
composites which would lead to E. coli inactivation.
5.2. Photocatalytic air pollution control
On the contrary, a very few papers in the literature, based on
TiO2 -graphene composites, have been applied to photocatalytic
degradation of air pollutants compared to photocatalytic waste
water applications. In Table 2 are summarized all these works,
where again, proportion of graphene/TiO2 , preparation method,
initial operating conditions, type of used lamp and photocatalytic
efciency are included. Some of them obtained titania-graphene
composites using the known TiO2 -P25 from Evonik, such as Zhang
et al. [48] who synthetized by a simple solvothermal method
TiO2 P25-graphene (G) composites, and were compared with TiO2
P25-carbon nanotubes (CNT) during photocatalytic degradation of
benzene vapor. The best photocatalytic performance was observed
25
with 0.5 wt% G, analogously to CNT. The authors suggest that G
acts similarly to any other carbon-based (CNT, fullerenes, and acti-
vated carbon) composite on enhancement of photocatalytic activity
of TiO2 , although structural and electronic characteristics make
G unique compared to other carbon allotropes. The 2D structure
with abundant oxygen-containing functional groups provides reac-
tive sites to interact with organic/inorganic systems; while the
induced photocurrent, recombination rate of photogenerated e /h+
and response to visible radiation, lead in turn to the observation of
much higher photocatalytic activity of G-TiO2 . The increase of G
or CNT ratio into the composite results in higher adsorptivity of
pollutants, consequently, the contact surface of TiO2 particles with
the light irradiation becomes reduced, which would provoke lower
photocatalytic activity. The stability and activity of TiO2 (P25)-G
nanocomposites resulted much higher than bare TiO2 . Wang et al.
[183] studied the effect of graphene content in the photocatalytic
degradation of acetone in air, resulting an optimal concentration
of 0.05 wt.% in the hierarchical macro/mesoporous TiO2 compos-
ite, at which the prepared materials improved the photocatalytic
activity of bare TiO2 and commercial P-25 by a factor of 1.7 and 1.6,
respectively.
Jo et al. [184] developed a TiO2 (P25)-GO-0.10 composite by
means of colloidal blending process which exhibited superior pho-
tocatalytic performance than unmodied P25-TiO2 for degradation
of vaporous aromatic pollutants (BTEX) under both visible-light
and UV irradiation, or Andryushina et al. [185] who also prepared
composites by an impregnation method to be applied in the pho-
tocatalytic gas-phase oxidation of ethanol and benzene vapors.
Roso et al. [186] deposited TiO2 (P25) and TiO2 (P25)-graphene
composites on membranes, and found that graphene based photo-
catalysts revealed a higher reaction rate on methanol gas-phase
degradation; moreover, the performance of the nanostructured
membranes could be restored several times by stripping with an
inert gas.
Also, some home-titania synthesis have been analyzed to
obtain graphene-based composites in air pollution control, such
as paper of Huang [199] developed a chemically bonded G2.5-
TiO2 composite with 2.5 wt.% graphene that effectively enhanced
the photocatalytic activity in photodegradation of formaldehyde
in air, or Chun et al. [149] who concluded that a two-dimensional
graphene oxide-coupled titania (GOTiO2 ) hybrid post-treated at
400 C does not presented appreciable loss of photocatalytic ef-
ciency after ve cycles for the degradation of low-concentration
gas-phase 2-ethyl-1-hexanol (2E1H) in continuous-ow mode
under visible-light illumination. Neppolian et al. [187] demon-
strated that GO-TiO2 was an excellent catalyst for the total
decomposition of toxic NOx gas that was achieved within 50 min.
Analogously, Trapalis et al. [188] studied the photocatalytic per-
formance in the abatement of NOx with two types of composites
TiO2 /G and TiO2 /rGO, each with graphene loadings 0.01-1%. The
TiO2 /rGO at low 0.1% graphene loading, exhibited superior ef-
ciency than the TiO2 /G under Vis radiation, due to interaction
between TiO2 -nanoparticles and graphene sheets.
On the basis of the observations could be concluded that the
capability of graphene oxide for accelerating the photocatalytic
transformations of pollutants in air depends on a balance between
two factors, in particular, (i) interaction of graphene oxide with
the titania nanocrystal surface via anchoring functional groups and
(ii) efciency of acceptance of the photogenerated TiO2 conduction
band electrons [179].
6. Future advances in the development of visible-light
active photocatalysts based on TiO2 -graphene
Photocatalytic process is a known technology efcient for treat-
ment of reduced volume of efuents and moderately contaminated.
26 M. Faraldos, A. Bahamonde / Catalysis Today 285 (2017) 1328
Continuous efforts have been done to develop new photocata-
lysts more active in the use of solar light; in this sense, different
strategies have been designed to dope the semiconductor obtain-
ing colored photocatalyst sensitized in the Vis region, composites
based on mixture of different semiconductors, oxides, carbona-
ceous materials or adsorbent structures [189]. New approaches
and more creative synthesis routes should emerge trying to avoid
the aggregation induced in TiO2 particles by reduction treatments
necessary to improve the crystallinity of graphene basal plane.
The use of UV radiation, microwave assisted or freeze-drying
treatments is promising in the future photocatalysts development
which combined with ultrasonication, dialysis and higher control
of suspensions stability by addition of adequate compounds, adjust
of ionic strength or shifting pH values, could arose more stable and
efcient photo-composites.
The use of functionalized graphene oxide seeks to improve the
composite materials linkage, gaining in photoefciency and sta-
bility. Currently, the discrimination of the amount of GO bonded
to TiO2 by chemical interaction (Ti C and/or Ti O C) from the
loosely interacting, and the different behavior of these both types
of GO in the photocatalytic processes, still supposes a difculty. In
this sense, characterization techniques such as XPS, complemented
by others (FTIR, UVvis, TGA, etc.) previously mentioned in sec-
tion 4, could deeply help to clarify the nature of interactions and
determine the real loading of GO in TiO2 -rGO composites.
One of the drawback for real applications is the recoverability of
catalyst, and more developments are needed to dene immobilized
systems like described in the form of membranes [186,160,190] or
bers [191193], but still low competitive compared to suspended
photocatalytic devices.
Applications of graphene-TiO2 photocatalysts are focused on
dyes photodegradation and only some tens of different pollutants
present in water and air, however very few was found up to now
about self-cleaning uses [58,194], when the possibility to produce
transparent lms with the presence of highly exfoliated graphene,
open an interesting eld.
7. Conclusions
The photocatalytic behavior is frequently difcult to understand
because numerous simultaneous processes are interrelated. The
more complex system the more difcult to nd a linear or direct
relationship between photoefciency and composition of photo-
catalyst, or amount of graphene oxide present in the composite, or
grade of oxidation of graphene surface, etc. Even the performance
varies with the different pollutants involved. Takind into account
that rate and efciency of heterogeneous photocatalytic reactions is
highly dependent on a certain number of parameters which govern
the kinetic of the process, where it must be also taken into account
that photocatalytic processes are mediated by photonic activation.
In this context, and since every single research group has carried
out their studies at different operating conditions, with different
photoreactors and light sources, results a very difcult task to try
to compare them and getting some comparative conclusions. How-
ever there are some points that seem to emerge along the majority
of the papers revised:
GO oxidized by Hummers method seems to be more efcient in
the photocatalytic degradation of pollutants than GO prepared
by Brodies method.
Control of graphene oxide reduction grade plays an important
role to achieve both good conductivity to promote photogener-
ated charges mobility and presence of enough oxygenated groups
in rGO surface to favor the advance of oxidation reaction.
Assurance of chemical bonding between graphene oxide and
titanium dioxide is required to obtain advantages such as Vis
absorption extension, transition of electron among conduction
band of TiO2 and graphene, increase of charges mobility, reduc-
tion of recombination, among others.
Optimization of GO/TiO2 ratio is an important detail, most of the
authors report optimal loadings lower than 5% of GO.
It is necessary to widen the scope where photocatalytic appli-
cations of graphene oxide-titanium dioxide composites could
be useful: different pollutants, real water efuents, self-cleaning
materials, biocide coatings, etc. are elds that still need to be
explored.
Acknowledgment
This work has been supported by the Spanish Plan Nacional de
I+D+i through the project CTM2015-64895-R.
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