A Review of TiO2 Nanostructured Catalysts For

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e3 2
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Review Article
A review of TiO2 nanostructured catalysts for

sustainable H2 generation
Mingzheng Ge a,1, Jingsheng Cai a,1, James Iocozzia b, Chunyan Cao a,

Jianying Huang a, Xinnan Zhang a, Jiali Shen a, Shanchi Wang a,
Songnan Zhang a, Ke-Qin Zhang a, Yuekun Lai a,*, Zhiqun Lin b,**
a
National Engineering Laboratory for Modern Silk, College of Textile and Clothing Engineering, Soochow University,
Suzhou, 215123, PR China
b
School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA, 30332, USA
article info abstract
Article history: Hydrogen is an attractive alternative to fossil fuels that addresses several environmental
Received 28 October 2016 and energy shortage issues. Nano-sized TiO2-based photocatalysts with unique structural
Received in revised form and functional properties are the most extensively studied photocatalytic nanomaterials
8 December 2016 for hydrogen production and pollutant degradation. However, titania is hampered by a
Accepted 12 December 2016 wide band gap, low utilization of solar light and a rapid recombination of electron/hole
Available online xxx pairs. These issues limit its photocatalytic performance. In this review, we present the
latest developments in the fabrication of different higher dimensional TiO2 nanostructured
Keywords: materials that aim to address these inherent limitations to an otherwise very promising
Hydrogen production material. Specifically, we will look into critical engineering strategies to enlarge the active
TiO2 nanostructure surface area, enhance visible light absorption and suppress the recombination of electrons/
Catalyst holes that benefit their photo/photoelectric-catalytic water splitting activity. Finally, the
Photocatalysis current challenges and perspectives for TiO2 nanostructures are also discussed. Contin-
Photoelectrocatalysis uous efforts are necessary to endow TiO2-based materials with novel advanced function-
ality and commercialization potential in the coming years.
© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Synthesis of multi-dimensional TiO2 nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Controlled growth of 0D TiO2 nanoparticles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Rational synthesis of 1D TiO2 nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
TiO2 nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
TiO2 nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
* Corresponding author.
** Corresponding author.
E-mail addresses: yklai@suda.edu.cn (Y. Lai), zhiqun.lin@mse.gatech.edu (Z. Lin).
1
These authors contributed equally to this work.
http://dx.doi.org/10.1016/j.ijhydene.2016.12.052
0360-3199/© 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Ge M, et al., A review of TiO2 nanostructured catalysts for sustainable H2 generation, International
Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2016.12.052
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e3 2
TiO2 nanorods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
TiO2 nanobelts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
TiO2 nanofibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Formation of 2D TiO2 nanostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Synthesis of 3D TiO2 hollow and hierarchical materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Porous TiO2 films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Porous/hierarchical hollow TiO2 spheres . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Solar water splitting by nanostructured TiO2 materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Pure TiO2 nanomaterials for hydrogen production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Synthesis of pristine TiO2-based active photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Enlargement of the photocatalytically active area . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Optimizing the crystallinity and exposed facets . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Development of visible light-sensitized photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Bulk doping with metal and non-metal elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Sensitization with noble metal particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Surface modification with graphene and narrow band gap semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Conclusions and perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 00
intrinsic drawbacks that have limited the wide application of

Introduction TiO2 in its many multidimensional nanostructure forms. With
a wide band gap, TiO2 (anatase: 3.2 eV, rutile: 3.0 eV) has a low
The rapid development of a global economy and associated utilization of the solar light spectrum. Furthermore, a fast
industrialization over the past century has brought about recombination of photo-generated electronehole pairs and a
serious concerns regarding global resource consumption. large overpotential for water splitting leads to low photo-
First, fossil fuel resources are rapidly depleting and becoming catalytic efficiency. Therefore, in order to achieve high
ever more inaccessible. Second, our rapid consumption of hydrogen production rates and stabilities, more efforts have
carbon-based fossil fuel energy sources has led to global been devoted to enlarging the effective photocatalytic surface,
warming and climate change concerns [1e4]. Despite these forming Schottky junctions or heterojunctions, and engi-
concerns, fossil fuels still remain the major energy source used neering the band structure to match particular energy levels
in people's daily lives. This has motivated an urgent need for [26e28].
renewable sources of clean energy. Photocatalytic hydrogen In this review, we present the state-of-the-art in the
(H2) generation from water splitting is considered an ideal development and fabrication of well-defined 0D, 1D, 2D and 3D
alternative to conventional fossil fuels for future energy de- TiO2 nanomaterials synthesized via hydrothermal methods,
mands because it is generated from abundant water resources solvothermal methods, solegel methods, template methods,
and its products are harmless [5e9]. With increased public electrospinning and electrochemical anodic oxidation. In
interest in water splitting, efficient and stable photocatalysts order to achieve higher efficiency for solar water splitting,
are in urgent demand to improve the hydrogen production heterogeneous structures are produced by combining
rates. different surface engineering strategies such as enlargement
Titanium dioxide (TiO2), since its first application in water of photocatalytically active areas, optimizing the crystallinity
splitting by Fujishima and Honda in 1972, has been heavily and exposed facets, development of visible light sensitized
investigated in photocatalysis [10,11], solar cells [12,13], photocatalysts by doping or modifying TiO2 with metals, non-
lithium ion battery electrodes [14,15], biomedical devices metals and narrow band gap semiconductors. Lastly, the
[16,17] and intelligent coatings [18,19]. Most initial in- challenges and future developments facing TiO2 nano-
vestigations were focused on 0D TiO2 nanoparticles which materials will be discussed.
exhibited excellent performance as photocatalyst, adsorbents
and sensors due to its large surface area and easy of fabrica-
tion [20e22]. However, the inherent disadvantages such as fast
recombination of electrons and holes, slow charge carrier Synthesis of multi-dimensional TiO2
transfer and high recycling cost limit its photocatalytic effi- nanostructures
ciency. Recently one-dimensional (nanotube, nanowire,
nanorod etc.), two-dimensional (nanosheets) and three- As nanostructure plays a key role in the properties and pho-
dimensional hierarchical structures have demonstrated tocatalytic efficiency of TiO2 nanomaterials, various synthetic
improved electron/hole separation, fast charge carrier trans- pathways have been developed for the formation of TiO2
fer and enlargement of active surface area compared to TiO2 nanostructures. Previous work has addressed hydrothermal
nanoparticles. This has led to improvement in the photo- methods, solegel methods, solvothermal methods, electro-
catalytic activity [23e25]. However, there are still some chemical anodic oxidation methods, microwave-assisted
i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e3 2 3
methods, template-assisted methods and reverse micro- et al. demonstrated a facile and practical hydrothermal
emulsion methods among others. In this section, we briefly approach to synthesize spindle-shaped nanoporous anatase
describe the numerous ways that have been recently devel- TiO2 particles composed of many tiny nanocrystals, which
oped for designing multi-dimensional (0D, 1D, 2D and 3D) TiO2 were used as a suitable support to fabricate the AgI/TiO2
materials with different sizes and morphologies, such as composites. Tetrabutyl titanate (2 ml) was added dropwise to
nanopowders, nanoparticles, nanotubes, nanorods, nano- 50 ml of acetic acid with continuous stirring. Then, the mixture
wires, nanobelts, nanofibers, porous films, porous spheres, 3D was transferred to a Teflon-lined stainless-steel autoclave and
hierarchical nanostructures and others [29e39]. kept at 200 C for 24 h. After several washing steps and
centrifugation at 10,000 rpm, spindle-shaped TiO2 nano-
Controlled growth of 0D TiO2 nanoparticles particles were obtained. As shown in Fig. 1b, the TiO2 nano-
particles are well-dispersed. The average size of TiO2 particles
0D nanostructures refer to those with spherical shapes with is 80 nm with a narrow dispersity and minimal aggregation
dimensions less than 100 nm [40]. As previously mentioned, [46]. Recently, Bruce et al. successfully synthesized nano-
there are several approaches to synthesize TiO2 nanoparticles particulate TiO2 (Fig. 1b) by a hydrothermal method followed
described in this section. In electro-deposition processes, ions by thermal treatment [47]. Briefly, glycolic acid is added to the
dispersed in a solution migrate deposit as particles on an mixture of H2O2 and NH3 in water with Ti metal to obtain a
electrode. Jiang et al. reported a simple electrochemical titanium glycolate complex. This is then subjected to hydro-
method for the deposition of TiO2 nanoparticles on multi- thermal treatment at 160 C for 30 min, and after the resulting
walled carbon nanotube arrays in an electrolyte containing solid was calcined at 300 C for 1 h, TiO2 was formed. TEM
10 mM H2O2, 3 M KCl and 10 mM Ti(SO4)2. The potential was imaging (Fig. 1c) demonstrated that the as-synthesized TiO2 is
0.10 V and the deposition time was 30 min with the multi- composed of smaller nanoparticles of with diameters between
walled carbon nanotube acting as the working electrode a 2.5 and 4.3 nm with relatively narrow size distributions.
Ag/AgCl electrode as the reference electrode and a Pt sheet as
the counter electrode [41]. The size and morphology of the as- Rational synthesis of 1D TiO2 nanostructures
prepared TiO2 nanoparticles were easily controlled by adjust-
ing the reaction temperature, time and pH. Fabrication of 0D In recent years, 1D TiO2 nanostructures have been extensively
size-controllable TiO2 nanoparticles with less agglomeration studied because of their specific morphologies and novel
and higher crystallization can be obtained by solvothermal properties. Several general methods have been developed to
methods. It is well known that smaller nanostructures and synthesize 1D TiO2 nanostructures with various morphology
limited dehydration give rise to better crystallinity in TiO2 types including hydrothermal processes, electrochemical
when performed in low dielectric constant organic solvents anodization, chemical vapor deposition, solegel methods,
[42,43]. By using titanium isopropoxide as the precursor and electro-spinning and solvothermal methods. In this section,
1,4-butanediol as the solvent, Kang et al. successfully obtained we will briefly introduce 1D TiO2 nanomaterials with different
TiO2 nanoparticles with diameters 20e50 nm under 300 C morphologies, including nanotubes, nanowires, nanorods and
after reaction for 50 min [44]. Combing solegel method with nanobelts prepared by the above methods.
solvothermal process, Chen et al. successfully synthesized
titanate/titania hybrid 20 nm nanoparticles with a high surface TiO2 nanotubes
area of 180 m2 g1 greatly improving the catalytic performance Kasuga et al. first developed TiO2 nanotubes by treating
(Fig. 1) [45]. The newly synthesized dual-phase-photocatalyst amorphous TiO2 powders with 10 M NaOH aqueous solution
surface shows unique affinity for dye adsorption, thereby via a hydrothermal process without sacrificial templates
facilitating efficient mineralization under UV and visible light [48e50]. First, precursors of TiO2 and the reaction solution are
due to sensitization with doped nitrogen. Through mesoscale enclosed in a stainless steel vessel under controlled temper-
assembly of crystallographically-oriented nanocrystals. Peng ature and pressure. The vessel was then rinsed with deionized
Fig. 1 e HRTEM image of the as-prepared photocatalyst with two phases. The inset is the diffraction pattern of the
monoclinic TiO2 and tetragonal anatase phases (a) [45]. TEM image of spindle-shaped TiO2 particles (b) [46] and HRTEM
image of a single TiO2 nanoparticle (c) [47].
water and acidic solution to neutralize excess base. The dispersed into 15 ml NaOH solution (10 M), then transferred
advantage of this method is the almost complete conversion into a 25 ml Teflon-lined stainless-steel autoclave with a
of the precursors to TiO2 nanotubes in one single process magnetic stirrer inside a silicon oil bath at 130 C for 24 h. After
without high temperature (Fig. 2). that, the autoclave was taken out from the oil bath and cooled
In a similar hydrothermal approach, Geng et al. used pure to room temperature. The sodium titanate was collected by
rutile TiO2 powder and 10 M NaOH to synthesize TiO2 nano- centrifugation, washed with deionized water several times to
tubes at 150 C for 72 h [51]. The calcination temperature reach a pH value of 9. After that, the samples were subjected
should not be too high (400 C) to prevent the TiO2 nanotubes to a hydrogen ion exchange process in HNO3 solution (0.1 M)
from sintering together and dislocating to form TiO2 nano- for three times. Finally, the suspension was centrifuged again
particles. The resulting samples are 200e400 nm in length and with deionized water for several times to reach a pH value of 7,
4 and 10 nm in inner and outer diameter, respectively (Fig. 3a). obtaining the hydrogen titanate nanotube materials.
Park et al. obtained TiO2 nanotubes via anodic alumina Alternatively, for obtaining highly ordered nanotubes
membrane (AAM) synthesis and hydrolysis by water vapor via perpendicularly-oriented to the surface of the electrode sub-
a solegel method. Fig. 3b shows SEM images of the as- strate electrochemical anodization of Ti foil has been well-
synthesized TiO2 nanotubes with diameters of 200 nm and established as a simple and efficient method to prepare self-
lengths of 50 mm (the thickness of the alumina membrane). aligned TiO2 nanotubes on a Ti substrate at ambient condi-
The results support that this method can easily prepare TiO2 tions [55,56]. Based on the electrolyte, it has been found that
nanotubes at room temperature. Traditional hydrothermal highly ordered anodic TiO2 nanotube arrays (TiO2 NTAs)
methods still have several disadvantages such as long reac- with long nanotubes can be categorized into 5 generations
tion times, limited applicability and non-uniformity of (Table 1).
resulting nanotubes [52]. To address these disadvantages,
Tang et al. grew elongated TiO2 nanotubes with lengths up to TiO2 nanowires
tens of micrometers via a modified stirring hydrothermal With better understanding of their growth and nucleation,
method (Fig. 4) [53,54]. In brief, P25 powder (0.1 g) was TiO2 nanowires have recently been extensively synthesized by
Fig. 2 e HRTEM image of the as-prepared multilayered TiO2 nanotubes (a, b), enlarged HRTEM image of TiO2 nanotubes (c),
structure model of one unit of H2Ti3O7 on the (010) projection (d), schematic drawing of the structure of the nanotubes (e, f) [49].
Fig. 3 e TEM image of TiO2 nanotubes in Geng's work (a) [51]. SEM image of the TiO2 nanotubes prepared in the alumina
membrane with a diameter of 200 nm at 298 K (b) [52]. SEM images of the first generation [57] nanotubes in the HF electrolyte
(c), third generation [59] in ethylene glycol/fluoride electrolytes (d), fifth generation [61] with two-step anodization in
ethylene glycol/fluoride electrolytes (e) and fifth generation [62] with three-step anodization in ethylene glycol/fluoride
electrolytes (f).
various methods. There are generally three steps in the for- orientations, TiO2 nanoparticles can be aligned to form TiO2
mation of TiO2 nanowires from layered titanate particles: (i) nanowires through the solegel method via oriented attach-
exfoliation of the layered Na2Ti3O7; (ii) formation of nano- ment. By using titanium tetraisopropoxide, isopropanol and
sheets; (iii) formation of nanowires. Highly ordered TiO2 acetic acid as the sol, Rodriguez-Reyes et al. successfully
nanowire arrays can be fabricated via electrophoretic depo- prepared TiO2 nanowires. Briefly, the sol was dried at 100 C
sition of TiO2 colloidal suspensions with an AAM template for 24 h to obtain the xerogel. Then, the xerogel was calcined
followed by the removal of template [63]. In addition, sol- in air at different temperatures (400, 500 and 600 C) for 1 h to
vothermal, physical vapor deposition (PVD) [64], and electro- allow crystallization (Fig. 5aec) [70]. TiO2 nanowires can also
deposition methods [65e67] also have been reported for pre- be prepared by treating solid TiO2 powders in a concentrated
paring TiO2 nanowires [68,69]. Depending on the crystal aqueous NaOH solution followed by hydrothermal reaction
Fig. 4 e Fabrication and characterization of TiO2 nanotubes with different aspect ratios. Schematic of the modified
hydrothermal method containing a stirring element (a). Digital photos of resulting TiO2 solution obtained via modified
hydrothermal method at 500 rpm (b, left) and 0 rpm (b, right) after sedimentation. SEM images of titanate nanotubes
obtained at 500 rpm (c). TEM image of nanotubes synthesized at 500 rpm, the arrow indicating the formation of the
nanotubular structure (d). XRD pattern of the products synthesized at different stirring speeds (e) and SEM images of the
titanate nanotubes obtained by hydrothermal reaction at 130 C for 24 h at different stirring rates (0, 300, 400, 500 and
1000 rpm) (f, g, h, i, j) [53,54].
[71,72]. Hydrothermal process typically yield large amounts of
[61,62]
Ref.
TiO2 nanowires with no substrates or seeding layer required.
[57]
[58]
[59]
[60]
Typically the nanowires were randomly oriented and existed
in powder form. For creating well-aligned TiO2 nanowire ar-
rays, Zheng et al. utilized TiO2 nanoparticle-seeded substrates
in a hydrothermal system [73e75]. The layers were produced
by spinning the TiO2 polymeric sol on the substrate followed
Smooth and hexagonal tube length: 2e10 mm, diameter:

by annealing at 450 C for 1 h. The well-aligned single-crys-
diameter: 100 nm, and wall thickness: 12 nm (Fig. 3d)

Disordered tube length: 30 mm, diameter: 20e40 nm,
10e100 nm, and wall thickness: 13e27 nm (Fig. 3c)
talline rutile TiO2 nanowires possessed good size uniformity
Smooth and ultra-long tube length: 5e1000 mm,

(Fig. 5d and e).
Short nanotube length: 200e500 nm, diameter:
100 nm, and wall thickness: 15e20 nm (Fig. 3f)

Rough wall with nanotube length: 0.5e2.4 mm,
diameter: 100 nm, and wall thickness: 12 nm
A typical ceramic processing technique, high temperature

pyrolysis combines a hydrothermal process for precursor
treatment followed by high temperature sintering. It is also
Morphology
and wall thickness: 10 nm (Fig. 3e)

used to fabric 1D TiO2 nanowires with a few modifications. Via
a molten NaCl salt-assisted pyrolysis process, Xu et al. suc-
cessfully synthesized 1D TiO2 nanowires in a reaction mixture
of TiCl4-ethyl acetate and Na2S ethyl acetate solutions.
Anatase TiO2 nanowires were obtained after calcination at
820 C and rutile TiO2 nanowires at 970 C (Fig. 5f and i) [76,77].
Sung et al. synthesized Au modified rutile TiO2 nanowires by
an oxidation and thermal evaporation method [78]. During the
vaporeliquidesol process, a quartz or sapphire substrate
covered with 500 nm Ti and 50 nm Au was placed at 1050 C
under Ar and O2 flow. High-density single-crystalline TiO2
nanowires with a rutile phase were successfully grown on the
two substrates. It is believed that the Ti buffer layers deposited
on the substrates prevent undesirable reactions between the
0.5 wt% NH4F þ 2 vol% H2O in ethylene glycol
0.5 wt% NH4F þ 2 vol% H2O in ethylene glycol
Ti vapor and substrates ensure the growth of TiO2 nanowires

by providing supplementary Ti vapor to the Au catalysts
(Fig. 5g and h).
1 M Na2SO4/(NH4)2SO4 þ 0.5 wt% NH4F
TiO2 nanorods
Electrolyte
Similarly to nanotubes and nanowires, TiO2 nanorods can also

be prepared by solegel or solvothermal methods using AAM or
ZnO as template [69,79,80]. Densely assembled TiO2 nanorods
with a diameter of 150e200 nm (Fig. 6a) and a length of several
Table 1 e Brief summary of various preparations of TiO2 nanotubes.
0.01e3 M HClO4
micrometers have been synthesized by Tanemura et al.

Anatase-TiO2 nanorods were prepared by dipping porous
0.5 wt% HF
AAMs into boiled TiO2 sol followed by a drying process and

heat treatment. The as-fabricated TiO2 nanorods had good
compositional uniformity and high crystallinity along their
entire length. Crystalline TiO2 nanorods have been prepared
by oxidation of titanium plates with hydrogen peroxide
[81e83]. Wu et al. reported the preparation of homogeneous
highly crystalline TiO2 nanorods through direct oxidation of
3rd generation organic electrolytes containing F
metallic Ti with H2O2 at low temperature (80 C) (Fig. 6b). The

5th generation multiple-step anodization in
size of TiO2 nanorods can be controlled with the aid of various

2nd generation electrolytes containing F
surfactants such as metal nanoparticles, semiconductors and

4th generation fluoride-free electrolytes
organics [84,85]. For example, Cozzoli et al. synthesized high

organic electrolytes containing F
aspect ratio anatase TiO2 nanorods via hydrolysis of titanium

tetraisopropoxide (TTIP) with the aid of oleic acid (OLEA)
1st generation (HF electrolyte)
surfactant at low temperatures (80e100 C) [86]. The fast hy-

drolysis process was carried out by rapidly injecting the
aqueous base solution into OLEA/TTIP mixtures (typical molar
ratio ranging from 15:1 to 130:1). Tertiary amines or quater-
nary ammonium hydroxides were added as catalysts for
TiO2 NTAs
polycondensation to ensure a crystalline product. The hy-

drolysis of TTIP was activated leading to gelation of the
mixture only when the temperature was between 80 C and
100 C. The as-synthesized TiO2 nanorods were 40 nm in
Fig. 5 e SEM images of TiO2 calcined at 400 C (a), 500 C (b) and 600 C (c) [70]. Cross-sectional view (e) and top view (d) of TiO2
nanowires on FTO substrates [73e75]. TEM images of the as-prepared anatase TiO2 nanowires (f) and the rutile TiO2
nanowires at 970 C (i) [76,77]. SEM images of TiO2 nanowires grown on sapphire (g) and quartz substrates (h), respectively [78].
length and 3e4 nm in diameter with the elongated crystalline formation of TiO2 nanobelts are shown in the following three
domain aligning with the c-axis direction (Fig. 6c and d). In a chemical equations (Equations (1)e(3)). First, the TiO2 pre-
related work, Melcarne et al. applied a nonaqueous, sol- cursor is dissolved by breaking the TieOeTi to form sodium
vothermal method to the synthesis of anatase TiO2 nanorods titanate nanobelts. Second, the sodium TiO2 nanobelts are
with a mixture of benzyl alcohol and acetic acid used for converted into hydrogen titanate nanobelts by ion-exchange.
morphology control [87]. The anatase TiO2 nanorods were a Finally, the hydrogen titanate nanobelt is annealed to form
product of the attachment of acetic acid to certain crystal TiO2 nanobelts [96e100]. Based on these three steps, three
facets preferentially limiting the deposition rates. The lower different TiO2 nanobelt morphologies from Na2Ti3O7, H2Ti3O7
acidity and lower pressure during the reaction were attributed and TiO2 can be obtained in a controlled fashion and the SEM
to the higher boiling point of benzyl alcohol compared to the images are shown in Fig. 7a.
growth conditions of rutile TiO2 nanorods. The TiO2 nanorods
orientation can be aligned by introducing single-crystalline 3 TiO2 þ 2NaOH / Na2Ti3O7 þ H2O (1)
substrates with matching crystal lattices that act as seed for
directed growth. By TTIP and Ti(OC3H7)4 as precursors, Chen Na2Ti3O7 þ 2HCl / H2Ti3O7 þ 2 NaCl (2)
et al. produced well aligned rutile TiO2 nanorods on (100)-
oriented sapphire substrates [88]. The densely packed rutile H2Ti3O7 / 3TiO2 þ H2O (3)
TiO2 nanorods were grown with similar heights and all in one
direction (Fig. 6e and f). Chemical vapor deposition (CVD) and Ti foils were also used for the hydrothermal synthesis of
microwave hydrothermal methods have also been developed TiO2 nanobelts [101]. The Ti foil was put into the Teflon-lined
to prepare TiO2 nanorods [89,90]. stainless steel autoclave containing 30 ml 1 M aqueous NaOH
solution. The hydrothermal process was kept at 220 C for
TiO2 nanobelts 24 h. The reaction leads to the formation of Na2Ti2O4(OH)2
TiO2 nanobelts with a large number of exposed active facets in nanobelt arrays, which change into H2Ti2O4(OH)2 nanobelts by
combination with exceptional properties have attracted much immersion in HCl solution. After calcination treatment at
attention for numerous applications [91]. Various methods 500 C for 1 h, the H2Ti2O4(OH)2 converted into TiO2 nanobelts.
have been reported for synthesizing TiO2 nanobelts including Their average width was 72 nm, and the growth direction
hydrothermal [92], electrochemical anodization [93], organo- was along the (100) direction of the anatase crystal (Fig. 7b).
metallic CVD [94], and oriented attachment methods [95]. Using a nickel catalyst, Amin et al. successfully grew TiO2
Different methods show different levels of control of length nanobelts at 850e920 C through a vaporeliquidesolid (VSL)
and thickness of the TiO2 nanobelts. Three steps in the growth mechanism. The advantage of this method is that the
Fig. 6 e TEM image of an individual anatase TiO2 nanorod (a) [79,80]. FESEM of the surface TiO2 nanorods on the Ti plate after
soaking in the 30 wt% H2O2 solution at 80 C for 72 h (b) [84,85]. TEM image overview (c) and HRTEM of a single TiO2 nanorod
prepared by the fast hydrolysis method with surfactant assistance (d) [86]. SEM images at 30 C tilted view (e) and cross-
section view (f) of vertically aligned and densely packed TiO2 nanorods on sapphire (100) substrate [88].
formation of the TiO2 nanostructures was substrate-inde- TiO2 nanofibers. Xia et al. prepared ultra-long TiO2 nanofibers
pendent (Fig. 7c) [102]. Apart from Ni, several other metals like with titanium tetraisopropoxide (Ti(OC3H7)4), polyvinyl pyr-
Au, Ag, Pt, and Pd can also assist in the growth of TiO2 nano- rolidone (PVP), acetic acid, and ethanol as starting materials
structures. Ni and Au in particular appear to provide higher [104]. In their study, the average diameter of the as-prepared
yields [103]. TiO2/PVP nanofibers was 78 nm. The diameter could be var-
ied by changing the electric field, the concentration of PVP and
TiO2 nanofibers Ti(OC3H7)4, and the feeding rate. The composite nanofibers
Compared with the previously described 1D TiO2 nano- were then heated at 500 C to remove the PVP and obtain pure
structures, TiO2 nanofibers possess additional advantages due TiO2 nanofibers with a reduced diameter of 53 nm (Fig. 8a and
to their size and large specific surface area for catalytic ac- b). Another typical structure obtained is hollow TiO2 fibers.
tivity. The most frequently used method to synthesize TiO2 Using activated carbon fibers (ACF) as templates, Yuan et al.
nanofibers is electrospinning which entails the following four successfully prepared hollow TiO2 fibers via a precursor
steps: (1) preparation of sol with the TiO2 precursor; (2) addi- impregnation and heat treatment. Briefly, ACF are immersed
tion of sol into polymer template for electrospinning; (3) in the mixture of titanium isopropoxide and anhydrous
electrospinning of the solution to obtain composite nano- ethanol (at a volume ratio of 1:6). Then, the filled ACF and
fibers; and (4) calcination to obtain single-phase crystalline solution are transferred into a stainless steel autoclave and
Fig. 7 e Typical SEM images of three different TiO2 nanobelt morphologies from Na2Ti3O7, H2Ti3O7 and TiO2 (a). TiO2
nanowire arrays obtained via calcination of the as-prepared H2Ti2O4(OH)2 nanowires (b). TiO2-urchin with nanowires,
the inset is a close-up view of the nanowires (c) [98e100].
heated at 150 C for 24 h. Finally, the composite fibers are TiO2 nanosheets also play an important role in the develop-
calcined at 600 C in air for 5 h to remove the ACF template ment of TiO2 nanostructures. The way to obtain this nano-
(Fig. 8c and d) [105]. structure morphology is to control the reaction conditions
precisely. Sun et al. successfully prepared TiO2 nanosheets by
Formation of 2D TiO2 nanostructures a hydrothermal method. The concentration of the NaOH so-
lution was decreased to 5e8 M and reacted at 140 C for 48 h
As the intermediate during the hydrothermal process for the [106]. TiO2 nanosheets could also be obtained by organic-
synthesis of TiO2 nanotubes, nanowires and nanorods, 2D stabilizer-free synthesis [107], continuous hydrothermal
Fig. 8 e SEM images of uniaxially-aligned nanofibers made of TiO2/PVP (a) and TiO2 (b), the insets of (b) shows enlarged SEM
images of the hollow TiO2 nanofibers. Overview of the TiO2 nanostructures with inset showing a single fiber (c). SEM of the
surface of the worm-like TiO2 nanostructure (d) [104,105].
routes [108], room temperature synthesis [109], and ionic Essential film properties, such as thickness, adhesion, ho-
liquid synthesis approaches [110]. Yang et al. prepared TiO2 mogeneity, roughness and mechanical stability, should be
anatase nanosheets with dominant (001) facets by the alcohol controlled during any fabrication method. For example, Agrios
solvothermal method. First, TiF4 was added into hydrochloric et al. prepared hierarchical TiO2 films with a mesoporous layer
acid (pH ¼ 1.8). Then 14.5 ml of the TiF4 aqueous solution, deposited from TiO2 nanoparticles (16 nm), and a top scat-
13.38 ml of 2-propanol and 0.5 ml of HF were added into a tering layer of particles ranging in size from 250 to 400 nm
Teflon-lined stainless steel autoclave and reacted at 180 C for (Fig. 10) [132]. Upon removal of the templates by calcinations,
5.5e44 h [111]. SEM images of the as-obtained single-crystal films with pore sizes approximately corresponding to the size
anatase TiO2 nanosheets are shown in Fig. 9a and b [112]. of the templates were obtained [133]. Michael et al. employed
Recently, delaminating a lepidocrocite-type layered protonic polystyrene (PS) spheres of sub-micrometer size to form
titanate was conducted to prepare the graphene-like layered macro-porous TiO2 films with cavities created by the removal
TiO2 nanosheets [110,113,114]. Specifically, Cs-titanate was of polystyrene the PS spheres (Fig. 11) [134].
formed by calcining TiO2 and Cs2CO3 [115e119]. Gao et al.
demonstrated that the exfoliation-precipitation method en- Porous/hierarchical hollow TiO2 spheres
ables the construction of a new nanoporous materials through Spherical morphologies of 3D TiO2 adopt diverse sampling of
the exfoliation of TiO2 nanosheets, co-precipitation with MgO architectures including spherical particle agglomerates,
nanoparticles and subsequent dissolution of MgO nanoporous spheres with periodic porosity, hierarchical hollow
particles. The process is summarized in Fig. 9c [120]. spheres and flower-like spheres. Several methods have been
reported for producing hierarchical hollow TiO2 spheres with
Synthesis of 3D TiO2 hollow and hierarchical materials defined shapes and tunable porosity. Hollow spherical TiO2
agglomerates can be obtained by spray-drying concentrated
With the development of the 0D, 1D and 2D TiO2 nano- sols. The uniformity of the spheres was greatly influenced by
structures; it is natural that 3D TiO2 materials have also been the ionic strength of the TiO2 sol as dictated by the amount of
widely studied in recent years. A focus on 3D TiO2 nano- added salt. Without proper control of the iconicity, the drop-
materials involves synthetic strategies for controlling the TiO2 lets can fragment during drying with the process and lead to
nanostructures in all three dimensions. As is typical, these the formation of fine powders (Fig. 12a and b) [135]. For other
materials can be characterized by their porosity with atten- 3D TiO2 nanostructures, Lee et al. prepared hierarchical
tion to pore-size distribution, the specific nature of the pores, porous F-doped TiO2 spheres by hydrothermal treatment of
and pore volume [121e131]. In this section, we review the TiF4 powder in 1 M HCl solution at low temperatures (180 C)
synthesis and characterization of 3D TiO2 materials including [136]. The spherical particles were about 1 mm in diameter and
porous films, porous spheres, hierarchical hollow spheres and composed of agglomerated anatase crystals with an average
spherical bundles of nanorods or nanowires. size of 13 nm containing 3 nm pores (Fig. 12c and d). Urchin-
like rutile TiO2 spheres were prepared via oxidative hydroly-
Porous TiO2 films sis of TiCl3 in the presence of NaCl to introduce Cl ions
Porous TiO2 films are widely used in fields including dye- without addition of acid. The reaction was also carried out at
sensitized solar cells, electrochromics, and self-cleaning lower temperatures (90 C) for 12 h. The reaction begins with
coatings among others. Owing to the inherent planar nature the formation of dense ball-like spheres assembled from
of many of its applications, methods for preparing porous TiO2 nanoparticles. With increased heating and reaction time, a
films on suitable substrates have been heavily investigated. gradual outgrowth of rutile TiO2 nanorods occurs as the
Fig. 9 e SEM images of the anatase TiO2 nanosheets synthesized with a reaction time of 11 h (a, b) [112]. The synthesis route
of TiO2 nanosheets by the exfoliation-precipitation method (c) [120].
Fig. 10 e SEM images of nanoporous films (a, b), scattering particles on top of the nanoporous film (c) and a cross-section
view of a nanoporous film topped with a scattering layer (d) [133].
spherical core is consumed to produce urchin-like morphol- by a cost-effective spray-drying method (Fig. 13) [138,139].
ogies (Fig. 12eeh). [137]. Macroporous brookite titania were prepared by spray drying a
In a related study, Iskandar et al. produced sub-micron suspension of brookite nanoparticles and polystyrene latex
spherical brookite particles with tunable sizes in the range of (PSL) particles, which were used for templating. Spherical PSL
200e400 nm and a highly organized hierarchical mesoporosity particles can be easily prepared from styrene monomers,
Fig. 11 e SEM images of films made from TiO2 containing various weight ratios loadings of PS microspheres. TiO2: PS ¼ 10: 1
(a) and TiO2: PS ¼ 20: 1 (b). SEM cross-sections of PS-templated TiO2 films (c and d). The magnified image reveals ellipsoidal
pores indicative of the presence of PS spheres prior to removal by calcination (d) [134].
Fig. 12 e SEM micrographs of spray-dried particles produced from TiO2 sols without added salt (a, b) [135]. SEM images of
porous F-doped TiO2 microspheres prepared by a hydrothermal treatment of TiF4 power (c), and an individual microsphere
showing details of the texture and porosity (d) [136]. Schematic illustration of the formation process of sub-micrometer
rutile spheres in a hydrothermal reaction of TiCl3 with salt, and FESEM images of the corresponding stages (eeh) [137].
which are relatively inexpensive; thus, the spray-drying because it also provides holes for the degradation of
method is a cost-effective method to produce porous TiO2 pollution.
particles.
TiO2 þ hv / e þ hþ (4)
Solar water splitting by nanostructured TiO2 Reduction: 2 Hþ þ 2e / H2 DE ¼ 0 V (5)

materials
Oxidation: 2H2O þ 4 hþ / O2 þ 4 Hþ DE ¼ 1.23 V (6)
With rapid economic development and ever increasing con-
sumption rate of natural fossil fuels, both environmental and Overall reaction: 2H2O / 2H2 þ O2 (DG ¼ þ237.2 kJ mol1) (7)
energy shortage concerns have become two long standing is-
sues that desperately need to be addressed. Thus there is a In general, there are two routes for the generation of H2 by a
real need to develop clean, renewable, cheap and sustainable photo-induced process. The first are the photocatalytic ap-
sources of energy to replace fossil fuels and meet increasing proaches and the second are the photoelectrochemical
energy demands [140e144]. Using solar energy and semi- methods. In photocatalysis (Fig. 14b), the electrons can be
conductors in photocatalytic and photoelectrochemical water excited from the valence band (VB) to the conduction band (CB)
splitting to produce hydrogen are two promising ways to upon light irradiation thus leaving holes in the VB. In this way,
address these concerns. While some semiconductors such as the photo-induced charges and holes are efficiently separated.
SiC and CdS cause photocorrosion, TiO2 have been shown to During this process, the water molecules are reduced by elec-
be ideal photocatalyst for hydrogen production and the trons to form H2 with the reduction potential (Hþ/H2) of water
decomposition of pollutants due to its suitable band structure, at 0 V. At the same time, H2O is also oxidized by holes to form O2
low-cost, non-toxicity, strong redox potential, and chemical with the oxidation potential (H2O/O2) at 1.23 V with respect to
stability [145e148]. the normal hydrogen electrode (NHE). From the view of ther-
A typical water splitting process is composed of two half- modynamics, the conduction band (CB) level should be more
reactions; the hydrogen evolution reaction and oxygen evo- negative than the hydrogen production level (0 V) while the
lution reaction (Equations (4)e(6)). The free energy DG valence band (VB) should be more positive than water oxida-
(DG ¼ þ237.2 kJ mol1) and the standard redox potential DE tion level (1.23 V) for efficient hydrogen production from water
(DE ¼ 1.23 V) of the multi-electron water splitting reaction [149e153]. Thus the redox potential of the photocatalyst re-
are given in Equations (6) and (7). It is known that the oxygen quires a band gap of more than 1.23 eV to convert water into
evolution reaction is an essential component of the water hydrogen. In addition, kinetic overpotentials and losses typi-
splitting system in environmental remediation applications cally push the required value to around 2 eV [154e157]. Thus
Fig. 13 e Microporous particle formation by spray-drying and colloidal templating of brookite nanoparticles in the
aerosol-assisted process, and SEM images of porous TiO2 particles prepared with precursor solutions consisting of only
brookite nanoparticles and with solutions containing different ratios of brookite nanoparticles and polystyrene latex (PSL)
particles of different sizes (a). 1:1 brookite nanoparticles to 300 nm PSL particles (b), 1:2 brookite nanoparticles to 300 nm PSL
particles (c), 1:3 brookite nanoparticles to 300 nm PSL particles (d), 1:2 brookite nanoparticles to 200 nm PSL particles (e), and
1:2 brookite nanoparticles to 400 nm PSL particles (f) [138].
TiO2 is the one of the most widely used catalysts in hydrogen the suppressed recombination of photo-generated electrons
production due to its suitable band structure (Fig. 14a). Photo- and holes. As shown in Fig. 14c, upon irradiation the electrons
catalysis is the simplest water-splitting approach; amenable to can be promoted from the valance band of TiO2 to the con-
cheap, large scale H2 production. However, it suffers from fast duction band and then driven to the counter electrode via the
electron/hole pair recombination, low quantum efficiency in external circuit by applied bias potential which can signifi-
the visible range and low solar-to-hydrogen (STH) efficiencies cantly facilitate the transfer of photocarriers and suppress the
(less than 0.1%). Therefore, bulk doping and surface engi- recombination of electron/hole pairs because electrons and
neering strategies have played a very important role in holes react with water at two spatially separated electrodes
improving the photo-generated charge transfer/separation thus leaving the holes on the surface of the TiO2 electrode. The
and shortening the transfer distance of photo-induced charge presence of abundant holes on the TiO2 surface is particularly
carriers to the surface reaction sites. ideal for environmental remediation applications as adsorbed
Compared to photocatalysis, photoelectrolysis using pho- pollutants are readily degraded upon contact and the harm-
tocatalyst electrodes with additional potential bias provided less byproducts simply diffuse away. The holes at the valance
by a photovoltaic element has been shown to be a promising band can react with water molecules to generate oxygen and
and simple route to improved water splitting with ultimately hydrogen ions, while the electrons at the counter electrode
higher STH efficiency (more than 5%) [158e161]. For photo- can react with hydrogen ions to generate hydrogen, similar to
catalytic water splitting, electrons at the valance band are the above discussed photocatalytic process [162e166]. Indeed,
excited to the conduction band of TiO2 upon illumination. photoelectrocatalytic water splitting goes far in addressing
Then hydrogen ions are reduced into hydrogen by the elec- the fast recombination of electron/hole pairs via physical
trons at the conduction band, while the generated holes at the separation of reduction and oxidation processes. However,
valence band oxidize water molecules into oxygen (or degrade the disadvantages associated with TiO2 inherently remain (i.e.
pollutants at the same time if they exist in the solution) fast recombination of electron/hole pairs, poor kinetics, low
(Fig. 14b). In contrast, photoelectrocatalytic water splitting has visible-light absorption and low solar-to-hydrogen). In the
shown promise for improving hydrogen evolution rates due to next section, we will systematically discuss some bulk doping
Fig. 14 e Relationship between the band structure of various semiconductors and the redox potentials associated with
water splitting (a) [153]. Schematic diagram of photocatalytic (b) and photoelectrocatalytic (c) water splitting on TiO2 [165].
approaches and surface engineering strategies in photo- nanoparticles, the 1D nanostructure is advantageous for water
electrocatalytic water splitting aimed at improved charge splitting owing to superior directional charge transport
separation and transfer, enlarging the surface area, optimized through resulting in lower charge recombination in 1D TiO2
surface facets and band gap positions, increasing visible-light nanostructures [189e191]. D'Ela et al. studied the influence of
absorption, reducing the cost and enhancing the surface re- the morphology of different nanostructured TiO2 samples on
action kinetics [167e175]. their water splitting capabilities. TiO2 nanotubes fabricated by
hydrothermal method were found to be more active than P25
Pure TiO2 nanomaterials for hydrogen production under UV irradiation due to enhanced charge separation [192].
Park et al. have successfully synthesized well-ordered and
Since the water splitting capabilities of titanium dioxide was aligned high surface area mesoporous TiO2 nanofibers by
discovered by Fujishima and Honda in 1972 [176], different electrospinning and calcination [193]. TiO2 nanofibers 500 nm
TiO2 nanostructures comprised of 0D nanoparticles, 1D in diameter and a few micrometers in length consist of densely
nanowires, nanotubes, nanorods, nanofibers, 2D nanosheets, packed spherical nanoparticles 20 nm in size with mesopores
3D hierarchical structures and mesocrystals have gained 3e4 nm in radius (Fig. 15aed). TiO2 nanofibers exhibited much
increased attention and widely used in applications such as higher photocatalytic water splitting activate compared to
photocatalytic degradation of pollutants [177], photocatalytic TiO2 nanoparticles (Fig. 15e). The photocatalytic superiority of
CO2 reduction into energy fuels [178,179], solar cells [180,181], TiO2 nanofibers is attributed to effects of mesoporosity and
supercapacitors [182,183], biomedical devices [184], and nanoparticle alignment which enables efficient charge sepa-
lithium-ion batteries [185,186]. Yu et al. applied commercial ration through inter-particle charge transfer along the nano-
TiO2 nanoparticles (P25) to water splitting in ethanol/water fiber framework. In addition, Tang et al. synthesized different
solution under UV light and it exhibited a low hydrogen gen- 1D TiO2 nanostructures (TiO2 nanowires and nanorods) by a
eration rate 13.7 mmol h1 g1 [187]. Janek et al. fabricated hydrothermal method [194]. They displayed different
mesoporous TiO2 films by solegel and template methods. The hydrogen generation performances depending on whether the
results showed that the use of mesoporous TiO2 films lead to a mode of application was a photoelectrochemical cell or a
10 times higher efficiency for water splitting as compared to direct heterogeneous reaction. On one hand, TiO2 nanowires
crystalline TiO2 nanoparticles [188]. Compared to TiO2 exhibited higher hydrogen production activity because of
Fig. 15 e SEM (a, c) and TEM (b, d) images of TiO2 nanofibers and TiO2 nanoparticles. Hydrogen production rate comparison
between TiO2 nanofibers and TiO2 nanoparticles in 10 v% ethanol solution under UV light irradiation (e) [193]. SEM image of
TiO2 nanowire (f) and nanorod (g), respectively. Schematic illustration of (A) the directional charge transfer in TiO2
nanowires for photoelectrocatalytic water splitting, and (B) high reactivity facets in TiO2 nanorods for photocatalytic
hydrogen generation (h). The SEM images shown at the lower right corner are the cross sectional images of the
corresponding samples [194].
intimate inter-particle contact and directional charge transfer Although TiO2 nanostructured materials have been widely
pathways facilitate efficient carrier transport and enhance employed in the photocatalytic degradation of pollutants,
photoelectrochemical cell performance. On the other hand, water splitting, solar cells, supercapacitors and lithium bat-
TiO2 nanorods exhibited higher hydrogen production rate due teries due to their low-cost and good physical and chemical
to the large number of exposed reactive (010) facets that pro- properties, they still show lower specific surface areas than
mote direct heterogeneous hydrogen evolution reactions desired for use in photocatalysis applications. Due to the wide
(Fig. 15feh). Xu et al. successfully synthesized 1D mesoporous band gap (anatase: 3.2 eV, rutile: 3.0 eV), TiO2 can only absorb
TiO2 nanotubes with lengths ranging from 100 nm to 400 nm ultraviolet light (3e5% solar light) which largely limits the
and diameters around 10 nm by a hydrothermal-calcination harvesting of solar light. The single crystalline phase also
process [195]. They exhibited excellent photocatalytic activ- leads to fast recombination of the electrons and holes. These
ity for simultaneous photocatalytic H2 production and Cu2þ drawbacks (low surface area, wide band gap, inactive under
removal from water. Jitputti et al. fabricated 3D flower-like visible light) limit its use in many applications. Considerable
TiO2 nanosheets by a hydrothermal method giving an activ- effort has been spent improving the performance of TiO2 over
ity of 100 mmol h1 g1 which is nearly 5 times higher than that the past several decades with the hope to bring it into indus-
of P25 (19 mmol h1 g1) because of the enlarged surface area trial scale application and commercialization [197e200].
[196]. Despite the variability in the overall shape of the above Common strategies in this effort include increasing the photo-
synthesized TiO2 nanostructures, it is demonstrative of just catalytically active sites and as well as material modification.
how important the surface area is in dictating the photo- Several of the main approaches will be discussed in the next
catalytic activity. sections.
Synthesis of pristine TiO2-based active photocatalysts surface area of TiO2 materials is by hydrothermal acid corro-
sion which creates intimate contact between the nanoparticles
Since pristine TiO2 nanostructured materials exhibited rela- and the multi-dimensional TiO2 nanostructures and facilitates
tively low hydrogen production rates, attention has been charge-carrier separation and transfer. Meng et al. grew sec-
directed toward o enlarging the photocatalytically active area, ond phase TiO2 nanorods on TiO2 nanofibers at high densities
optimizing the crystallinity and exposing high-energy facets. by combining electrospinning and hydrothermal methods
Improvements in these areas have led to larger solar-to- [113]. After treatment, the active surface area of the hierar-
hydrogen efficiencies. chical TiO2 nanostructures was doubled. As a result, the pho-
tocatalytic activity of the material was found to be superior to
Enlargement of the photocatalytically active area that of pristine TiO2 nanofibers. Chen et al. prepared TiO2
Since pristine TiO2 nanostructured materials exhibited rela- nanobelts by electrochemical anodization and a maximum
tively low hydrogen production rates, many researchers and photoconversion efficiency of up to 4.51% at an applied voltage
scientists have paid much attention to how to enlarge the of about 0.1 V can be achieved. This value is much higher than
photocatalytically active area, optimize the crystallinity and that of TiO2 nanotubes obtained using the same synthetic
expose high-energy facets. It is well known that photocatalytic method (2.43% at 0.39 V) (Fig. 16c and d) [202].
reactions occur at active sites on the surface of multi-
dimensional TiO2. Thus, the amount of active sites directly Optimizing the crystallinity and exposed facets
influences the performance of photocatalyst. Two typical and It is well known that the absorbance is highly dependent on the
effective methods are conducted to enlarge the specific surface crystal phase of TiO2 and the temperature used during calci-
are: (1) constructing coarse surfaces with uniform nano- nation and synthesis. Zhou et al. reported that the light ab-
particles and (2) incorporating a second material (nano- sorption edge of TiO2 nanobelts changes with changing
particles, nanobelts, nanorods, nanoporous etc.) on the surface calcination temperature as the crystalline phase evolves from
of the primary TiO2 nanostructure of interest. Tang et al. pro- as-synthesized H2Ti3O7 to TiO2(B), to anatase, and finally to
duced a hybrid TiO2 nanoflake/nanoparticle hierarchical rutile [29]. The band gap of TiO2 nanobelts obtained at 100, 400,
structure at 500 C that exhibited a higher photocatalytic ac- 600, 800, 900 and 1000 C are 2.85, 2.8, 2.9, 3.05, 3.1 and 2.9 eV,
tivity for the degradation of organic compounds than before respectively. Since these values are different from that of bulk
(Fig. 16a and b) [201]. However, some drawbacks still exist TiO2 it suggests that the increase in the band gap values is
including difficulty controlling particle size, size distribution, associated with the phase transition from TiO2(B) with a band
and connectivity between the nanoparticle and the TiO2 gap value of 2.8 eV and to anatase with a band gap of 3.1 eV
nanobelt substrate. One effective way to enlarge the active [22,23]. However, materials with a combination of phases are
Fig. 16 e SEM image of hybrid nanoflake/nanoparticle hierarchical structures (a) and the corresponding photocatalytic
activity (b) [201]. Cross-sectional SEM image of the TiO2 nanobelt arrays from nanotubes arrays (c) and the photocatalytic
degradation efficiency of RhB by using TiO2 nanobelt arrays (d) [202].
usually obtained and the rutile nanomaterials obtained after limited doping depth [216,217]. Ti alloy anodization is only
the highest temperature process have higher degrees of crys- used for TiO2 nanotube arrays and has limited application in
tallinity than others. Rutile and anatase TiO2 materials have other higher dimensional structures [218,219]. Thermal treat-
different catalytic properties largely due to the different ment in N2, H2, and Ar atmosphere is recognized as a facile and
exposed crystalline facets which dictate the photocatalytic widely utilized doping technique. Among all of the non-metal
activity [112,203]. For example, superoxide radicals (SR) act as elements, Carbon and Nitrogen doping are the most investi-
an intermediate in the oxidization of organic molecules [204]. gated. The substitutional doping by N was a highly effective
The SR originates from the adsorption of oxygen molecules strategy for band-gap narrowing by mixing p states with O 2p
that trap the photogenerated electrons on the surface of TiO2 states. For C and P doping, the dopant introduces deep states in
nanostructures. Anatase TiO2 nanostructures have two domi- the gap [220]. Although doping with S shows a similar band-gap
nant (101) crystalline facets which are less energetically narrowing, it is difficult to incorporate it into the TiO2 crystal
favored. However, it has the ability to promote the adsorption because of its large ionic radius, as evidenced by a much larger
of oxygen molecules, which is beneficial for producing super- formation energy required for the substitution of S than that
oxide radicals. It is reported that the reactivity of the TiO2 (110) required for the substitution of N [211,221,222]. In addition, the
facets is primarily governed by the surface species such as intrinsic defects of TiO2, such as reduced Ti species and oxygen
oxygen vacancies and bridging hydroxyls. Changing these vacancies after calcination, also lower energy excitation
surface moieties may vary the surface electronic structure of pathway. Shao et al. prepared nitrogen and carbon doped TiO2
TiO2 materials. As a fairly new phase, TiO2(B) has attracted nanoparticle composites using chitosan as a natural nitrogen
much attention as an alternative photocatalyst for its relatively and carbon source in a hydrothermal and heat treatment
open structure, despite having a generally lower photoactivity method [223]. The doped C, N species decreased the band gap
than anatase [205]. Several groups have reported impressive and created a sub-band gap above the valence band of TiO2
photocatalytic activity of different phases of TiO2 for hydrogen which lead to the visible light response of the composites.
production [206,207]. In addition, different crystalline planes Thus, the composites exhibited higher photocatalytic activity
have different reduction or oxidation potentials, so photo- under visible light. Furthermore, ultrafine nitrogen-doped TiO2
generated electrons and holes may migrate to different photocatalysts with enhanced photocatalytic water-splitting
planes separating from each other upon photoexcitation. properties were successfully fabricated using PVP as a nitro-
gen source via a solvothermal method [224]. Zhang et al. suc-
Development of visible light-sensitized photocatalysts cessfully synthesized F-doped TiO2 nanosheets. The rectangle
nanosheets displayed widths and thicknesses of 3e6 mm and
While TiO2 is by far one of the most widely used photo- approximately 200 nm, respectively (Fig. 17aed) [225]. As
catalysts, it suffers from an intrinsic drawback due to its wide compared to the pure TiO2 nanosheets, F-doped TiO2 nano-
band gap. As a result, it only utilizes UV light which consti- sheets exhibited markedly enhanced hydrogen production
tutes only 3e5% of the solar spectrum. For improved photo- efficiency because of their absorption in the visible-light region
activity, it is essential to extend the absorption into the visible and fast transfer of charge carriers. Schmuki et al. fabricated N-
and infrared range by sensitizing TiO2 with metals, non- doped TiO2 nanotube arrays for hydrogen generation by ion
metals, and other semiconductors. implantation [226]. Interestingly, the tube layers that were
exposed to a low N dose showed a strongly enhanced activity.
Bulk doping with metal and non-metal elements Whereas the tubes implanted with higher doses showed
The photoelectrical activity of TiO2 nanomaterials is related to virtually no effect. To a large extent, this phenomenon can be
its structure and chemical composition. Titanium (cation) and explained by not only two observations. First, the formation of
oxygen (anion) can be replaced by metal and non-metal doping amorphous domains within the anatase structure due to ion-
particularly at the surface of the nanostructures [208e210]. beam damage detrimentally affects the structures in terms of
Therefore, introducing a secondary active cation and/or anion electrical and photoelectrochemical properties. Second, the
species into the lattice of TiO2 is suitable for sensitizing to large N doping leads to an increase in the sub-band-gap
visible light as well as suppressing the recombination of elec- response in anatase which drastically reduces the charge-
tron/hole pairs. Nitrogen-doped TiO2 was first reported by transfer resistance. The benefits of low-dose nitrogen im-
sputtering in a nitrogen-containing gas mixture by Asahi et al. plantation are much more pronounced for the longer TiO2
It was shown to be highly effective for band-gap narrowing and nanotube arrays than for the shorter tubes. After N-doping, the
enhancing photocatalytic activity [211]. Since then, other non- Fermi level lies closer to the conduction band in the implanted
metals such as C, B, S, F and P have also been incorporated into zone. The meeting point of implant and implant-free locations
the TiO2 lattice by various methods. These dopants have also produces a homo-junction in the tube wall (Fig. 17eeg).
been able to narrow the band gap of TiO2 as well as enhance the Therefore, a highly synergistic combination of light and elec-
visible light absorption [212e215]. Conventional techniques tron harvesting leading to high photocatalytic water splitting
include hydrothermal methods, thermal treatment in a gas activity can be achieved. Behara et al. co-doped hydrogenated
atmosphere (N2, CO, Ar, etc.), plasma ion implantation or TiO2 nanoparticles with N and S under annealing in hydrogen
sputtering in special atmosphere and Ti alloy anodization etc. atmosphere [227]. The introduction of N and S shifted the va-
Among these methods, ion implantation and sputtering in lance band upward. While the formation of Ti3þ states and
special atmosphere have been shown to be particularly effec- oxygen vacancies lowered the conduction band resulting in a
tive doping methods. However, these methods require high narrow band gap and faster transfer of charge carriers. Addi-
energy accelerators, harsh experimental conditions, and tionally, the dopants and vacancies extended the visible light
Fig. 17 e FESEM image (a) and high magnification image of the section marked in red (b), STEM-EDS elemental mapping
images (c) and HRTEM image (d) of TiO2 nanosheets [225]. Photocatalytic H2 evolution from long (6 mm) and short (500 nm)
TiO2 nanotube arrays under AM 1.5 (100 mW cm¡2) (e). Photocurrent transients taken at 405 nm in 0.1 M Na2SO4 at 500 mV
(vs. Ag/AgCl) for pure and N-doping short tubes (f). Schematic illustration of N-doping TiO2 nanotube arrays for hydrogen
production (g) [226]. (For interpretation of the references to color in this figure legend, the reader is referred to the web
version of this article.)
absorption. Therefore, N and S co-doped hydrogenated TiO2 a smaller crystallite size and higher specific surface area than
exhibited high solar-to-hydrogen efficiency (6.6%) and dopant-free TiO2 photocatalysts. In addition, first-principle
enhanced photoelectrocatalytic hydrogen production. Binary density functional theory calculations showed that Fe can
or ternary doping of hydrogenated TiO2 with noble metals and induce the formation of impurity levels near the valence band
other semiconductors is also being widely investigated for leading to a reduction of the band gap, electronehole sepa-
improving photocatalytic and photoelectrocatalytic activity ration, high electron transfer efficiency and the improvement
[228e230]. of photocatalytic water splitting activity.
In situ fluorine doping of TiO2 superstructures for efficient Kerkez-Kuyumcu et al. compared the performances of M/
visible-light driven hydrogen generation: Fig. 1c shows that TiO2 (M ¼ Cu, Ni, Co, Fe, Mn and Cr) photocatalysts under
ion implantation can have a strong effect on the photo- visible light irradiation [240]. After loading by transition metal
catalytic H2 production rate. Interestingly the tube layers elements, it was found to have significant influences on the
that were exposed to a low-N-dose show a strongly enhanced crystallographic structure, physical properties and optical
activity, while the tubes implanted with a higher dose show absorption properties of titania based catalysts, as well as
virtually no or only a small effect. Moreover, the beneficial overall enhanced photocatalytic activity compared to pristine
effect of low-dose nitrogen implantation is much more pro- TiO2. The optical reflection edge was shifted into the visible
nounced for the longer TiO2-NTs than for the short tubes. light range with the transition metal additives. The band gap
TiO2 doped with transition metal cations such as Fe, Cu, V, energies of the doped TiO2 samples were considerably nar-
Co and Mn has been verified to widen the visible light ab- rower than that of undoped TiO2. Among all the catalysts, Cu/
sorption range, suppress the recombination of photo- TiO2 exhibited the highest photocatalytic activity under
generated electron/hole pairs and improve the photoelectric visible light for both of the dyes owing to the low band gap
performance [231e234]. Fe is one of the most frequently used energy and delayed electronehole recombination. Hu et al.
transition metals due to its strong oxidizing capabilities when also incorporated Cu into TiO2 films under different atmo-
paired with hydrogen peroxide (Fenton's reagent) [235,236]. spheres by a facile magnetron sputtering method [241]. The
Lin et al. doped TiO2 nanotube arrays with Fe3þ, and investi- Cu-doped TiO2 sample fabricated under an oxygen-rich at-
gated the effect of different concentrations of Fe ion on pho- mosphere displayed high H2 evolution rates on the order of
tocatalytic performance. These heterogeneous composites 2.80 mmol cm2 h1. This performance is 55 times higher than
exhibited stability and high photocatalytic and photo- that of pure TiO2 which is surprising and encouraging as it
electrocatalytic activity [237,238]. Zhao et al. synthesized Fe- shows that significant improvements can be made with rela-
doped TiO2 photocatalysts by the microwave-hydrothermal tively simple modifications. Further, ternary Cu2þ/Fe3þ/TiO2
method [239]. These Fe-doped TiO2 photocatalysts exhibited and quaternary Fe/Co/Ni/TiO2 systems were also investigated
with the synergistic effect of different transition metal cations supporting arrays of highly ordered porous Au nanoparticles
serving to improve the performance [242,243]. It is noted that (Fig. 18b and f) [259]. The metal nanoparticle size, shape, and
when the doping content is too high, blockages in the chan- distribution were well-controlled and the final nanoporous
nels of TiO2 nanotubes may occur and act as recombination Au/TiO2 nanostructures showed an enhanced photocatalytic
centers. Thus rather than facilitating electronehole separa- hydrogen production in ethanol/water mixtures. Similarly,
tion it leads to a decrease in the photo/photoelectrocatalytic Zheng et al. reported a room-temperature photochemical
activity. This adverse effect can be avoided by tailoring the strategy to fabricate a highly stable, atomically-dispersed Pd
doping amount [244e246]. catalyst (Pd/TiO2) on ultrathin TiO2 nanosheets with Pd
loading up to 1.5% (Fig. 18c and g) [260]. The composite exhibits
Sensitization with noble metal particles higher catalytic activity and stability than commercial Pd/C.
Since TiO2 can only absorb UV light, it is meaningful to Wang et al. successfully fabricated novel 3D urchin-like TiO2
sensitize TiO2 with metallic nanoparticles by taking advantage microstructures decorated with Ag nanoparticles by a one-
of the localized surface plasmon resonance (LSPR) effect to step solvothermal method (Fig. 18d and h) [261]. The work
enhance the visible light harvesting potential [247e250]. The systematically investigated the effect of AgNO3 solution con-
primary noble metal nanoparticles investigated are Au, Ag, Pt, centration, reaction time and temperature on the morphology,
Pd and their alloys because they can be optically excited in the microstructure, crystallinity and composition of the compos-
visible region (i.e. absorb in the visible region) [251e254]. Upon ite materials. The composites exhibited superior photo-
visible light illumination, plasmon can “excite” the electrons catalytic activity attributed to the enhanced visible light
in the conduction band to produce highly energetic “hot absorption and effective separation of electron/hole pairs.
electrons” via the LSPR effect, which acts as an electron sink. Given that several of these methods have poor control over the
Then these “hot electrons” can transfer to the conduction metal particle size and dispersion, Ye et al. reported a facile
band of TiO2 in direct contact thereby forming a metal- hydrothermal strategy for sensitizing TiO2 nanotube arrays
esemiconductor Schottky junction. Simultaneously, the SPR with Pd QDs (Pd QDs@TiO2 NTAs) with superior performance
effect can form a strong local electronic field to enhance the in photoelectrocatalytic water splitting [62,262]. After hydro-
energy of trapped electrons facilitating their transfer and re- thermal reaction, Pd quantum dots with sizes of 3.3 ± 0.7 nm
action with electron acceptors. As a result photo-generated were uniformly dispersed over the entire surface of the
electronehole pairs are efficiently separated [255e257]. Stra- nanotubes on both the inside and outside of the nanotubes
tegies used for decorating TiO2 nanomaterials with noble (Fig. 19a and b). TiO2 NTAs modified with noble metals can
metal nanoparticles typically include UV reduction, plasma effectively prohibit electron/hole recombination and enhance
sputtering, electrodeposition, electrospinning or hydrother- visible light absorption due to the SPR effect ultimately leading
mal methods. Zhu et al. have synthesized hollow Pt/TiO2 to higher hydrogen generation rates (Fig. 19c and d). Zhang
spheres using a simple solegel method (Fig. 18a and e) [258]. In et al. have demonstrated the photoelectrocatalytic glucose
comparison with pure hollow TiO2 sphere, Pt/TiO2 hollow oxidation to promote hydrogen production over Pd QDs@NTAs
spheres shows an higher photocatalytic water splitting activ- synthesized by a modified hydrothermal method which is
ity under visible light as a result of improved donor density more efficient than pure water oxidation [263]. The results
and reduced recombination of photogenerated electronehole showed that the photoelectrocatalytic hydrogen production
pairs. Schmuki et al. demonstrated a novel sputtering- rate reached 164.8 mmol cm2 over Pd QDs@NTAs, which was
dewetting-dealloying approach for fabricating a photo- 3e4 times higher than that of electrocatalytic and photo-
catalytic platform consisting of anodic TiO2 nanotubes catalytic water splitting (Fig. 19e and h). In addition, silver
Fig. 18 e SEM (a) and TEM (e) images of Pt/TiO2 hollow sphere composites [258]. TiO2 nanotubes after 10 nm Au sputtering (b)
and porous Au nanoparticles after dealloying in HNO3 (f) [259]. TEM (c) and HRTEM (g) images of a Pt/TiO2 nanosheet [260].
TEM images (d, h) of 3D urchin-like TiO2 microstructures decorated with Ag nanoparticles [261].
Fig. 19 e SEM (a) and TEM (b) images of Pd QDs@TiO2 NTAs produced by hydrothermal methods. Hydrogen generated by
TiO2 nanotubes and Pd/NTAs nanocomposites as photoanodes and Pt foil and Pd/NTAs nanocomposites as cathodes at
¡0.3 VSCE in a PEC cell containing 2 M Na2CO3 and 0.5 M ethylene glycol solutions under 320 mW cm¡2 irradiation (c).
Schematic of Pd/NTAs employed in photoelectrocatalytic water splitting (d) [262]. SEM (e) and TEM (f) images of Pd QDs@TiO2
NTAs produced by a modified hydrothermal method. Hydrogen generated using TiO2 with one and three-step anodization
and Pd QDs@NTAs as the photoanode and Pt sheet as cathode at a bias potential of ¡0.3 V (vs. SCE) in a 0.5 mol L¡1 KOH
solution containing 0.1 mol L¡1 glucose under simulated solar irradiation (g). Schematic diagram of the basic operating
mechanism for hydrogen production from biomass-derived oxygenates (CxHyOz) (h) [263].
halide nanoparticles (AgCl, AgBr, AgI) [264e267], can also serve reagents to initiate pollution degradation (oxidation). There-
as electron acceptors where they have been shown to enhance fore, graphene/TiO2 composites exhibited extremely high
visible light absorption and facilitate the transfer of photo- hydrogen generation and photocatalytic degradation activity
generated electrons and hoes within TiO2 nanomaterials. in wastewater. Li et al. prepared reduced TiO2-graphene oxide
heterostructures. The obtained heterostructures achieved an
Surface modification with graphene and narrow band gap extended optical response ranging from ultraviolet to visible
semiconductors and improved charge conduction due to graphene oxide [281].
Another important approach for extending the light absorp- As shown in Fig. 20a and b, TiO2 showed favorable dispersion
tion range of TiO2 into the visible as well as improve charge in the GO matrix remained in good contact with GO. Moreover,
transfer is to decorate TiO2 with graphene and colored (nar- a maximum H2 production rate of 16 mmol h1 g1 was
row band gap) semiconductors such as CdS, CdSe, and MoS2 measured using Pt as a co-catalyst under simulated sunlight
[268e272]. irradiation. A high solar energy conversion efficiency of 14.3%
Graphene, a single layer of two-dimensional sp2 hybridized was achieved (Fig. 20c and d). Dang et al. reported a green,
carbon atoms, has been widely used to modify TiO2 due to its facile one-step hydrothermal method to prepare TiO2 nano-
superior mechanical, electrical, and thermal properties since tube/graphene (TNT/GR) photocatalysts with various gra-
it was discovered by Geim and co-workers [273e278]. Hao et al. phene contents (0.5, 1, 2, 5, and 10 wt%) [282]. During the
anchored TiO2 with graphene quantum dots by an in-situ hydrothermal reaction, the reduction of graphene oxide into
photo-assisted approach that greatly enhanced photo- graphene and the formation of 1D TiO2 nanotubes were ach-
catalytic H2 evolution activity in methanol aqueous solution ieved simultaneously resulting in the direct growth of well-
[279]. The graphene quantum dots not only acted as efficient defined TiO2 nanotubes uniformly distributed on the gra-
electron reservoirs and a solid-state electron transfer reagent phene substrates (Fig. 20e and f). A significantly enhanced
from the conduction band of TiO2, but also as excellent pho- photocatalytic hydrogen production (12.1 mmol h1) was ob-
tosensitizers for TiO2. In addition, graphene quantum dots tained for the composition-optimized TNT/GR composite
increase the contact area with the TiO2. This is conducive to (with 1.0 wt% GR). This value is three times higher than that of
rapidly transfer photo-generated electrons. Zhang et al. pure TNTs (4.0 mmol h1) which is attributed to the more
modified TiO2 nanoparticles with graphene by hydrothermal efficient photo-induced charge separation and enhanced
methods [280]. The resulting TiO2 nanoparticles (10e20 nm) visible-light absorption (Fig. 20g and h). In an opposite fashion,
were uniformly dispersed on reduced graphene oxide. During Xu et al. deposited graphene quantum dots onto three-
the water splitting process, the graphene could function as an dimensional hierarchical TiO2 nanorods by an electrodeposi-
active site by accepting electrons to induce H2 generation and tion technique [283]. The composites delivered a high IPCE
further inhibit the recombination of electronehole pairs. At value and photoelectrocatalytic hydrogen production rate
the same time, the separated holes could react with sacrificial because the hierarchical structure can simultaneously offer a
Fig. 20 e SEM image of pure TiO2 nanoparticles (a). SEM (b) and TEM (c) images of GO/TiO2 composites. Photocatalytic
hydrogen evolution performance and stability test of GO/TiO2 under AM 1.5G irradiation (d). TEM images of pure TiO2
nanotubes (e) and graphene/TiO2 nanotubes with 10 wt.% graphene (f) [282]. Photocatalytic H2 evolution vs. irradiation time
for the TNT/GR samples with various graphene contents (from 0 to 10 wt%) under 300 W Xe-lamp light illumination (g).
Schematic diagram of charge transport in TNT/GR photocatalysts under Xe-lamp irradiation (h) [283].
large quantity of photocatalytic sites, excellent light-trapping greatly improved leading to enhanced photocatalytic and
characteristics, as well as a highly conductive pathway for the photoelectrocatalytic activity [290e293]. Cadmium sulfide
collection of charge carriers. Recently, there have been more (CdS) is a well-known semiconductor and most widely used to
works on ternary graphene/TiO2 composites modified with modify TiO2 by constructing nen heterojunctions due to its
noble metal nanoparticles such as Au and Ag. The photo- narrower band gap (2.4 eV) and more negative conduction
catalytic activity of such materials has improved a lot due to band. Zhao et al. incorporated CdS nanoparticles into meso-
the synergistic effects between graphene and noble metal porous anatase TiO2 by a chemical bath deposition method
nanoparticles [284,285]. [294]. CdS nanoparticles were uniformly dispersed in the
Since TiO2 is an n-type semiconductor, it would an effec- framework of mesoporous anatase TiO2 beads. The photo-
tive strategy to enhance photocatalytic activity by construct- catalyst displayed a broad absorption band in the visible re-
ing a pen or nen junction with another p-type or n-type gion and exhibited high photocatalytic activity and stability
semiconductor due to the existence of an internal electric field for hydrogen evolution. In a related work, Li et al. developed
at the interface [286e289]. When the junction is constructed, highly active CdS/TiO2 nanotube heterostructure photo-
the resulting local electric field drives the photo-generated catalysts for hydrogen production under visible light irradia-
electrons to the n-type semiconductor side while holes tion by the same method [295]. The potential gradient at the
transfer in the opposite direction (Fig. 21). As a result, the interface between CdS nanoparticles and TiO2 nanotubes
separation of photo-induced electronehole pairs can be helped to facilitate the diffusion of photo-generated electrons
Fig. 21 e Schematic diagram of charge transfer in a photocatalytic system with nen heterojunctions (a) and pen
heterojunctions (b) [282].
from CdS particles to TiO2 nanotubes. This led to high pho- transfer and separation of the photo-generated electronehole
tocatalytic activity and consequently improved hydrogen pairs.
production. In addition, different strategies have been inves- In addition to nen junctions, pen junctions and multi-
tigated for constructing CdS/TiO2 heterojunctions with other junctions have also been constructed to improve photo-
TiO2 morphologies such as nanowire, nanorod and nanosheet catalytic water splitting activity. The p-type semiconductor
to further improve photo-activity and hydrogen generation Cu2O has been long considered an attractive photocatalyst to
[296e300]. Quang et al. synthesized a 3D branched TiO2/CdS couple with TiO2 for photocatalytic water reduction. Tamio-
nanorod coreeshell structure by hydrothermal and chemical lakis et al. fabricated mesoporous structures of Cu2O and TiO2
bath deposition methods [301]. The CdS nanoparticles were nanoparticles for highly efficient photocatalytic hydrogen
uniformly dispersed on the surface of the branched TiO2 generation from water [309]. The composites exhibited high
nanorods. The 3D branched TiO2/CdS nanorod structures H2 evolution rate, quantum efficiency and photon conversion
showed improved photo-to-current conversion efficiencies efficiency under visible light because of the large surface area
and photoelectrocatalytic hydrogen generation rates when and efficient separation of electron/hole pairs due the pen
compared with a typical nanorod array structure due to the junction formation. Similarly, Chang et al. synthesized pen
larger surface area, enhanced visible-light absorption and junction Cu2O-doped TiO2 nanotube arrays by a square wave
improved separation of electron/hole pairs (Fig. 22aed). In voltammetry electrochemical deposition method [310]. In
addition to CdS, CdSe nanoparticle-enhanced TiO2 nanotube contrast to pristine TiO2 nanotube arrays, the Cu2O/TiO2
array electrodes produced by electrodeposition have also been nanotube arrays displayed enhanced photoelectrocatalytic
explored as the photoanode for driving the photogeneration of hydrogen and enhanced photoelectrocatalytic
electrocatalytic generation of hydrogen and simultaneous degradation of ibuprofen at a bias potential of 1 V by reducing
degradation of organic pollutants [302,303]. Other nen heter- recombination of electronehole pairs and prolonging the
ojunctions such as perovskite MTiO3/TiO2 heterostructures lifetime of electrons. Furthermore, Liu et al. reported the
(M ¼ Sr, Ca, Ba, Mg etc.), produced by hydrothermal treatment synthesis of TiO2 (core)/Cu2O (thin shell) nanorods by a redox
are ideal photocatalysts for hydrogen generation due to their reaction between Cu2þ and in-situ generated Ti3þ when Cu2þ-
excellent solar light harvesting capabilities [304e307]. Sun exchanged H-titanate nanotubes are calcined in air [311]. The
et al. modified TiO2 nanotube arrays (TiO2 NTAs) with SrTiO3/ effect of different Cu2O loadings on the performances was also
TiO2 hetero-nanoparticles by a two-step hydrothermal tech- discussed. The anatase TiO2 nanorods demonstrated a well
nique [308]. The photoelectrocatalytic hydrogen production ordered and uniform tubular structure with diameters of
rate of TiO2 NTAs can be significantly improved by using 8e15 nm and lengths of several hundred nanometers. The
SrTiO3eTiO2 hetero-nanoparticles and reached a value of Cu2O thin films had thicknesses less than 7 nm (Fig. 22e and f).
314.9 mmol cm2 h1 (2.1 times higher than that of the un- Owing to the strong TiO2eCu2O interfacial interaction, TiO2
modified TiO2 NTAs). This is attributed to the improved (core)/Cu2O (thin shell) nanorods are highly active and stable
Fig. 22 e SEM images of 3D branched TiO2 (a) and TiO2/CdS nanorods (b). Photoconversion efficiency of the TiO2 nanorods,
3D branched TiO2 nanorods, TiO2/CdS nanorods, and 3D branched TiO2/CdS nanorods under AM 1.5 G (c). Hydrogen
generation rate of 3D branched TiO2 nanorods, TiO2/CdS nanorods and 3D branched TiO2/CdS nanorods measured at
zero bias (vs. SCE) (d) [301]. TEM (e), HRTEM (f) and STEM images and corresponding EDX mapping images (g) of TiO2
(core)/Cu2O (thin shell) nanorods (1 wt%-Cu2O/TiO2). Photocatalytic activity for water reduction under simulated solar light
of TiO2 (core)/Cu2O (thin shell) nanorods with different loading amounts of Cu2O (h). Illustration of the proposed charge
transfer mechanism within Cu2O/TiO2 composites (i) [311].
during photocatalytic water reduction under solar light. Dur- In this review, we highlight the state-of-the-art fabrication
ing the photocatalytic water reduction process, the TiO2 core routes for 0D, 1D, 2D and 3D TiO2 nanomaterials with
acts as the photosensitizer and the Cu2O shell acts as the co- well-defined structures. The production methods addressed
catalyst. The photo-excited electrons in the conduction band include hydrothermal methods, solvothermal methods,
and the holes in the valence band of the TiO2 core are trans- solegel methods, template methods, electrospinning and
ferred to the conduction band and the valence band of the electrochemical anodic oxidation. Among them, the hydro-
Cu2O ultrathin film shell to efficiently catalyze water reduc- thermal route is by far the most popular for the synthesis of
tion to produce H2 (Fig. 22g and h). In addition, Zhang et al. TiO2 nanomaterials with different morphologies due to its ease
have proposed an electrochemical deposition method to of operation and control of the formed nanostructures. In
synthesize BiOI/TiO2 heterojunctions [312]. The resulting general, in order to achieve solar water splitting efficiency,
composite films exhibits a high photocurrent density of heterogeneous structures are produced by combining different
2.97 mA cm2 at 1.23 V under solar light and the IPCE response surface engineering strategies such as enlargement of the
at 500 nm can reach 30%. The superior photoelectrocatalytic active photocatalytic area, optimization of the crystallinity and
performance can be attributed to the effective charge sepa- exposed facets, development of visible light sensitized photo-
ration of photo-induced electronehole pairs and the fast catalysts via doping or modification with metals, non-metals
interfacial charge transfer caused by the heterojunction. This and narrow band gap semiconductors. Over the past several
work provides a strategy to prepare a heterojunction with an decades, much effort has been invested in the rational design
enhanced visible light response. It is also applicable to pro- of such heterogeneous structures and systematical investiga-
duce other BiOX (X ¼ Cl, Br, I)-based heterostructures. Multi- tion of many other doping strategies. And significant progress
heterojunctions such as Cu2O/RGO/TiO2, NiO/RGO/TiO2 have has truly been made in constructing heterogeneous photo-
been widely investigated to improve photocatalytic perfor- catalysts with improved hydrogen generation efficiency. There
mance and yield higher activity than single heterojunctions or are still many earth-abundant metal oxides and other new
bare TiO2 [313,314]. materials which have not yet to be investigated for use with
P-type Cu2O has been long considered as an attractive TiO2.
photocatalyst for photocatalytic water reduction. Here, we However, there still exist several challenges limiting the
report the synthesis of TiO2 (core)/Cu2O(ultrathin film shell) functionality and performance of TiO2 nanostructures. Due to
nano-rods by a redox reaction between Cu2þ and in-situ its wide band gap, TiO2 has a low utilization of solar light. In
generated Ti3þ when Cu2þ-exchanged H-titanate nanotubes addition, fast recombination of electron/hole pairs limits its
are calcined in air. In conclusion, we have proposed an elec- photocatalytic efficiency. It is necessary to investigate the
trochemical deposition method to synthesize the BiOI/TiO2 synergistic effects of the different engineering strategies as
heterojunction. Their significant PEC performance can be one single strategy alone will not likely be sufficient for all end
contributed to the effective charge separation of photoin- uses. For example, enlarging the surface area makes TiO2
duced electronehole pairs and fast interfacial charge transfer more active, but it is still inactive in solar light. Thus it is also
caused by the heterojunction. This work provides a strategy to necessary to sensitize TiO2 with visible-light photocatalysts.
prepare the heterojunction with an enhanced visible light Special attention should be given to the loading of binary or
response, which is also applicable to fabricate other BiOI- ternary TiO2 composites. These materials can not only
based heterostructure. enhance the kinetics of water oxidation and reduction, but
also suppress the recombination of photo-generated electrons
and holes due to the synergistic effects. We expect that the
Conclusions and perspectives large library of novel or unexplored candidates would offer a
wealth of potentially useful for high efficient energy materials.
Nanomaterials have attracted much attraction and they have It is clear that more effort should be invested in further un-
been used in many novel research areas including materials derstanding the detailed thermodynamics and kinetics of
development, medicine and energy and environmental tech- interfacial electron and hole transfer on the surface of these
nology. In light of diminishing fossil fuel reserves and envi- structures. A thorough understanding of the intrinsic charge-
ronmental concerns, there is an ever growing desire to transfer dynamics and photocatalytic mechanistic at the
improve the conversion of water and solar energy into clean nanometer and atomic levels will be beneficial for finding the
hydrogen using earth-abundant materials. Solar water split- key efficiency-limiting factors and developing more effective
ting using nanomaterials accompanied with photocatalytic strategies for improving photocatalytic activity. Since the solar-
pollutant degradation is recognized as a potential technology to-hydrogen efficiency is low (<10%), it is essential to increase
for addressing these two concerns. However, TiO2 nano- the solar-to-hydrogen efficiency and fabricate stable photo-
materials exhibit insufficient visible light absorption and fast catalysts with long performance times. Until now, KOH, meth-
charge recombination due to a wide band gap. These two anol, Na2S, NaSO3 have been the common sacrificial agents for
properties greatly limit the photo-conversion efficiency po- water splitting. There is a long way to go to produce hydrogen
tential of pure TiO2 nanostructures. Despite these inherent without added sacrificial agents in water. With more efforts put
limitations, TiO2-based photocatalysts are still being heavily into clean and renewable energy resources, we expect multi-
investigated for photocatalytic applications. This is because dimensionally crafted TiO2-heterostructure nanomaterials to
the drawbacks can be solved with a synergistic combination of play an increasingly important role in our daily lives and with
structural and engineering strategies to effectively modify the the commercialization of TiO2-based materials for efficient
shape, morphology and chemical composition of plain TiO2. hydrogen production realized in the near future.
core/shell arrays on carbon textiles for lithium-ion battery

Acknowledgements applications. Energy Environ Sci 2012;5:6559e66.
[15] Zhu CR, Xia XH, Liu JL, Fan ZX, Chao DL, Zhang H, et al. TiO2
The authors thank the National Natural Science Foundation of nanotube@SnO2 nanoflake core-branch arrays for lithium-
China (21501127; 51502185), Natural Science Foundation of ion battery anode. Nano Energy 2014;4:105e12.
[16] Li HQ, Lai YK, Huang JY, Tang YX, Yang L, Chen Z, et al.
Jiangsu Province of China (BK20140400), Natural Science
Multifunctional wettability patterns prepared by laser
Foundation of the Jiangsu Higher Education Institutions of processing on superhydrophobic TiO2 nanostructured
China (15KJB430025). We also acknowledge the funds from the surfaces. J Mater Chem B 2015;3:342e7.
project of the Priority Academic Program Development of [17] Lai YK, Huang JY, Cui ZQ, Ge MZ, Zhang KQ, Chen Z, et al.
Jiangsu Higher Education Institutions (PAPD). M.Z. Ge and J.S. Recent advances in TiO2-based nanostructured surfaces
Cai contributed equally to this work. M.Z. Ge acknowledges with controllable wettability and adhesion. Small
2016;12:2203e24.
the financial support from the China Scholarship Council.
[18] Huang JY, Li SH, Ge MZ, Wang LN, Xing TL, Chen GQ, et al.
Robust superhydrophobic TiO2@fabrics for UV shielding,
self-cleaning and oil-water separation. J Mater Chem A
references 2015;3:2825e32.
[19] Li SH, Huang JY, Ge MZ, Cao CY, Deng S, Zhang SN, et al.
Robust flower-like TiO2@cotton fabrics with special
[1] Sang YH, Zhao ZH, Tian J, Hao P, Jiang HD, Liu H, et al. wettability for effective self-cleaning and versatile oil/water
Enhanced photocatalytic property of reduced graphene separation. Adv Mater Interfaces 2015;2. 1500220.
oxide/TiO2 nanobelt surface heterostructures constructed [20] Zeng L, Lu Z, Li MH, Yang J, Song WL, Zeng DW, et al. A
by an in situ photochemical reduction method. Small modular calcination method to prepare modified N-doped
2014;10:3775e82. TiO2 nanoparticle with high photocatalytic activity. Appl
[2] Tian J, Leng YH, Zhao ZH, Xia Y, Sang YH, Hao P, et al. Catal B-Environ 2016;183:308e16.
Carbon quantum dots/hydrogenated TiO2 nanobelt [21] Chuang HY, Chen DH. Fabrication and
heterostructures and their broad spectrum photocatalytic photoelectrochemical study of Ag@TiO2 nanoparticle
properties under UV, visible, and near-infrared irradiation. thin film electrode. Int J Hydrogen Energy
Nano Energy 2015;11:419e27. 2011;36:9487e95.
[3] Xie GC, Zhang K, Guo BD, Liu Q, Fang L, Gong JR. Graphene- [22] Liu B, Xiao JZ, Xu L, Ya YJ, Costa BFO, Domingos VF, et al.
based materials for hydrogen generation from light-driven Gelatin-assisted sol-gel derived TiO2 microspheres for
water splitting. Adv Mater 2013;25:3820e39. hydrogen storage. Int J Hydrogen Energy 2015;40:4945e50.
[4] Han ZJ, Qiu F, Eisenberg R, Holland PL, Krauss TD. Robust [23] Haider Z, Kang YS. Facile preparation of hierarchical TiO2
photogeneration of H2 in water using semiconductor nanostructures: growth mechanism and enhanced
nanocrystals and a nickel catalyst. Science 2012;338:1321e4. photocatalytic H2 production from water splitting using
[5] Winther JB, Fraser K, Ong C, Forsyth M, MacFarlane DR. methanol as a sacrificial reagent. ACS Appl Mater Interfaces
Conducting polymer composite materials for hydrogen 2014;6:10342e52.
generation. Adv Mater 2010;22:1727e30. [24] Tang YX, Lai YK, Gong DG, Goh KH, Lim TT, Dong ZL, et al.
[6] Krafft KE, Wang C, Lin WB. Metal-organic framework Ultrafast synthesis of layered titanate microspherulite
templated synthesis of Fe2O3/TiO2 nanocomposite for particles by electrochemical spark discharge spallation.
hydrogen production. Adv Mater 2012;24:2014e8. Chem Eur J 2010;16:7704e8.
[7] Tedsree K, Li T, Jones S, Chan CWA, Yu KMK, Bagot PAJ, [25] Naik BB, Moon SY, Kim SH, Park JY. Enhanced
et al. Hydrogen production from formic acid decomposition photocatalytic generation of hydrogen by Pt-deposited
at room temperature using a Ag-Pd core-shell nanocatalyst. nitrogen-doped TiO2 hierarchical nanostructures. Appl Surf
Nature 2011;6:302e7. Sci 2015;354:347e52.
[8] Baran E, Yazici B. Effect of different nanostructured Ag [26] Chen XB, Liu L, Huang FQ. Black titanium dioxide (TiO2)
doped TiO2-NTs fabricated by electrodeposition on the nanomaterials. Chem Soc Rev 2015;44:1861e85.
electrocatalytic hydrogen production. Int J Hydrogen Energy [27] Froschl T, Ho€ rmann U, Kubiak P, Kuc erova G, Pfanzelt M,
2016;41:2498e511. Weiss CK, et al. High surface area crystalline titanium
[9] Yanagida S, Azuma T, Kawakami H, Kizumoto H, Sakurai H. dioxide: potential and limits in electrochemical energy
Photocatalytic carbon-carbon bond formation with storage and catalysis. Chem Soc Rev 2012;41:5313e60.
concurrent hydrogen evolution on the Pt/TiO2 nanotube. [28] Park H, Kim H, Moon GH, Choi W. Photoinduced charge
Appl Surf Sci 2015;325:86e90. transfer processes in solar photocatalysis based on
[10] Bagheri S, Julkapli NM. Synergistic effects on hydrogenated modified TiO2. Energy Environ Sci 2016;9:411e33.
TiO2 for photodegradation of synthetic compounds [29] Zhou W, Liu H, Boughton RI, Du G, Lin J, Wang J, et al. One-
pollutants. Int J Hydrogen Energy 2016;41:14652e64. dimensional single-crystalline Ti-O based nanostructures:
[11] Wang YL, Zhu LZ, Wang M, Zhang MQ, Yang Y, Zhu Q, et al. properties, synthesis, modifications and applications.
Microstructure and photocatalytic activity of porous TiO2- J Mater Chem 2010;20:5993e6008.
Fe2O3 composite film by PEO coupled with post heat [30] Gupta B, Melvin AA, Matthews T, Dash S, Tyagi AK. TiO2
treatment. Int J Hydrogen Energy 2016;41:15703e9. modification by gold (Au) for photocatalytic hydrogen (H2)
[12] Ye MD, Zheng DJ, Lv MQ, Chen C, Lin CJ, Lin ZQ. production. Renew Sust Energy Rev 2016;58:1366e75.
Hierarchically structured nanotubes for highly efficient [31] Sun T, Liu EZ, Liang XH, Hu XY, Fan J. Enhanced hydrogen
dye-sensitized solar cells. Adv Mater 2013;25:3039e44. evolution from water splitting using Fe-Ni codoped and Ag
[13] Ye MD, Xin XK, Lin CJ, Lin ZQ. High efficiency dye-sensitized deposited anatase TiO2 synthesized by solvothermal
solar cells based on hierarchically structured nanotubes. method. Appl Surf Sci 2015;347:696e705.
Nano Lett 2011;11:3214e20. [32] Fornari AMD, Araujo MBD, Duarte CB, Machado G,
[14] Luo YS, Luo JS, Jiang J, Zhou WW, Yang HP, Qi XY, et al. Teixeira SR, Weibel DE. Photocatalytic reforming of aqueous
Seed-assisted synthesis of highly ordered TiO2@alpha-Fe2O3 formaldehyde with hydrogen generation over TiO2
nanotubes loaded with Pt or Au nanoparticles. Int J [52] Lee S, Jeon C, Park Y. Fabrication of TiO2 tubules by template
Hydrogen Energy 2016;41:11599e607. synthesis and hydrolysis with water vapor. Chem Mater
[33] Wang FL, Jin ZM, Jiang YG, Backus EHG, Bonn M, Lou SN, 2004;16:4292e5.
et al. Probing the charge separation process on In2S3/Pt-TiO2 [53] Tang YX, Zhang YY, Deng JY, Qi DP, Leo WR, Wei JQ, et al.
nanocomposites for boosted visible-light photocatalytic Unravelling the correlation between the aspect ratio of
hydrogen production. Appl Catal B-Environ 2016;198:25e31. nanotubular structures and their electrochemical
[34] Iervolino G, Vaiano V, Murcia JJ, Rizzo L, Ventre G, Pepe G, performance to achieve high-rate and long-life lithium-ion
et al. Photocatalytic hydrogen production from degradation batteries. Angew Chem Int Ed 2014;53:13488e92.
of glucose over fluorinated and platinized TiOþ catalysts. [54] Tang YX, Zhang YY, Deng JY, Wei JQ, Hon TL, Chandran BK,
J Catal 2016;339:47e56. et al. Mechanical force-driven growth of elongated bending
[35] Bashiri R, Mohamed NM, Kait CF, Sufian S. Hydrogen TiO2-based nanotubular materials for ultrafast
production from water photo-splitting using Cu/TiO2 rechargeable lithium ion batteries. Adv Mater
nanoparticles: effect of hydrolysis rate and reaction 2014;26:6111e8.
medium. Int J Hydrogen Energy 2015;40:6021e37. [55] Gong D, Grimes CA, Varghese OK, Hu W, Singh RS, Chen Z,
[36] Li YP, Wang BW, Liu SH, Duan XF, Hu ZY. Synthesis and et al. Titanium oxide nanotube arrays prepared by anodic
characterization of Cu2O/TiO2 photocatalysts for H2 oxidation. J Mater Res 2001;16:3331e4.
evolution from aqueous solution with different scavengers. [56] Mor GK, Shankar K, Paulose M, Varghese OK, Grimes CA.
Appl Surf Sci 2015;324:736e44. Enhanced photocleavage of water using titania nanotube
[37] Li LL, Cheng B, Wang YX, Yu JG. Enhanced photocatalytic arrays. Nano Lett 2005;5:191e5.
H2-production activity of bicomponent NiO/TiO2 composite [57] Zwilling V, Darque-Ceretti E, Boutry-Forveille A, David D,
nanofibers. J Colloid Interf Sci 2015;449:115e21. Perrin MY, Aucouturier M. Structure and physicochemistry
[38] Li YF, Zhang WP, Shen X, Peng PF, Xiong LB, Yu Y. Octahedral of anodic oxide films on titanium and TA6V alloy. Surf
Cu2O-modified TiO2 nanotube arrays for efficient Interface Anal 1999;27:629e37.
photocatalytic reduction of CO2. Chin J Catal 2015;36:2229e36. [58] Macak JM, Sirotna K, Schmuki P. Self-organized porous
[39] Kalyani R, Gurunathan K. PTh-rGO-TiO2 nanocomposite for titanium oxide prepared in Na2SO4/NaF electrolytes.
photocatalytic hydrogen production and dye degradation. Electrochim Acta 2005;50:3679e84.
J Photochem Photobio A 2016;329:105e12. [59] Paulose M, Prakasam HE, Varghese OK, Peng L, Popat KC,
[40] Zhang YY, Jiang ZL, Huang JY, Lim LD, Li WL, Deng JY, et al. Mor GK, et al. TiO2 nanotube arrays of 1000 mm length by
Titanate and titania nanostructured materials for anodization of titanium foil: phenol red diffusion. J Phys
environmental and energy applications: a review. RSC Adv Chem C 2007;111:14992e7.
2015;5:79479e510. [60] Hahn R, Macak JM, Schmuki P. Rapid anodic growth of TiO2
[41] Jiang LC, Zhang WD. Electrodeposition of TiO2 nanoparticles and WO3 nanotubes in fluoride free electrolytes.
on multiwalled carbon nanotube arrays for hydrogen Electrochem Commun 2007;9:947e52.
peroxide sensing. Electroanalysis 2009;8:988e93. [61] Ge MZ, Li SH, Huang JY, Zhang KQ, Al-Deyab SS, Lai YK. TiO2
[42] Liu J, Zhao Y, Shi LY, Yuan S, Fang JH, Wang ZY, et al. nanotube arrays loaded with reduced graphene oxide films:
Solvothermal synthesis of crystalline phase and shape facile hybridization and promising photocatalytic
controlled Sn4þ-doped TiO2 nanocrystals: effects of reaction application. J Mater Chem A 2015;3:3491e9.
solvent. ACS Appl Mater Interfaces 2011;3:1261e8. [62] Ye MD, Gong JJ, Lai YK, Lin CJ, Lin ZQ. High-efficiency
[43] Nam CT, Yang WD, Duc LM. Solvothermal synthesis of TiO2 photoelectrocatalytic hydrogen generation enabled by
photocatalysts in ketone solvents with low boiling points. palladium quantum dots-sensitized TiO2 nanotube arrays.
J Nanomater 2013;2013. 627385. J Am Chem Soc 2012;134:15720e3.
[44] Kang M, Lee SY, Chung CH, Cho SM, Han GY, Kim BM. [63] Lin Y, Wu GS, Yuan XY, Xie T, Zhang LD. Fabrication and
Characterization of a TiO2 photocatalyst synthesized by the optical properties of TiO2 nanowire arrays made by sol-gel
solvothermal method and its catalytic performance for CHCl3 electrophoresis deposition into anodic alumina
decomposition. J Photochem Photobiol A 2001;144:185e91. membranes. J Phys Condens Matter 2003;15:2917e22.
[45] Cheng YH, Huang Y, Kanhere PD, Subramaniam VP, Gong D, [64] Xiang B, Zhang Y, Wang Z, Luo XH, Zhu YW, Zhang HZ, et al.
Zhang S, et al. Dual-Phase Titanate/anatase with nitrogen Field-emission properties of TiO2 nanowire arrays. J Phys D
doping for enhanced degradation of organic dye under Appl Phys 2005;38:1152e5.
visible light. Chem Eur J 2011;17:2575e8. [65] Lei Y, Zhang LD, Fan JC. Fabrication, characterization and
[46] Yang L, Gao MG, Dai B, Guo XH, Liu ZY, Peng BH. Synthesis Raman study of TiO2 nanowire arrays prepared by anodic
of spindle-shaped AgI/TiO2 nanoparticles with enhanced oxidative hydrolysis of TiCl3. Chem Phys Lett
photocatalytic performance. Appl Surf Sci 2016;386:337e44. 2001;338:231e6.
[47] Ren Y, Liu Z, Pourpoint F, Armstrong AR, Grey CP, Bruce PG. [66] Liu S, Huang K. Titanium dioxide nanomaterials synthesis,
Nanoparticulate TiO2 (B): an anode for lithium-ion batteries. properties, modifications, and applications. Sol Energy
Angew Chem Int Ed 2012;51:2164e7. Mater Sol Cells 2004;85:125e31.
[48] Kasuga T, Hiramatsu M, Hoson A, Sekino T, Niihara K. [67] Wen B, Liu C, Liu Y. Bamboo-shaped Ag-doped TiO2
Formation of titanium oxide nanotube. Langmuir nanowires with heterojunctions. Inorg Chem
1998;14:3160e3. 2005;44:6503e5.
[49] Kasuga T, Hiramatsu M, Hoson A, Sekino T, Niihara K. [68] Wen B, Liu C, Liu Y. Depositional characteristics of metal
Titania nanotubes prepared by chemical processing. Adv coating on single-crystal TiO2 nanowires. J Phys Chem B
Mater 1999;11:1307e11. 2005;109:12372e5.
[50] Chen Q, Zhou WZ, Du GH, Peng LM. Trititanate nanotubes [69] Miao L, Tanemura S, Toh S, Kaneko K, Tanemura MJ.
made via a single alkali treatment. Adv Mater Fabrication, characterization and Raman study of anatase-
2002;14:1208e11. TiO2 nanorods by a heating-sol-gel template process. J Cryst
[51] Geng JQ, Yang D, Zhu JH, Chen DM, Jiang ZY. Growth 2004;264:246e52.
Nitrogen-doped TiO2 nanotubes with enhanced [70] Marlene RR, He ctor JDR. A simple route to obtain TiO2
photocatalytic activity synthesized by a facile wet nanowires by the sol-gel method. J SoleGel Sci Technol
chemistry method. Mater Res Bull 2009;44:146e50. 2011;59:658e61.
[71] Armstrong AR, Armstrong G, Canales J, Garcia R, Bruce PG. [91] Zhao Z, Tian J, Sang Y, Cabot A, Liu H. Structure, synthesis,
Lithium-ion intercalation into TiO2-B nanowires. Adv Mater and applications of TiO2 nanobelts. Adv Mater
2005;7:862e5. 2015;27:2557e82.
[72] Nian JN, Teng HS. Hydrothermal synthesis of single- [92] Nguyen-Phan TD, Song MB, Kim EJ, Shin EW. Influence of
crystalline anatase TiO2 nanorods with nanotubes as the alkali-treatment temperature on the one-dimensional
precursor. J Phys Chem B 2006;110:4193e8. structure of nanosized TiO2. Res Chem Intermed
[73] Liu B, Aydil ES. Growth of oriented single-crystalline 2010;36:613e9.
rutile TiO2 nanorods on transparent conducting substrates [93] Wang J, Zhao L, Lin VS-Y, Lin Z. Formation of various TiO2
for dye-sensitized solar cells. J Am Chem Soc nanostructures from electrochemically anodized titanium.
2009;131:3985e90. J Mater Chem 2009;19:3682e7.
[74] Hwang YJ, Hahn C, Liu B, Yang P. Photoelectrochemical [94] Hoa NTQ, Kim ET. Self-catalytic growth of TiO2-d nanobelts
properties of TiO2 nanowire arrays: a study of the and nanosheets using metallorganic chemical vapor
dependence on length and atomic layer deposition coating. deposition. Electrochem Solid State Lett 2008;11:K1e3.
ACS Nano 2012;6:5060e9. [95] Wang Y, Wan RG, Guo C, Miao J, Tian Y, Ren T, et al. Path-
[75] Cho IS, Chen Z, Forman AJ, Kim DR, Rao PM, Jaramillo TF, directed and maskless fabrication of ordered TiO2
et al. Branched TiO2 nanorods for photoelectrochemical nanoribbons. Nanoscale 2012;4:1545e8.
hydrogen production. Nano Lett 2011;11:4978e84. [96] Lim YWL, Tang YX, Cheng YH, Chen Z. Morphology, crystal
[76] Xu C, Zhan Y, Hong K, Wang G. Growth and mechanism of structure and adsorption performance of hydrothermally
titania nanowires. Solid State Commun 2003;126:545e9. synthesized titania and titanate nanostructures. Nanoscale
[77] Wang G, Li G. Titania from nanoclusters to nanowires and 2010;2:2751e7.
nanoforks. Eur Phys J D 2003;24:355e60. [97] Zhang DR, Kim CW, Kang YS. A Study on the
[78] Lee JC, Park KS, Kim TG, Choi HJ, Sung YM. Controlled Crystalline Structure of sodium titanate nanobelts
growth of high-quality TiO2 nanowires on sapphire and prepared by the hydrothermal method. J Phys Chem C
silica. Nanotechnology 2006;17:4317e21. 2010;114:8294e301.
[79] Jiang CR, Lee KY, Parlett CMA, Bayazit MK, Lau CC, Ruan QS, [98] Yang HG, Zeng HC. Synthetic architectures of
et al. Size-controlled TiO2 nanoparticles on porous hosts for TiO2/H2Ti5O11$H2O, ZnO/H2Ti5O11$H2O,
enhanced photocatalytic hydrogen production. Appl Catal A ZnO/TiO2/H2Ti5O11$H2O, and ZnO/TiO2 nanocomposites.
Gen 2016;521:133e9. J Am Chem Soc 2005;127:270e8.
[80] Miao L, Tanemura S, Toh S, Kaneko K, Tanemura M. [99] Pang LX, Wang XY, Tang XD. Enhanced photocatalytic
Heating-sol-gel template process for the growth of TiO2 performance of porous TiO2 nanobelts with phase
nanorods with rutile and anatase structure. Appl Surf Sci junctions. Solid State Sci 2015;39:29e33.
2004;238:175e9. [100] Wu D, Liu J, Zhao XN, Li AD, Chen YF, Ming NB. Sequence of
[81] Wu JM. Low-temperature preparation of titania nanorods events for the formation of titanate nanotubes, nanofibers,
through direct oxidation of titanium with hydrogen nanowires, and nanobelts. Chem Mater 2006;18:547e53.
peroxide. J Cryst Growth 2004;269:347e55. [101] Liao JY, Lei BX, Chen HY, Kuang DB, Su CY. Oriented
[82] Wu JM, Zhang TW, Zeng YW, Hayakawa S, Tsuru K, hierarchical single crystalline anatase TiO2 nanowire arrays
Osaka A. Large-scale preparation of ordered titania on Ti-foil substrate for efficient flexible dye-sensitized solar
nanorods with enhanced photocatalytic activity. Langmuir cells. Energy Environ Sci 2012;5:5750e7.
2005;21:6995e7002. [102] Amin SS, Nicholls AW, Xu TT. A facile approach to
[83] Wu JM, Zhang TW. Photodegradation of rhodamine B in synthesize single-crystalline rutile TiO2 one-dimensional
water assisted by titania films prepared through a novel nanostructures. Nanotechnology 2007;18:445609e17.
procedure. J Photochem Photobio A 2004;162:171e7. [103] Xia D, Jiang YB, He X, Brueck SRJ. Titania nanostructure
[84] Cozzoli PD, Fanizza E, Curri ML, Laub D, Aqostiano A. arrays from lithographically defined templates. Appl Phys
Low-dimensional chainlike assemblies of TiO2 Lett 2010;97. 223106.
nanorod-stabilized Au nanoparticles. Chem Commun [104] Li D, Wang YL, Xia YN. Electrospinning of polymeric and
2005;7:942e4. ceramic nanofibers as uniaxially, aligned arrays. Nano Lett
[85] Buonsanti R, Grillo V, Carlino E, Giannini C, Curri ML, 2003;3:555e60.
Innocenti C, et al. Seeded growth of asymmetric binary [105] Yuan RS, Fu XZ, Wang XC, Liu P, Wu L, Xu YM, et al.
nanocrystals made of a semiconductor TiO2 rod-like section Template Synthesis of hollow metal oxide fibers with
and a magnetic g-Fe2O3 spherical domain. J Am Chem Soc hierarchical architecture. Chem Mater 2006;18:4700e5.
2006;128:16953e70. [106] Chang Z, Liu J, Liu JF, Sun XM. Titanate nanosheets and
[86] Cozzoli PD, Kornowski A, Weller H. Low-temperature nanotubes: alkalinity manipulated synthesis and catalyst
synthesis of soluble and processable organic-capped support application. J Mater Chem 2011;21:277e82.
anatase TiO2 nanorods. J Am Chem Soc 2003;125:14539e48. [107] Zhao B, Chen F, Gu XN, Zhang JL. Organic-stabilizer-free
[87] Melcarne G, De Marco L, Carlino E, Martina F, Manca M, synthesis of layered protonic titanate nanosheets. Chem
Cingolani R, et al. Surfactant-free synthesis of pure anatase Asian J 2010;5:1546e9.
TiO2 nanorods suitable for dye-sensitized solar cells. J Mater [108] Zhang Z, Goodall JBM, Brown S, Karlsson L, Clark RJH,
Chem 2010;20:7248e54. Hutchison JL, et al. Continuous hydrothermal synthesis of
[88] Chen CA, Chen YM, Korotcov A, Huang YS, Tsai DS, extensive 2D sodium titanate (Na2Ti3O7) nanosheets. Dalton
Tiong KK. Growth and characterization of well-aligned Trans 2010;39:711e4.
densely-packed rutile TiO2 nanocrystals on sapphire [109] Sutradhar N, Sinhamahapatra A, Pahari SK, Bajaj HC,
substrates via metal-organic chemical vapor deposition. Panda AB. Room temperature synthesis of protonated
Nanotechnology 2008;19. 075611. layered titanate sheets using peroxo titanium carbonate
[89] Pradhan SK, Reucroft PJ, Yang F, Dozier A. Growth of TiO2 complex solution. Chem Commun 2011;47:7731e3.
nanorods by metalorganic chemical vapor deposition. [110] Kijima N, Kuwabara M, Akimoto J, Kumagai T, Igarashi K,
J Cryst Growth 2003;256:83e8. Shimizu T. Synthesis and electrochemical properties of a
[90] Ma G, Zhao X, Zhu J. Microwave hydrothermal synthesis of porous titania fabricated from exfoliated nanosheets.
rutile TiO2 nanorods. Int J Mod Phys B 2005;19:2763e8. J Power Sources 2011;196:7006e10.
[111] Yang L, Viste M, Hossick SJ, Sheldon BW. Internal stress inorganic-organic hybrid materials. Chem Soc Rev
evolution during field-induced crystallization of anodic 2012;41:5131e42.
tantalum oxide. Electrochim Acta 2012;81:90e7. [130] Innocenzi P, Malfatti L, Soler IG. Hierarchical mesoporous
[112] Yang HG, Liu G, Qiao SZ, Sun CH, Jin YG, Smith SC, et al. films: from self-assembly to porosity with different length
Solvothermal synthesis and photoreactivity of anatase TiO2 scales. Chem Mater 2011;23:2501e9.
nanosheets with dominant {001} facets. J Am Chem Soc [131] Orilall MC, Wiesner U. Block copolymer based composition
2009;131:4078e83. and morphology control in nanostructured hybrid materials
[113] Meng AY, Zhang J, Xu DF, Yu JG. Enhanced photocatalytic for energy conversion and storage: solar cells, batteries, and
H2-production activity of anatase TiO2 nanosheet by fuel cells. Chem Soc Rev 2011;40:520e35.
selectively depositing dual-cocatalysts on {101} and {001} [132] Agrios AG, Cesar I, Comte P, Nazeeruddin MK, Gratzel M.
facets. Appl Catal B Environ 2016;198:286e94. Nanostructured composite films for dye-sensitized solar
[114] Sasaki T, Watanabe M. Osmotic swelling to exfoliation. cells by electrostatic layer-by-layer deposition. Chem Mater
Exceptionally high degrees of hydration of a layered 2006;18:5395e7.
titanate. J Am Chem Soc 1998;120:4682e9. [133] Cho TY, Han CW, Jun Y, Yoon SG. Formation of artificial
[115] Gunjakar JL, Kim TW, Kim HN, Kim IY, Hwang SJ. pores in nano-TiO2 photo-electrode films using acetylene-
Mesoporous layer-by-layer ordered nanohybrids of layered black for high-efficiency, dye-sensitized solar cells. Sci Rep
double hydroxide and layered metal oxide: highly active 2013;3:1496e9.
visible light photocatalysts with improved chemical [134] Thi TTP, Bessho T, Mathews N, Zakeeruddin SM, Lam YM,
stability. J Am Chem Soc 2011;133:14998e5007. Mhaisalkar S, et al. Light scattering enhancement from sub-
[116] Ma R, Sasaki T, Bando Y. Layer-by-layer assembled micrometer cavities in the photoanode for dye-sensitized
multilayer films of titanate nanotubes, Ag- or Au-loaded solar cells. J Mater Chem 2012;22:16201e4.
nanotubes, and nanotubes/nanosheets with polycations. J [135] Lyonnard S, Bartlett JR, Sizgek E, Finnie KS, Zemb T,
Am Chem Soc 2004;126:10382e8. Woolfrey JL. Role of interparticle potential in controlling the
[117] Sakai N, Fukuda K, Omomo Y, Ebina Y, Takada K, Sasaki T. morphology of spray-dried powders from aqueous
Hetero-nanostructured films of titanium and manganese nanoparticle sols. Langmuir 2002;18:10386e97.
oxide nanosheets: photoinduced charge transfer and [136] Ho W, Yu JC, Lee S. Synthesis of hierarchical nanoporous
electrochemical properties. J Phys Chem C F-doped TiO2 spheres with visible light photocatalytic
2008;112:5197e202. activity. Chem Commun 2006;10:1115e7.
[118] Kim HN, Kim TW, Kim IY, Hwang SJ. Cocatalyst-free [137] Park KS, Min KM, Jin YH, Seo SD, Lee GH, Shim HW, et al.
photocatalysts for efficient visible-light-induced H2 Enhancement of cyclability of urchin-like rutile TiO2
production: porous assemblies of CdS quantum dots and submicron spheres by nanopainting with carbon. J Mater
layered titanate nanosheets. Adv Funct Mater Chem 2012;22:15981e6.
2011;21:3111e8. [138] Iskandar F, Nandiyanto ABD, Yun KM, Hogan CJ,
[119] Kim TW, Hur SG, Hwang SJ, Park H, Choi W, Choy JH. Okuyama K, Biswas P. Enhanced photocatalytic
Heterostructured visible-light-active photocatalyst of performance of brookite TiO2 macroporous particles
chromia-nanoparticle-layered titanate. Adv Funct Mater prepared by spray drying with colloidal templating. Adv
2007;17:307e14. Mater 2007;19:1408e12.
[120] Gao T, Fjellvag H, Norby P. Crystal structures of titanate [139] Takezawa Y, Imai H. Bottom-up synthesis of titanate
nanotubes: a raman scattering study. Inorg Chem nanosheets with hierarchical structures and a high specific
2009;48:1423e32. surface area. Small 2006;2:390e3.
[121] Smarsly B, Fattakhova RD, Mitzi DB. Solution processing of [140] Li YB, Cooper JK, Liu WJ, Sutter FCM, Amani M, Beeman JW,
inorganic materials. New York: John Wiley & Sons Inc; 2009. et al. Defective TiO2 with high photoconductive gain for
p. 283. efficient and stable planar heterojunction perovskite solar
[122] Dickerson MB, Sandhage KH, Naik RR. Protein and eptide- cells. Nat Commun 2016;7:12446e51.
directed syntheses of inorganic materials. Chem Rev [141] Yoneyama H, Yamashita Y, Tamura H. Heterogeneous
2008;108:4935e78. photocatalytic reduction of dichromate on n-type
[123] Stein A, Li F, Denny NR. Morphological control in colloidal semiconductor catalysts. Nature 1979;282:817e8.
crystal templating of inverse opals, hierarchical structures, [142] Zou ZG, Ye JH, Sayama K, Arakawa H. Direct splitting of
and shaped particles. Chem Mater 2007;20:649e66. water under visible light irradiation with an oxide
[124] Sanchez C, Boissiere C, Grosso D, Laberty C, Nicole L. semiconductor photocatalyst. Nature 2001;414:625e7.
Design, synthesis, and properties of inorganic and hybrid [143] Lang XJ, Zhao JC, Chen XD. Visible-light-induced
thin films having periodically organized nanoporosity. photoredox catalysis of dye-sensitized titanium dioxide:
Chem Mater 2008;20:682e737. selective aerobic oxidation of organic sulfides. Angew Chem
[125] Boissiere C, Grosso D, Chaumonnot A, Nicole L, Sanchez C. Int Ed 2016;55:4697e700.
Aerosol route to functional nanostructured inorganic and [144] Liu J, Yang L, Liu NY, Han YZ, Zhang X, Huang H, et al.
hybrid porous materials. Adv Mater 2011;23:599e623. Metal-free efficient photocatalyst for stable visible water
[126] Pan JH, Zhao XS, Lee WI. Block copolymer-templated splitting via a two-electron pathway. Science
synthesis of highly organized mesoporous TiO2-based films 2015;347:970e4.
and their photoelectrochemical applications. Chem Eng J [145] Kim YK, Lima SK, Hyunwoong P, Michael RH, Soonhyun K.
2011;170:363e80. Trilayer CdS/carbon nanofiber (CNF) mat/Pt-TiO2 composite
[127] Innocenzi P, Malfatti L. Mesoporous thin films: properties structures for solar hydrogen production: effects of CNF
and applications. Chem Soc Rev 2013;42:4198e216. mat thickness. Appl Catal B Environ 2016;196:216e22.
[128] Zhang RY, Elzatahry AA, Al-Deyab SS, Zhao DY. [146] Liu QH, He JF, Yao T, Sun ZH, Cheng WR, He S, et al. Aligned
Mesoporous titania: from synthesis to application. Nano Fe2TiO5-containing nanotube arrays with low onset
Today 2012;7:344e66. potential for visible-light water oxidation. Nat Commun
[129] Rawolle M, Niedermeier MA, Kaune G, Perlich J, Lellig P, 2014;5:5122e6.
Memesa M, et al. Fabrication and characterization of [147] Setvin M. Reaction of O2 with subsurface oxygen vacancies
nanostructured titania films with integrated function from on TiO2 anatase (101). Science 2015;349. 1295e1295.
[148] Zhang YY, Wu B, Tang YX, Qi DP, Wang N, Wang XT, et al. [165] Ge MZ, Li QS, Cao CY, Huang JY, Li SH, Zhang SN, et al. One-
Prolonged electron lifetime in ordered TiO2 mesophyll cell- dimensional TiO2 nanotube photocatalysts for solar water
like microspheres for efficient photocatalytic water splitting. Adv Sci 2016;3. 1600152.
reduction and oxidation. Small 2016;12:2291e9. [166] Ge MZ, Cao CY, Huang JY, Li SH, Chen Z, Zhang KQ, et al. A
[149] Abe R. Recent progress on photocatalytic and review of one-dimensional TiO2 nanostructured materials
photoelectrochemical water splitting under visible light for environmental and energy applications. J Mater Chem A
irradiation. J Photochem Photobio C 2010;11:179e209. 2016;4:6772e801.
[150] Ni M, Michael KHL, Dennis YCL, Sumathy K. A review and [167] Vebber MC, Faria ACR, Dal AN, Beal LL, Fetter G, Machado G,
recent developments in photocatalytic water-splitting et al. Hydrogen production by photocatalytic water splitting
using TiO2 for hydrogen production. Renew Sust Energ Rev using poly (allylamine hydrochloride)/poly (acrylic acid)/
2007;11:401e25. TiO2/copper chlorophyllin self-assembled thin films. Int J
[151] Rajaambal S, Sivaranjani K, Gopinath CS. Recent Hydrogen Energy 2016;40:17995e8004.
developments in solar H2 generation from water splitting. [168] Salgado SYA, Zamora RMR, Zanella R, Peral J, Malato S,
J Chem Sci 2015;127:33e47. Maldonado MI. Photocatalytic hydrogen production in a
[152] Etacheri V, Valentin CD, Schneider J, Bahnemann D, solar pilot plant using an Au/TiO2 photo catalyst. Int J
Pillai SC. Visible-light activation of TiO2 photocatalysts: Hydrogen Energy 2016;41:11933e40.
advances in theory and experiments. J Photochem Photobio [169] Wen JQ, Li X, Liu W, Fang YP, Xie J, Xu YH. Photocatalysis
C 2015;25:1e29. fundamentals and surface modification of TiO2
[153] Babu VJ, Vempati S, Uyar T, Ramakrishna S. Review of one- nanomaterials. Chin J Catal 2015;36:2049e70.
dimensional and two-dimensional nanostructured [170] Xu Y, Xu R. Nickel-based cocatalysts for photocatalytic
materials for hydrogen generation. Phys Chem Chem Phys hydrogen production. Appl Surf Sci 2015;351:779e93.
2015;17:2960e86. [171] Xing Z, Li Z, Wang G, Zhou W. In-situ S-doped porous
[154] Li LD, Yan JQ, Wang T, Zhao ZJ, Zhang J, Gong JL, et al. Sub- anatase TiO2 nanopillars for high-efficient visible-light
10 nm rutile titanium dioxide nanoparticles for efficient photocatalytic hydrogen evolution. Int J Hydrogen Energy
visible-light-driven photocatalytic hydrogen production. 2016;41:1535e41.
Nat Commun 2015;6:5881. [172] Hu JH, Wang LJ, Zhang P, Liang CH, Shao GS. Construction of
[155] Murdoch M, Waterhouse GIN, Nadeem MA, Metson JB, solid-state Z-scheme carbon-modified TiO2/WO3 nanofibers
Keane MA, Howe RF, et al. The effect of gold loading and with enhanced photocatalytic hydrogen production. J Power
particle size on photocatalytic hydrogen production from Sources 2016;328:28e36.
ethanol over Au/TiO2 nanoparticles. Nat Chem [173] Tan Y, Zhang SG, Shi RX, Wang WW, Liang KX. Visible light
2011;3:489e92. active Ce/Ce2O/CeO2/TiO2 nanotube arrays for efficient
[156] Tanigawa S, Irie H. Visible-light-sensitive two-step overall hydrogen production by photoelectrochemical water
water-splitting based on band structure control of titanium splitting. Int J Hydrogen Energy 2016;41:5437e44.
dioxide. Appl Catal B Environ 2016;180:1e5. [174] Liu YX, Wang ZL, Huang WX. Influences of TiO2 phase
[157] Yu JG, Qi LF, Jaroniec M. Hydrogen production by structures on the structures and photocatalytic hydrogen
photocatalytic water splitting over Pt/TiO2 nanosheets production of CuOx/TiO2 photocatalysts. Appl Surf Sci
with exposed (001) facets. J Phys Chem C 2016;389:760e7.
2010;114:13118e25. [175] Javier PC, Pilar A, Sergio O, Gerardo C, Eduardo RH. TiO2-clay
[158] Ager JW, Shaner MR, Walczak KA, Sharp ID, Ardo S. based nanoarchitectures for enhanced photocatalytic
Experimental demonstrations of spontaneous, solar-driven hydrogen production. Micropor Mesopor Mater
photoelectrochemical water splitting. Energy Environ Sci 2016;22:120e7.
2015;8:2811e24. [176] Fujishima A, Honda K. Electrochemical photolysis of water
[159] Zhen C, Chen RZ, Wang LZ, Liu G, Cheng HM. Tantalum at a semiconductor electrode. Nature 1972;238:37e8.
(oxy) nitride based photoanodes for solar-driven water [177] Wang MY, Ioccozia J, Sun L, Lin CJ, Lin ZQ. Inorganic-
oxidation. J Mater Chem A 2016;4:2783e800. modified semiconductor TiO2 nanotube arrays for
[160] Chen JQ, Yang DH, Song D, Jiang JH, Ma AB, Hu MZ, et al. photocatalysis. Energy Environ Sci 2014;7:2182e202.
Recent progress in enhancing solar-to-hydrogen efficiency. [178] Dimitrijevic NM, Vijayan BJK, Poluektov OG, Rajh T,
J Power Sources 2015;280:649e66. Gray KA, He HY, et al. Role of water and carbonates in
[161] Shi XJ, Zhang K, Shin KH, Ma M, Kwon J, Choi IT, et al. photocatalytic transformation of CO2 to CH4 on Titania.
Unassisted photoelectrochemical water splitting beyond J Am Chem Soc 2011;133:3964e71.
5.7% solar-to-hydrogen conversion efficiency by a wireless [179] Wang WN, An WJ, Ramalingam B, Mukherjee S,
monolithic photoanode/dye-sensitised solar cell tandem Niedzwiedzki DM, Gangopadhyay S, et al. Size and structure
device. Nano Energy 2015;13:182e91. matter: enhanced CO2 photoreduction efficiency by size-
[162] Li YG, Wei XL, Zhu BW, Wang H, Tang YX, Sum TC, et al. resolved ultrafine Pt nanoparticles on TiO2 single crystals.
Hierarchically branched Fe2O3@TiO2 nanorod arrays for J Am Chem Soc 2012;134:11276e81.
photoelectrochemical water splitting: facile synthesis and [180] Bach U, Lupo D, Comte P, Moser JE, Weisso € rte F, Salbeck J,
enhanced photoelectrochemical performance. Nanoscale et al. Solid-state dye-sensitized mesoporous TiO2 solar cells
2016;8:11284e90. with high photon-to-electron conversion efficiencies.
[163] Yu X, Han X, Zhao ZH, Zhang J, Guo WB, Pan CF, et al. Nature 1998;395:583e5.
Hierarchical TiO2 nanowire/graphite fiber [181] Oregan B, Gratzel M. A low-cost, high-efficiency soler-cell
photoelectrocatalysis setup powered by a wind-driven based ondye-sensitized colloidal TiO2 films. Nature
nanogenerator: a highly efficient photoelectrocatalytic 1991;353:737e40.
device entirely based on renewable energy. Nano Energy [182] Wang Q, Wen ZH, Li JH. A hybrid supercapacitor fabricated
2015;11:19e27. with a carbon nanotube cathode and a TiO2-B nanowire
[164] Tang L, Den YC, Zeng GM, Hu W, Wang JJ, Zhou YY, et al. anode. Adv Funct Mater 2006;16:2141e6.
CdS/Cu2S co-sensitized TiO2 branched nanorod arrays of [183] Yang Y, Kim DH, Yang M, Schmuki P. Vertically aligned
enhanced photoelectrochemical properties by forming mixed V2O5-TiO2 nanotube arrays for supercapacitor
nanoscale heterostructure. J Alloy Compd 2016;662:516e27. applications. Chem Commun 2011;47:7746e8.
[184] Lai YK, Lin LX, Pan F, Huang JY, Song R, Huang YX, et al. structure for improved photocatalytic activity. J Phys Chem
Bioinspired patterning with extreme wettability contrast on C 2012;116:2772e80.
TiO2 nanotube array surface: a versatile platform for [202] Chen QH, Liu HL, Xin YJ, Cheng XW, Li JJ. Enhanced
biomedical applications. Small 2013;9:2945e53. photoelectrochemical and photocatalytic performance of
[185] Tang YX, Zhang YY, Li WL, Ma B, Chen XD. Rational single-crystalline anatase TiO2 (101) nanobelts arrays
material design for ultrafast rechargeable lithium-ion originating from nanotubes arrays. Appl Surf Sci
batteries. Chem Soc Rev 2015;44:5926e40. 2013;264:476e84.
[186] Tang YX, Zhang YY, Rui XH, Qi DP, Luo YF, Leow WR, et al. [203] Xu F, Xiao W, Cheng B, Yu J. Direct Z-scheme anatase/rutile
Conductive inks based on a lithium titanate nanotube gel bi-phase nanocomposite TiO2 nanofiber photocatalyst with
for high-rate lithium-ion batteries with customized enhanced photocatalytic H2-production activity. Int J
configuration. Adv Mater 2016;28:1567e76. Hydrogen Energy 2014;39:15394e402.
[187] Yu JG, Hai Y, Cheng B. Enhanced photocatalytic H2- [204] Fox MA, Chen CC. Mechanistic features of the
production activity of TiO2 by Ni(OH)2 cluster modification. semiconductor photocatalyzed olefin-to-carbonyl oxidative
J Phys Chem C 2011;115:4953e8. cleavage. J Am Chem Soc 1981;103:6757e9.
[188] Hartmann P, Lee DK, Smarsly BM, Janek J. Mesoporous TiO2: [205] Xiang G, Li T, Zhuang J, Wang X. Large-scale synthesis of
comparison of classical sol-gel and nanoparticle based metastable TiO2 (B) nanosheets with atomic thickness and
photoelectrodes for the water splitting reaction. ACS Nano their photocatalytic properties. Chem Commun
2010;4:3147e54. 2010;46:6801e3.
[189] Lv MQ, Zheng DJ, Ye MD, Sun L, Xiao J, Guo WX, et al. [206] Ohtani B, Handa JI, Nishimoto SI, Kagiya T. Highly active
Densely aligned rutile TiO2 nanorod arrays with high semiconductor photocatalyst: extra-fine crystallite of
surface area for efficient dye-sensitized solar cells. brookite TiO2 for redox reaction in aqueous propan-2-ol
Nanoscale 2012;4:5872e9. and/or silver sulfate solution. Chem Phys Lett
[190] Wang MY, Zheng DJ, Ye MD, Zhang CC, Xu BB, Lin CJ, et al. 1985;120:292e4.
One-dimensional densely aligned perovskite-decorated [207] Kandiel TA, Feldhoff A, Robben L, Dillert R,
semiconductor heterojunctions with enhanced Bahnemann DW. Tailored titanium dioxide nanomaterials:
photocatalytic activity. Small 2015;11:1436e42. anatase nanoparticles and brookite nanorods as highly
[191] Xie KP, Sun L, Wang CL, Lai YK, Wang MY, Chen HB, et al. active photocatalysts. Chem Mater 2010;22:2050e60.
Photoelectrocatalytic properties of Ag nanoparticles loaded [208] Liu G, Wang LZ, Sun CH, Yan XX, Wang XW, Chen ZG, et al.
TiO2 nanotube arrays prepared by pulse current deposition. Band-to-band visible-light photon excitation and
Electrochim Acta 2010;55:7211e8. photoactivity induced by homogeneous nitrogen doping in
[192] D'Elia D, Beauger C, Hochepied JF, Rigacci A, Berger MH, layered titanates. Chem Mater 2009;21:1266e74.
Keller N, et al. Impact of three different TiO2 morphologies [209] Bahadur N, Pasricha R, Govind, Chand S, Kotnala RK. Effect
on hydrogen evolution by methanol assisted water of Ni doping on the microstructure and high Curie
splitting: nanoparticles, nanotubes and aerogels. Int J temperature ferromagnetism in sol-gel derived titania
Hydrogen Energy 2011;36:14360e73. powders. Mater Chem Phys 2012;133:471e9.
[193] Choi SK, Kim S, Lim SK, Park H. Photocatalytic comparison [210] Umebayashi T, Yamaki T, Itoh H, Asai K. Analysis of
of TiO2 nanoparticles and electrospun TiO2 nanofibers: electronic structures of 3d transition metal-doped TiO2
effects of mesoporosity and interparticle charge transfer. based on band calculations. J Phys Chem Solids
J Phys Chem C 2010;114:16475e80. 2002;63:1909e20.
[194] Jiang ZL, Tang YX, Tay QL, Zhang YY, Malyi OI, Wang DP, [211] Asahi R, Morikawa T, Ohwaki T, Aoki K, Taga Y. Visible-light
et al. Understanding the role of nanostructures for efficient photocatalysis in nitrogen doped titanium oxides. Science
hydrogen generation on immobilized photocatalysts. Adv 2001;293:269e71.
Energy Mater 2013;3:1368e80. [212] Lai YK, Huang JY, Zhang HF, Subramaniam VP, Tang YX,
[195] Xu SP, Ng JW, Du AJH, Liu JC, Sun DD. Highly efficient TiO2 Gong DG, et al. Nitrogen-doped TiO2 nanotube array films
nanotube photocatalyst for simultaneous hydrogen with enhanced photocatalytic activity under various light
production and copper removal from water. Int J Hydrogen sources. J Hazard Mater 2010;184:855e63.
Energy 2011;36:6538e45. [213] Long MC, Zheng LH, Tan BH, Shu HP. Photocatalytic self-
[196] Jitputti J, Rattanavoravipa T, Chuangchote S, Pavasupree S, cleaning cotton fabrics with platinum (IV) chloride modified
Suzuki Y, Yoshikawa S. Low temperature hydrothermal TiO2 and N-TiO2 coatings. Appl Surf Sci 2016;386:434e41.
synthesis of monodispersed flower-like titanate [214] Su JY, Zhu L, Geng P, Chen GH. Self-assembly graphitic
nanosheets. Catal Commun 2009;10:378e82. carbon nitride quantum dots anchored on TiO2 nanotube
[197] Liu SH, Han L, Duan YY, Asahina S, Terasaki O, Cao YY, arrays: an efficient heterojunction for pollutants
et al. Synthesis of chiral TiO2 nanofibre with electron degradation under solar light. J Hazard Mater
transition-based optical activity. Nat Commun 2016;316:159e68.
2012;3:1215. [215] Lin YH, Hsueh HT, Chang CW, Chu H. The visible light-
[198] Chueh YL, Hsieh CH, Chang MT, Chou LJ, Lao CS, Song JH, driven photodegradation of dimethyl sulfide on S-doped
et al. RuO2 nanowires and RuO2/TiO2 core/shell nanowires: TiO2: characterization, kinetics, and reaction pathways.
from synthesis to mechanical, optical, electrical, and Appl Catal B Environ 2016;199:1e10.
photoconductive properties. Adv Mater 2007;19:143e9. [216] Ghicov A, Macak JM, Tsuchiya H, Kunze J, Haeublein V,
[199] Setvin M, Aschauer U, Hulva J, Simschitz T, Daniel B, Kleber S, et al. TiO2 nanotube layers: dose effects during
Schmid M, et al. Following the reduction of oxygen on TiO2 nitrogen doping by ion implantation. Chem Phys Lett
anatase (101) step by step. J Am Chem Soc 2006;419:426e9.
2016;138:9565e71. [217] Ghicov A, Macak JM, Tsuchiya H, Kunze J, Haeublein V,
[200] Lee JS, You KH, Park CB. Highly photoactive, low bandgap Frey L, et al. Ion implantation and annealing for an efficient
TiO2 nanoparticles wrapped by graphene. Adv Mater N-doping of TiO2 nanotubes. Nano Lett 2006;6:1080e2.
2012;24:1084e8. [218] Kim MS, Tsuchiya H, Erami T, Fujimoto S. Formation of
[201] Tang YX, Wee PX, Lai YK, Wang XP, Gong DG, Kanhere PD, nano-structured oxide layers formed on Ti-Fe alloys by
et al. Hierarchical TiO2 nanoflakes and nanoparticles hybrid anodization. Mater Trans 2016;57:519e24.
[219] Ning XW, Wang XX, Yu XF, Zhao JL, Wang ML, Li HR, et al. [235] Niu JF, Dai PX, Wu BG, Yao BH, Yu XJ, Zhang Q. Preparation
Outstanding supercapacitive properties of Mn-doped TiO2 and application of Fe(III) doped titania photocatalyst with
micro/nanostructure porous film prepared by anodization hollow structure. Integr Ferroelectr 2015;167:123e36.
method. Sci Rep 2016;6:22634. [236] Yuan RF, Zhou BH, Zhang XM, Guan HH. Photocatalytic
[220] Chen XB, Burda C. The electronic origin of the visible-light degradation of humic acids using substrate-supported Fe3þ
absorption properties of C-, N- and S-doped TiO2 doped TiO2 nanotubes under UV/O3 for water purification.
nanomaterials. J Am Chem Soc 2008;130:5018e9. Environ Sci Pollut Res 2015;22:17955e64.
[221] Varley JB, Janotti A, Walle CGVD. Mechanism of visible-light [237] Yu JD, Wu Z, Gong C, Xiao W, Sun L, Lin CJ. Fe3þ doped TiO2
photocatalysis in nitrogen-doped TiO2. Adv Mater nanotube arrays on Ti-Fe alloys for enhanced
2011;23:2343e7. photoelectrocatalytic activity. Nanomaterials 2016;6:107.
[222] Pei FY, Xu SG, Zuo W, Zhang ZR, Liu YL, Cao SK. [238] Su YF, Wu Z, Wu YN, Yu JD, Sun L, Lin CJ. Acid orange II
Effective improvement of photocatalytic hydrogen degradation through a heterogeneous fenton-like reaction
evolution via a facile in-situ solvothermal N-doping using Fe-TiO2 nanotube arrays as a photocatalyst. J Mater
strategy in N-TiO2/N-graphene nanocomposite. Int J Chem A 2015;3:8537e44.
Hydrogen Energy 2014;39:6845e52. [239] Zhao WR, Li YJ, Zhang M, Chen JS, Xie LH, Shi QM, et al.
[223] Shao Y, Cao CS, Chen SL, He M, Fang JL, Chen J, et al. Direct microwave-hydrothermal synthesis of Fe-doped
Investigation of nitrogen doped and carbon species titania with extended visible-light response and enhanced
decorated TiO2 with enhanced visible light photocatalytic H2-production performance. Chem Eng J 2016;283:105e13.
activity by using chitosan. Appl Catal B Environ [240] Kerkez KO, Kibar E, Dayıog €
lu K, Gedik F, Akın AN, Ozkara A. A
2015;179:344e51. comparative study for removal of different dyes over M/TiO2
[224] Liu TY, Chen W, Liu XH, Zhu JW, Lu LD. Well-dispersed (M¼Cu, Ni, Co, Fe, Mn and Cr) photocatalysts under visible
ultrafine nitrogen-doped TiO2 with polyvinylpyrrolidone light irradiation. J Photochem Photobio A 2015;311:176e85.
(PVP) acted as N-source and stabilizer for water splitting. [241] Hu QQ, Huang JQ, Li GJ, Jiang YB, Lan H, Guo W, et al. Origin
J Energy Chem 2016;25:1e9. of the improved photocatalytic activity of Cu incorporated
[225] Zhang P, Tachikawa T, Fujitsuka M, Majima T. In situ TiO2 for hydrogen generation from water. Appl Surf Sci
fluorine doping of TiO2 superstructures for efficient 2016;382:170e7.
visible-light driven hydrogen generation. Chemsuschem [242] Lu CY, Guan WS, Hoang TKA, Guo JF, Gou HG, Yao YL.
2016;9:617e23. Visible-light-driven catalytic degradation of ciprofloxacin
[226] Zhou XM, Ha € ublein V, Liu N, Nguyen NT, Zolnhofer EM, on metal (Fe, Co, Ni) doped titanate nanotubes synthesized
Tsuchiya H, et al. TiO2 nanotubes: nitrogen-ion by one-pot approach. J Mater Sci Mater Electron
implantation at low dose provides noble-metal-free 2016;27:1966e73.
photocatalytic H2-evolution activity. Angew Chem Int Ed [243] Neubert S, Mitoraj D, Shevlin SA, Pulisova P, Du MHY,
2016;55:3763e7. Goh GKL, et al. Highly efficient rutile TiO2 photocatalysts
[227] Behara DK, Ummireddi AK, Aragonda V, Gupta PK, Pala RGS, with single Cu(II) and Fe(III) surface catalytic sites. J Mater
Sivakumar S. Coupled optical absorption, charge Chem A 2016;4:3127e38.
carrier separation, and surface electrochemistry in [244] Wen YP, Wu WP, Li YY, Li Y, Qin TF, Tang Y, et al. Thieno
surface disordered/hydrogenated TiO2 for enhanced PEC [2,3-b] indole-based organic dyes for dye-sensitized solar
water splitting reaction. Phys Chem Chem Phys cells: effect of p-linker on the performance of isolated dye
2016;18:8364e77. and interface between dyes and TiO2. Org Electron
[228] Luo J, Li DL, Yang Y, Liu HQ, Chen JY, Wang HY. Preparation 2016;38:61e8.
of Au/reduced graphene oxide/hydrogenated TiO2 nanotube [245] Lu NM, Yeh YP, Wang GB, Feng TY, Shih YH, Chen D.
arrays ternary composites for visible-light-driven Dye-sensitized TiO2 catalyzed photodegradation of
photoelectrochemical water splitting. J Alloy Compd sulfamethoxazole under blue or yellow light. Environ Sci
2016;661:380e8. Pollut Res 2017;24:489e99. http://dx.doi.org/10.1007/s11356-
[229] Samsudin EM, Hamid SBA, Juan JC, Basirun WJ, Centi G. 016-7815-6.
Synergetic effects in novel hydrogenated F-doped TiO2 [246] Singh MJ, Kurchania R, Ball RJ, Sharma GD. Efficiency
photocatalysts. Appl Surf Sci 2016;370:380e93. enhancement in dye sensitized solar cells through step
[230] Zhu SS, Zhang PP, Chang L, Zhong Y, Wang K, Shao HB, wise cosensitization of TiO2 electrode with N719 and metal
et al. Photochemical fabrication of 3D hierarchical free dye. Indian J Pure Appl Phy 2016;54:656e64.
Mn3O4/H-TiO2 composite films with excellent [247] Wang MY, Pang XC, Zheng DJ, He YJ, Sun L, Lin CJ, et al.
electrochemical capacitance performance. Phys Chem Nonepitaxial growth of uniform and precisely size-tunable
Chem Phys 2016;18:8529e36. core/shell nanoparticles and their enhanced plasmon-
[231] Yang SB, Jiang DM, Zeng QZ. Room temperature driven photocatalysis. J Mater Chem A 2016;4:7190e9.
ferromagnetism of Fe-doped and (Fe, Cu)-codoped TiO2 [248] Wang XN, Long R, Liu D, Yang D, Wang CM, Xiong XY.
powders prepared by mechanical alloying. J Mater Sci Mater Enhanced full-spectrum water splitting by confining
Electron 2016;27:6570e7. plasmonic Au nanoparticles in N-doped TiO2 bowl
[232] Jung M, Hart JN, Scott J, Ng YH, Jiang YJ, Amal R. Exploring nanoarrays. Nano Energy 2016;24:87e93.
Cu oxidation state on TiO2 and its transformation during [249] Wang M, Ye MD, Iocozzia J, Lin CJ, Lin ZQ. Plasmon-
photocatalytic hydrogen evolution. Appl Catal A Gen mediated solar energy conversion via photocatalysis in
2016;521:190e201. noble metal/semiconductor composites. Adv Sci 2016;3.
[233] Li Y, Zhang TT, Wang J, Zhu Z, Jia B, Yu J. Catalytic 1600024.
combustion of n-hexanal using Cu-Mn composite oxide [250] Ge MZ, Cao CY, Huang JY, Li SH, Zhang SN, Deng S, et al.
supported on TiO2. Acta Phys Chim Sin 2016;32:2084e92. Synthesis, modification, and photo/photoelectrocatalytic
[234] Tobaldi DM, Piccirillo C, Rozman N, Pullar RC, Seabra MP, degradation applications of TiO2 nanotube arrays: a review.
Skapin AS, et al. Effects of Cu, Zn and Cu-Zn addition on the Nanotechnol Rev 2016;5:75e112.
microstructure and antibacterial and photocatalytic [251] Lv SC, Wang JW, Zhang CY, Xu S, Shi M, Zhang J. Silver-
functional properties of Cu-Zn modified TiO2 nano- catalyzed amidiniumation of alkynes: isolation of a silver
heterostructures. J Photochem Photobio A 2016;330:44e54. intermediate, synthesis of enamine amido carbene
precursors, and an unprecedented umpolung of visible-light active photocatalyst for destruction of

propiolamide. Angew Chem Int Ed 2015;54:14941e6. ibuprofen and bacteria. J Mater Chem 2012;22:23149e58.
[252] Tedsree K, Li T, Jones S, Chan CWA, Yu KMK, Bagot PAJ, [268] Kurapati R, Kostarelos K, Prato M, Bianco A. Biomedical uses
et al. Hydrogen production from formic acid decomposition for 2D materials beyond graphene: current advances and
at room temperature using a Ag-Pd core-shell nanocatalyst. challenges ahead. Adv Mater 2016;28:6052e74.
Nat Nanotechnol 2011;6:302e7. [269] Zhao L, Lin ZQ. Crafting semiconductor organic-inorganic
[253] Zhao WJ, Wang SF, Liu B, Verzhbitskiy I, Li SS, Giustiniano F, nanocomposites via placing conjugated polymers in
et al. Exciton-plasmon coupling and electromagnetically intimate contact with nanocrystals for hybrid solar cells.
induced transparency in monolayer semiconductors Adv Mater 2012;24:4353e68.
hybridized with Ag nanoparticles. Adv Mater [270] Zhao L, Pang XC, Adhikary R, Petrich JW, Jeffries ELM,
2016;28:2709e15. Lin ZQ. Organic-inorganic nanocomposites by placing
[254] Ge MZ, Cao CY, Li SH, Tang YX, Wang LN, Qi N, et al. In situ conjugated polymers in intimate contact with quantum
plasmonic Ag nanoparticle anchored TiO2 nanotube arrays rods. Adv Mater 2011;23:2844e9.
as visible-light-driven photocatalysts for enhanced water [271] Zhu LL, Ang CY, Li X, Nguyen KT, Tan SY, Agren H, et al.
splitting. Nanoscale 2016;8:5226e34. Luminescent color conversion on cyanostilbene-
[255] Tian Y, Tatsuma T. Plasmon-induced functionalized quantum dots via in-situ photo-tuning. Adv
photoelectrochemistry at metal nanoparticles supported on Mater 2012;24:4020e4.
nanoporous TiO2. Chem Commun 2004;36:1810e1. [272] Lai YK, Lin ZQ, Huang JY, Sun L, Chen Z, Lin CJ. Controllable
[256] Tian Y, Tatsuma T. Mechanisms and applications construction of ZnO/TiO2 patterning nanostructures by
of plasmon-induced charge separation at TiO2 films superhydrophilic/superhydrophobic templates. New J
loaded with gold nanoparticles. J Am Chem Soc Chem 2010;34:44e51.
2005;127:7632e7. [273] Novoselov KS, Geim AK, Morozov SV, Jiang D, Zhang Y,
[257] Fei JB, Li JB. Controlled preparation of porous TiO2-Ag Dubonos SV, et al. Electric field effect in atomically thin
nanostructures through supramolecular assembly for carbon films. Science 2004;306:666e9.
plasmon-enhanced photocatalysis. Adv Mater [274] Kim YD, Kim H, Cho YJ, Ryoo JH, Park CH, Kim P, et al. Bright
2015;27:314e9. visible light emission from graphene. Nat Nanotechnol
[258] Zhu Z, Kao CT, Tang BH, Chang WC, Wu RJ. Efficient 2015;10:676e81.
hydrogen production by photocatalytic water-splitting [275] Lee H, Choi TK, Lee YB, Cho HR, Ghaffari R, Wang L, et al. A
using Pt-doped TiO2 hollow spheres under visible light. graphene-based electrochemical device with
Ceram Int 2016;42:6749e54. thermoresponsive microneedles for diabetes monitoring
[259] Nguyen NT, Altomare M, Yoo JE, Schmuki P. Efficient and therapy. Nat Nanotechnol 2016;11:566e72.
photocatalytic H2 evolution: controlled dewetting- [276] Chen YN, Egan GC, Wan JY, Zhu SZ, Jacob RJ, Zhou WB, et al.
dealloying to fabricate site-selective high-activity Ultra-fast self-assembly and stabilization of reactive
nanoporous Au particles on Highly ordered TiO2 nanotube nanoparticles in reduced graphene oxide films. Nat
arrays. Adv Mater 2015;27:3208e15. Commun 2016;7:12332.
[260] Liu PX, Zhao Y, Qin RX, Mo SG, Chen GX, Gu L, et al. [277] Wu GT, Wei XL, Gao S, Chen Q, Peng LM. Tunable
Photochemical route for synthesizing atomically dispersed graphene micro-emitters with fast temporal response
palladium catalysts. Science 2016;352:797e801. and controllable electron emission. Nat Commun
[261] Wang P, Peng CH, Yang M. Ag decorated 3D urchin-like TiO2 2016;7:11513.
microstructures synthesized via a one-step solvothermal [278] Liu XQ, Yang JB, Zhao W, Wang Y, Li Z, Lin ZQ. A simple
method and their photocatalytic activity. J Alloy Compd route to reduced graphene oxide-draped nanocomposites
2015;648:22e8. with markedly enhanced visible-light photocatalytic
[262] Yang SY, Wang HJ, Yu H, Zhang SG, Fang YP, Zhang SQ, performance. Small 2016;12:4077e85.
et al. A facile fabrication of hierarchical Ag nanoparticles- [279] Hao XQ, Jin ZL, Xu J, Min SX, Lu GX. Functionalization of
decorated N-TiO2 with enhanced photocatalytic hydrogen TiO2 with graphene quantum dots for efficient
production under solar light. Int J Hydrogen Energy photocatalytic hydrogen evolution. Superlattice Microst
2016;41:3446e55. 2016;94:237e44.
[263] Zhang YJ, Zhao GH, Shi HJ, Zhang YN, Huang WN, [280] Zhang Q, Zheng DD, Xu LS, Chang CT. Photocatalytic
Huang XF, et al. Photoelectrocatalytic glucose oxidation to conversion of terephthalic acid preparation wastewater to
promote hydrogen production over periodically ordered hydrogen by graphene-modified TiO2. Catal Today
TiO2 nanotube arrays assembled of Pd quantum dots. 2016;274:8e14.
Electrochim Acta 2015;174:93e101. [281] Li LH, Yu LL, Lin ZY, Yang GW. Reduced TiO2-graphene
[264] Ma XL, Tang YX, Tao HJ, Lai YK, Zhang YY, Zhou XR, et al. oxide heterostructure as broad spectrum-driven efficient
Uniform spatial distribution of a nanostructured Ag/AgCl water-splitting photocatalysts. ACS Appl Mater Interfaces
plasmonic photocatalyst and its segregative membrane 2016;8:8536e45.
towards visible light-driven photodegradation. [282] Dang HF, Dong XF, Dong YC, Huang JS. Facile and green
CrystEngComm 2016;18:3725e33. synthesis of titanate nanotube/graphene nanocomposites
[265] Tang YX, Subramaniam VP, Lau TH, Lai YK, Gong DG, for photocatalytic H2 generation from water. Int J Hydrogen
Kanhere PD, et al. In situ formation of large-scale Ag/AgCl Energy 2013;38:9178e85.
nanoparticles on layered titanate honeycomb by gas phase [283] Xu Z, Yin M, Sun J, Ding GQ, Lu LF, Chang PC, et al. 3D
reaction for visible light degradation of phenol solution. periodic multiscale TiO2 architecture: a platform decorated
Appl Catal B Environ 2011;106:577e85. with graphene quantum dots for enhanced
[266] Wang PH, Tang YX, Dong ZL, Chen Z, Lim TT. Ag- photoelectrochemical water splitting. Nanotechnology
AgBr/TiO2/RGO nanocomposite for visible-light 2016;27:115401.
photocatalytic degradation of penicillin G. J Mater Chem A [284] Rather RA, Singh S, Pal B. Core-shell morphology of Au-
2013;1:4718e27. TiO2@graphene oxide nanocomposite exhibiting enhanced
[267] Wang XP, Tang YX, Chen Z, Lim TT. Highly stable hydrogen production from water. J Ind Eng Chem
heterostructured Ag-AgBr/TiO2 composite: a bifunctional 2016;37:288e94.
[285] Yang YH, Liu EZ, Dai HZ, Kang LM, Wu HT, Fan J, et al. [300] Pan YX, Zhou TH, Han JY, Hong JD, Wang YB, Zhang W,
Photocatalytic activity of Ag-TiO2-graphene ternary et al. CdS quantum dots and tungsten carbide supported on
nanocomposites and application in hydrogen evolution by anatase-rutile composite TiO2 for highly efficient visible-
water splitting. Int J Hydrogen Energy 2014;39:7664e71. light-driven photocatalytic H2 evolution from water. Catal
[286] Chen HL, Wen XW, Zhang J, Wu TM, Gong YJ, Zhang X, et al. Sci Technol 2016;6:2206e13.
Ultrafast formation of interlayer hot excitons in atomically [301] Quang ND, Kim D, Hien TT, Kim D, Hong SK, Kim CJ. Three-
thin MoS2/WS2 heterostructures. Nat Commun dimensional hierarchical structures of TiO2/CdS branched
2016;7:12512. core-shell nanorods as a high-performance
[287] Chi MH, Zhang CD, Shi HW, Chu CP, Chen CH, Chang CYS, photoelectrochemical cell electrode for hydrogen
et al. Determination of band alignment in the single-layer production. J Electrochem Soc 2016;163:434e9.
MoS2/WSe2 heterojunction. Nat Commun 2015;6:7666. [302] Wang WC, Li F, Zhang DQ, Leung DYC, Li GS.
[288] Zhao J, Minegishi T, Zhang L, Zhong M, Gunawan, Photoelectrocatalytic hydrogen generation and
Nakabayashi M, et al. Enhancement of solar hydrogen simultaneous degradation of organic pollutant via
evolution from water by surface modification with CdS and CdSe/TiO2 nanotube arrays. Appl Surf Sci 2016;362:490e7.
TiO2 on porous CuInS2 photocathodes prepared by an [303] Wu HJ, Zhang ZH. Photoelectrochemical water splitting and
electrodeposition-sulfurization method. Angew Chem Int simultaneous photoelectrocatalytic degradation of organic
Ed 2014;53:11808e12. pollutant on highly smooth and ordered TiO2 nanotube
[289] Pawar SA, Patil DS, Jung HR, Park JY, Mali SS, Hong CK, et al. arrays. J Solid State Chem 2011;184:3202e7.
Quantum dot sensitized solar cell based on TiO2/CdS/CdSe/ [304] Zhang XM, Huo KF, Hu LS, Wu ZW, Chu PK. Synthesis
ZnS heterostructure. Electrochim Acta 2016;203:74e83. and photocatalytic activity of highly ordered TiO2 and
[290] Ma K, Yehezkeli O, Domaille DW, Funke HH, Cha JN. SrTiO3/TiO2 nanotube arrays on Ti substrates. J Am Ceram
Enhanced hydrogen production from DNA-assembled Soc 2010;93:2771e8.
Z-scheme TiO2-CdS photocatalyst systems. Angew Chem [305] Ye MD, Wang MY, Zheng DJ, Zhang N, Lin CJ, Lin ZQ.
Int Ed 2015;54:11490e4. Garden-like perovskite superstructures with enhanced
[291] Zhao WW, Liu Z, Shan S, Zhang WW, Wang J, Ma ZY, et al. photocatalytic activity. Nanoscale 2014;6:3576e84.
Bismuthoxyiodide nanoflakes/titania nanotubes arrayed [306] Ji L, McDaniel MD, Wang SJ, Posadas AB, Li XH, Huang HY,
p-n heterojunction and its application for et al. A silicon-based photocathode for water reduction with
photoelectrochemical bioanalysis. Sci Rep 2014;4:4426. an epitaxial SrTiO3 protection layer and a nanostructured
[292] Li X, Yu JG, Low JX, Fang YP, Xiao J, Chen XB. Engineering catalyst. Nat Nanotechnol 2015;10:84e90.
heterogeneous semiconductors for solar water splitting. [307] Luo JH, Maggard PA. Hydrothermal synthesis and
J Mater Chem A 2015;3:2485e534. photocatalytic activities of SrTiO3-coated Fe2O3 and BiFeO3.
[293] Ge MZ, Cao CY, Li SH, Zhang SN, Deng S, Huang JY, et al. Adv Mater 2006;18:514e7.
Enhanced photocatalytic performances of n-TiO2 [308] Wu Z, Su YF, Yu JD, Xiao W, Sun L, Lin CJ. Enhanced
nanotubes by uniform creation of p-n heterojunctions with photoelectrocatalytic hydrogen production activity of
p-Bi2O3 quantum dots. Nanoscale 2015;7:11552e60. SrTiO3-TiO2 hetero-nanoparticle modified TiO2 nanotube
[294] Zhao D, Wu Q, Wang S, Zhao CX, Yang CF. Visible light arrays. Int J Hydrogen Energy 2015;40:9704e12.
driven photocatalytic hydrogen evolution over CdS [309] Tamiolakis I, Papadas IT, Spyridopoulos KC, Armatas GS.
incorporated mesoporous anatase TiO2 beads. Res Chem Mesoporous assembled structures of Cu2O and TiO2
Intermed 2016;42:5479e93. nanoparticles for highly efficient photocatalytic hydrogen
[295] Li CL, Yuan J, Han BY, Jiang L, Shangguan WF. TiO2 generation from water. RSC Adv 2016;6:54848e55.
nanotubes incorporated with CdS for photocatalytic [310] Chang KL, Sun QN, Peng YP, Lai SW, Sung MH, Huang CY,
hydrogen production from splitting water under visible et al. Cu2O loaded titanate nanotube arrays for
light irradiation. Int J Hydrogen Energy 2010;35:7073e9. simultaneously photoelectrochemical ibuprofen oxidation
[296] Gonzalez MJR, Garcia BY, Rocco MLM, Pereira MB, and hydrogen generation. Chemosphere 2016;150:605e14.
Princival JL, Almeida LC, et al. Effects of the large [311] Liu YX, Zhang BS, Luo LF, Chen XY, Wang ZL, Wu EL, et al.
distribution of CdS quantum dot sizes on the charge TiO2/Cu2O core/ultrathin shell nanorods as efficient and
transfer interactions into TiO2 nanotubes for photocatalytic stable photocatalysts for water reduction. Angew Chem Int
hydrogen generation. Nanotechnology 2016;27. 285401. Ed 2015;54:15260e5.
[297] Wu GS, Tian M, Chen AC. Synthesis of CdS quantum-dot [312] Zhang XF, Yang H, Zhang BY, Shen Y, Wang MK. BiOI-TiO2
sensitized TiO2 nanowires with high photocatalytic activity nanocomposites for photoelectrochemical water splitting.
for water splitting. J Photochem Photobiol A 2012;233:65e71. Adv Mater Interfaces 2016;3:1500273e82.
[298] Su FL, Lu JW, Tian Y, Ma XB, Gong JL. Branched TiO2 [313] Yu X, Zhang J, Zhao ZH, Guo WB, Qiu JC, Mou XN, et al.
nanoarrays sensitized with CdS quantum dots for highly NiO-TiO2 p-n heterostructured nanocables bridged by
efficient photoelectrochemical water splitting. Phys Chem zero-bandgap rGO for highly efficient photocatalytic water
Chem Phys 2013;15:12026e32. splitting. Nano Energy 2015;16:207e17.
[299] Cui XF, Jiang GY, Zhu M, Zhao Z, Du LC, Weng YX, et al. [314] Fan WQ, Yu XQ, Lu HC, Bai HY, Zhang C, Shi WD.
TiO2/CdS composite hollow spheres with controlled Fabrication of TiO2/RGO/Cu2O heterostructure for
synthesis of platinum on the internal wall for the efficient photoelectrochemical hydrogen production. Appl Catal B
hydrogen evolution. Int J Hydrogen Energy 2013;38:9065e73. Environ 2016;181:7e15.

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i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e3 2

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

A review of TiO2 nanostructured catalysts for

Mingzheng Ge a,1, Jingsheng Cai a,1, James Iocozzia b, Chunyan Cao a,

article info abstract

intrinsic drawbacks that have limited the wide application of

[71,72]. Hydrothermal process typically yield large amounts of

Smooth and hexagonal tube length: 2e10 mm, diameter:

diameter: 100 nm, and wall thickness: 12 nm (Fig. 3d)

Smooth and ultra-long tube length: 5e1000 mm,

100 nm, and wall thickness: 15e20 nm (Fig. 3f)

A typical ceramic processing technique, high temperature

and wall thickness: 10 nm (Fig. 3e)

0.5 wt% NH4F þ 2 vol% H2O in ethylene glycol

Ti vapor and substrates ensure the growth of TiO2 nanowires

Similarly to nanotubes and nanowires, TiO2 nanorods can also

micrometers have been synthesized by Tanemura et al.

AAMs into boiled TiO2 sol followed by a drying process and

metallic Ti with H2O2 at low temperature (80 C) (Fig. 6b). The

size of TiO2 nanorods can be controlled with the aid of various

surfactants such as metal nanoparticles, semiconductors and

organics [84,85]. For example, Cozzoli et al. synthesized high

aspect ratio anatase TiO2 nanorods via hydrolysis of titanium

surfactant at low temperatures (80e100 C) [86]. The fast hy-

polycondensation to ensure a crystalline product. The hy-

Solar water splitting by nanostructured TiO2 Reduction: 2 Hþ þ 2e / H2 DE ¼ 0 V (5)

core/shell arrays on carbon textiles for lithium-ion battery

precursors, and an unprecedented umpolung of visible-light active photocatalyst for destruction of

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