Fang, Xing, Zhang - 2017 - Modifications On Reduced Titanium Dioxide Photocatalysts A Review

Journal of Photochemistry and Photobiology C: Photochemistry Reviews 32 (2017) 21–39
Contents lists available at ScienceDirect
Journal of Photochemistry and Photobiology C:

Photochemistry Reviews
journal homepage: www.elsevier.com/locate/jphotochemrev
Invited Review
Modifications on reduced titanium dioxide photocatalysts: A review

Wenzhang Fang, Mingyang Xing ∗ , Jinlong Zhang ∗
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry and Chemical Engineering, East China University of Science and
Technology, 130 Meilong Road, Shanghai 200237, PR China
a r t i c l e i n f o a b s t r a c t
Article history: A large variety of reduced titanium dioxide (TiO2-x ) materials have been reported recently. Reduced TiO2 ,
Received 27 March 2017 usually resulting from the removal of oxygen atoms or hydrogen incorporation, is proved to be efficient for
Received in revised form 5 May 2017 achieving highly photocatalytic performance including photodegradation of organic compounds, hydro-
Accepted 12 May 2017
gen generation from water splitting, CO2 reduction for CH4 evolution, solar cells, etc. To further improve
Available online 19 May 2017
the properties and activities of TiO2-x , a combination of the Ti3+ self-doping and other traditional modifi-
cations like nonmetals doping has been proposed in the past decades. This paper provides a general and
Keywords:
critical review on the further modifications on reduced TiO2 samples, including non-metal elements (N,
Reduced TiO2
TiO2-x
B, S, F and I) doping, noble-metal (Au, Pt, Pd and Ag) and iron-group metal (Fe, Co and Ni) grafting, metal
Modifications oxide compositing, carbon (nanotubes and graphene) and carbon-based-material compositing, special
Doping facets exposure (mainly dual {001}-{101} and {111}-{110} facets) of TiO2-x and ordered structure con-
Photocatalysis trolling of TiO2-x . These modifications enhance the physical and/or chemical properties of the reduced
TiO2 , or create new features for the modified TiO2-x samples, which finally leads to the enhancement
of photocatalytic performance. Key examples such as N-doping, Au grafting and graphene-based com-
positing are discussed carefully, and the mechanisms for solar light enhancement, electron transfer and
charge separation are also investigated. Finally, some challenging issues on TiO2-x catalysts are also pro-
posed to encourage new approaches for preparation of TiO2-x catalysts with efficiently photocatalytic
performance.
© 2017 Elsevier B.V. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2. TiO2-x photocatalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .22
2.1. Preparation of TiO2-x photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2. Properties and characterizations of TiO2-x photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
2.3. Applications of TiO2-x photocatalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3. TiO2-x photocatalysts doped with non-metal elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.1. Doping with nitrogen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
3.2. Doping with boron, sulfur, fluorine or iodine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4. Metal-based TiO2-x materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.1. Noble-metal-based TiO2-x materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
4.2. Non-noble-metal-based TiO2-x materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
4.3. Metal-compounds-based TiO2-x materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5. Carbon-based TiO2-x materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.1. Graphene-based composite materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
5.2. Other carbon-based composite materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
5.3. Carbon-compound-based composite materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
∗ Corresponding authors.
E-mail addresses: [email protected] (M. Xing), [email protected]
(J. Zhang).
https://doi.org/10.1016/j.jphotochemrev.2017.05.003
1389-5567/© 2017 Elsevier B.V. All rights reserved.
22 W. Fang et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 32 (2017) 21–39
6. TiO2-x with special morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

6.1. TiO2-x with special facets exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
6.2. TiO2-x nanotube arrays . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
6.3. TiO2-x with ordered structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
7. Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
Recently, reduced TiO2 (TiO2-x ) materials have received much

Wenzhang Fang is a PhD student in East China Univer-
sity of Science and Technology (ECUST, Shanghai, China). attentions, owing to the high photocatalytic and photoelectro-
He received his bachelor degree in applied chemistry from chemical (PEC) performance [4–10]. The material was reported to
ECUST and then joined Prof. Jinlong Zhang’s group in 2011, show unique properties such as extended absorption edge of solar
focusing on the research of nanomaterials. In 2014, he
worked as joint-PhD student in Institut de recherches light and colorful appearance (ranging from yellow [11–13], red
sur la catalyse et l’environnement de Lyon (IRCELYON, [14], blue [15–17], grey [18–21] to black [22–25] color), along with
Lyon, France) for two years under the supervision of Prof. structural changes on the surface and/or in the bulk: generation
Stephane Daniele and Dr. Shashank Mishra, funded by
China Scholarship Council (CSC). His current interests
of Ti3+ species and oxygen vacancies, formation of disordered lay-
include the design, characterization and applications of ers on the surface, improvement of Ti-H species or Ti-OH bonds,
nanomaterials such as TiO2 photocatalysts, graphene, up- narrowed bandgap of the catalyst, modified electron density, etc.
conversion materials, etc.
Until now, plenty of efforts have been devoted to study the prop-
erties and applications of TiO2-x materials. Compared to the pristine
Dr. Mingyang Xing is the Associate Professor, supervisor
TiO2 catalyst, TiO2-x nanomaterials have shown improved photo-
of postgraduate in the School of Chemistry and Molecular
Engineering, East China University of Science and Tech- catalytic activities under solar light irradiation. However, further
nology (ECUST). He obtained his Doctoral Degree in 2012 modification of TiO2-x photocatalyst and enhancement of its photo-
from ECUST, and then worked in University of California, catalytic performance are required, to match the rising demand for
Riverside as a visiting scholar for one year. His research
focuses on the preparation of functional nanomaterials energy and environmental protection. Therefore, new approaches
and applications to the environmental and energy filed. are developed for the further enhancement of the photocatalytic
He has published more than 50 papers in SCI journals in performance of TiO2-x photocatalyst.
these areas, which have been cited more than 2400 times.
In this review, we try to discuss the further modifications on
reduced TiO2 photocatalysts, and the mechanism of the obtained
modified TiO2-x , including non-metal or metal doping, noble metal
deposition, metal oxide composition, carbon-based composite,
special facets exposure, morphology controlling, etc. These modifi-
Prof. Dr Jinlong Zhang obtained his Bachelor Degree in cations improve the physical and/or chemical properties of TiO2-x ,
1985 and his Ph.D. in 1993 from East China University of or create some new features for the photocatalysis. It is hoped that
Science and Technology, Shanghai, China. Professor Zhang
joined the East China University of Science and Technol- this review would be helpful for understanding the current devel-
ogy in 1993. He worked in Osaka Prefecture University as a opment of reduced TiO2 photocatalysts, and also encourage further
Postdoctor (JSPS) collaborated with Prof. Anpo from 1996 modifications to improve the photocatalytic activities.
to 2000. He became a full professor in 2000. He has pub-
lished over 350 original papers, which were cited more
than 12000 times (H-index: 56). He is currently on the
Editorial Boards of “Applied Catalysis B: Environmental”
2. TiO2-x photocatalysts
and “Scientific Reports”. He is also the associate editor of
“Res. Chem. Intermed”. His research interests include pho- 2.1. Preparation of TiO2-x photocatalysts
tocatalysis, mesoporous materials, and materials science.
He has been selected as the “Most Cited Chinese Researchers” in China by “Elsevier”
in 2014, 2015 and 2016. In general, reduced TiO2 can be prepared either by the
reduction of Ti(IV) precursors or the oxidation of low-oxidation-
state titanium compounds. Until now, a variety of methods
have been reported for the synthesis of reduced TiO2 , including
1. Introduction calcination under H2 atmosphere [4,11,26], vacuum activa-
tion [13,27,28], metal reduction [10,20,29,30], electrochemical
Titanium dioxide (TiO2 ) is one of the most investigated semi- reduction [9,31–33], UV irradiation [34–36], plasma treatment
conductors since the discovery of its water splitting property in [25,37–40], partial oxidation starting from Ti [6,17,41], Ti(II)
1970s [1]. Owning to the abundance, non-toxicity and chemical sta- [42–44] and Ti(III) [45,46] precursors, etc. The design for the prepa-
bility, TiO2 shows great applications in catalysis, cosmetic, paints, ration of reduced TiO2 makes a significant effect on the intrinsic
antibacterial agents, lithium ion batteries (LIBs), dye-sensitized properties of the final catalysts.
solar cells (DSSCs), etc [2]. However, the white color and wide Since Chen et al. reported black hydrogen doped TiO2 (H-TiO2 )
bandgap (3.2 eV for anatase phase) of pristine TiO2 deeply limit layer in 2011 [4], thermal treatment under H2 seems to be an ideal
its applications to the UV part of solar light spectrum [3]. Only a way to introduce “disordered” layer outside the crystalized TiO2
small part of the solar energy (∼5%) can be well utilized by pristine (Fig. 1a). After hydrogen incorporation, the pristine TiO2 became
TiO2 and most of the solar energy is wasted. Even the photons are black-colored (Fig. 1b), and it exhibited enhanced photocatalytic
absorbed by the TiO2 catalyst, the photogenerated electrons and hydrogen generation rate from water splitting. Leshuk et al. and
holes will quench quickly because of the charge recombination. Wang et al. investigated the effect of temperature on the hydro-
Therefore, it is necessary to extend the absorption edge of solar genation of TiO2 materials [11,26]. With increasing temperature of
spectrum to the visible region and reduce the recombination of the hydrogenation treatment, the color of the obtained TiO2 cata-
electron-hole pairs to enhance the photocatalytic activity of TiO2 . lyst became deeper. Although TiO2-x is likely to be hydrogenated
W. Fang et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 32 (2017) 21–39 23
Fig. 1. (a) Schematic illustration of the density of states (DOS) of the hydrogenated TiO2 samples. (b) The photos of pristine white TiO2 and black hydrogenated TiO2 catalysts.
Reprinted with permission from ref. [4], Copyright 2011 Science Publishing Group.
at high temperature and high H2 pressure, Lu et al. developed a

safe and facile method for the hydrogenation of commercial P25 at
room temperature [47]. H2 -gas hydrogenation treatment of TiO2
catalysts were also reported by other literatures [48–50].
Annealing TiO2 under other reducing atmospheres at high tem-
perature are also typically used. Zuo et al. reported that the pristine
TiO2 was reduced by CO and NO through thermal treatment pro-
cess which was generate in-situ from the oxidative decomposition
of the adding 2-ethylimidazole [51,52]. Cheng et al. and Mao et al.
used hydrazine hydrate to promote Ti3+ formation into the TiO2
samples [53,54]. In addition, heating TiO2 in the presence of urea
can also provide strong reducing ability for the formation of Ti3+
and oxygen vacancies [55,56].
In order to avoid the high temperature requirement and exces-
sive energy consumption in the H2 -gas hydrogenation process, Fig. 2. Photos of TiCl4 dissolved in ethanol before and after the adding of Zn powder.
mild approaches are required for the hydrogenation of TiO2 sam- Reprinted with permission from ref. [29], Copyright 2013 Royal Society of Chemistry.
ples. Xing et al. used NaBH4 as the reductant for the synthesis of
TiO2-x photocatalysts [57]. The hydrogen generation was realized
by the hydrolysis of NaBH4 . Since then, a lot of approaches were Furthermore, Zhang et al. reported that TiO2 could be electro-
developed for the synthesis of TiO2-x using NaBH4 as the reduc- chemically reduced under negative potential and Ti3+ was then
tant [7,12,23,58,59]. This facile method was also reported in the generated from the reduction of Ti4+ by electrons [31]. However,
synthesis of special materials such as 3D mesoporous black TiO2 Mo et al. hold the view that atomic H was generated at the refer-
(MBT)/MoS2 /MBT sandwich-like nanosheets [60], Ni2+ and Ti3+ co- ence Ag electrode and diffused into TiO2 during the electrochemical
doped porous black TiO2 [61] and shell structured TiO2 @TiO2-x reduction process [9]. Compared with gas-hydrogen incorporation,
nanomaterials [62]. atom-hydrogen incorporation induced by electrochemical process
The properties of reduced TiO2 under vacuum treatment was mainly promotes the formation of O H bonds with the closest
early investigated decades ago [63–66], but the photocatalytic oxygen ions and the generation of interstitial H atoms, based on
activities of vacuum-treated TiO2-x was recently reported by Xing the result of density functional theory (DFT) calculations [9]. Simi-
et al. [27,28]. The presence of oxygen vacancies was early evi- larly, Chen et al. reported the generation of O H bonds and highly
denced by atomic-resolution scanning tunneling microscope (STM) mobile H species in the lattice of electrochemical treated Nb2 O5 ,
[64,65], and they were proved to introduce enhance solar light WO3 polycrystals and TiO2 crystals [32]. Besides, electrochemical
absorption of the catalyst and promote improved photocatalytic cathodization [33,74,75] and anodization [76,77] procedures were
activities under visible light irradiation [13,67]. reported for introducing Ti3+ species into TiO2 samples. Zhang et al.
Besides, metals such as zinc, aluminum, iron and magnesium reported that Ti3+ ions and oxygen vacancies were produced at the
were also used as the reductants for the synthesis of TiO2-x . Metal- oxide/metal interface during the anodization process due to the
lic zinc was reported to be an efficient reducing agent to generate insufficient supply of oxygen (Fig. 3) [76].
Ti3+ species in TiO2 samples (Fig. 2) [29]. The obtained TiO2-x was Under UV-light irradiation, defects are proposed to generate
stabilized by the formation of ZnO on the surface of TiO2 , according in TiO2 photocatalyst as the result of oxygen removal by the UV
to some literatures [29,68,69]. However, Zhao et al. demonstrated effect [34], evidenced by STM [35] and friction force microscopy
that the obtained blue TiO2-x catalyst was stable enough through (FFM) [78]. It was reported that the oxygen defects induced by
HCl aqueous solution washing for 12 h [70]. The role of Zn was UV-irradiation were located at the surface few monolayers of TiO2
reported to reduce Ti4+ to generate Ti3+ and also avoid the oxidation [36,79], and they were not stable and easy to be oxidized by oxygen
of the obtained Ti3+ [70]. Yang et al. developed a two-zone molten in air and water [80]. However, Wu et al. obtained stable yel-
aluminum reduction method for preparing disordered black TiO2 low TiO2 nanoparticles via UV-irradiation treatment which could
photocatalyst with Ti3+ and oxygen vacancies [10], and this method be exposed in air for several months [81]. The combination of
was employed to modify commercial P25 [30] and TiO2 nanotubes UV-irradiation and post-thermal-treatment contributed to the sta-
[71]. In addition, other metals such as iron [72] and magnesium bilization of the obtained TiO2-x nanomaterials [82].
[20,73] were also reported for the generation of Ti3+ species. The incorporation of H or removal of oxygen is the key factor for
the successful synthesis of TiO2-x materials. Wang et al. employed
hydrogen plasma method to prepare black TiO2-x samples (Fig. 4)
2.2. Properties and characterizations of TiO2-x photocatalysts
Chen et al. reported that the disorder lattice introduced mid-

gap states inside band gap of black H-TiO2 and blue shift of valence
band, which was stabilized via the hydrogen incorporation by pas-
sivating dangling bonds [4]. The authors demonstrated that the
enhanced solar light absorption over black TiO2 was caused by
the disordered surface layers, rather than traditional Ti3+ doping
[96]. No Ti3+ species was detected in both X-ray photoemission
spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) in
hydrogenated black TiO2 nanoparticles [96]. Almost at the same
time, Tao et al. reported a dopant-free TiO2 with reduced band
Fig. 3. Schematic illustration of the formation of oxygen vacancies during the
gap by ion sputtering and vacuum annealing treatments [5]. A new
electrochemical anodization process. Reprinted with permission from ref. [76],
Copyright 2016 Elsevier. ordered TiO2 phase was observed by STM [5]. The generation of
disordered layer and VB band tail after hydrogenation of TiO2 was
also reported by Cai et al. [49]. Lu et al. prepared hydrogenated TiO2
using the same method as Chen et al. published but starting from
the commercial P25, and disordered layers were still generated
after the hydrogenation on the surface of P25 [47].
However, Liu et al. observed amorphous rims both around refer-
ence and black TiO2 samples, and they regarded this feature often
observed for high-resolution transmission electron microscopy
(HRTEM) images of nanoparticles [97]. Interestingly, the hydro-
genated TiO2 synthesized by Wang et al. presented the generation
of oxygen vacancies and hydroxyl group [11,26], and no shift of
valence band was observed [11]. That is, the hydrogen corporation
results into the generation of Ti3+ species and oxygen vacancies,
rather than the formation of disordered layers on the surface of
TiO2 . The interaction between H atoms and oxygen vacancies was
Fig. 4. (a) Diffuse reflectance spectra of the pristine TiO2 , high-pressure hydro- confirmed by Mo et al. via DFT calculations [9]. Except oxygen
genated TiO2 and hydrogen plasma treated TiO2-x Hx samples. (b) The photos of vacancies, Wang et al. and Saputera et al. observed Ti3+ species in
pristine TiO2 and hydrogen plasma treated TiO2-x Hx samples. Reprinted with per- electron paramagnetic resonance (EPR) [21,48]. Furthermore, Hu
mission from ref. [37], Copyright 2013 Wiley-VCH.
et al. confirmed both the presence of Ti3+ in the bulk of TiO2 and
disorders on the surface [50].
In general, reduced TiO2 catalysts could be considered as the
removal of a neutral oxygen atom on the surface or/and in the bulk
of TiO2 , and/or the incorporation of H atoms into the TiO2 catalysts.
and they demonstrated that the reduction of TiO2 was achieved The generation of oxygen vacancies induced by the removal of oxy-
by the formation of Ti-H bonds, rather than the removal of oxygen gen atoms will cause charge imbalance, promoting the formation of
atoms (i.e., the doping of Ti3+ ) [37]. During the hydrogen plasma neighboring Ti3+ species. And the subsequent introduction of Ti3+
process, oxygen vacancies will be filled with H atoms and no Ti3+ will induce localized electronic states below the conduction band
will be detected, as evidenced by EPR or XPS characterizations [37]. minimum (CBM) [51,98]. The obtained localized states may act as
The reduction of TiO2 materials via hydrogen plasma treatment was the recombination centers of photogenerated electron-hole pairs
early studied [83–85]. Recently, Tian et al. and Lepcha et al. suc- and hinder the photocatalytic performance of TiO2-x samples. How-
cessfully synthesized black TiO2-x nanowires [25] and fibers [39], ever, with continuous formation of oxygen vacancies, the localized
respectively. An et al. treated TiO2 anatase and brookite with hydro- states will enrich and mix with the CBM, narrowing the band gap
gen plasma procedure [38]. In addition, water plasma treatment of TiO2 [30,45,51].
[40], frame-spraying [86,87] and laser ablation techniques [88,89] Meanwhile, the up-shifting of valence band maximum (VBM)
were also reported for the preparation of TiO2-x materials. with a band tail was also observed in the so-called “black” TiO2
Theoretically, except for reduction of TiO2 materials or Ti(IV) catalysts which were obtained by H2 thermal treatment [4,24,50]
precursors, the synthesis of TiO2-x photocatalysts can be achieved or plasma process which provided the active H species [40]. DFT
by partial oxidation of low-oxidation-state titanium compounds calculation shows that while H atoms are incorporated into TiO2
such as metallic Ti, Ti(II) and Ti(III) precursors. Zuo et al. used metal- materials via thermal treatment, the H atoms will occupy the
lic Ti powder as the starting material, and hydrochloride acid as the location of oxygen vacancies, and attract electrons from the neigh-
solvent via hydrothermal method [6]. H2 was supposed to release boring Ti and O atoms, resulting into high electron density of the
during the reaction between Ti and HCl in the high-temperature H atoms [9]. As a result, a shallow donor state will be introduced
and high-vapor-pressure condition. Liu et al. obtained Ti3+ self- into TiO2 . Besides, the blue-shift of band tail for hydrogenated P25
doped TiO2-x nanoparticles via hydrothermal treatment of TiH2 in catalyst was confirmed by Naldoni et al. from ∼1.2 eV below the
H2 O2 aqueous solution [15], and this method was then typically Fermi level to about −0.3 eV, as shown in Fig. 5 [24].
used for the synthesis of TiO2-x materials [90–92]. Xu and co- To probe the Ti3+ and oxygen vacancies in reduced TiO2 samples,
workers combined TiH2 /H2 O2 oxidation method with post-thermal XPS, EPR, STM, extended X-ray absorption fine structure (EXAFS)
treatment [42,43], and the post-thermal process was demonstrated and other characterization techniques are employed. XPS is a com-
to improve Ti3+ concentration and promote the migration of Ti3+ mon technique to analyze the surface chemical composition and
into the bulk of TiO2 . In addition, Ti2 O3 [46,93,94] and TiCl3 [45,95] the oxidation states of the elements. However, XPS can only reach
were also reported as the titanium sources for the synthesis of few layers of the surface of TiO2 samples, which limits the detect
TiO2-x photocatalyst. depth to ∼10 nm. To probe Ti3+ in the bulk or subsurface of TiO2 ,
Fig. 5. Schematic illustration of the structure and DOS of pure P25 (a) and black hydrogenated P25 (b) samples, respectively. The hydrogenated P25 catalyst showed a band
tail above the VBM with a shift from 1.20 eV to −0.3 eV. Reprinted with permission from ref. [24], Copyright 2012 American Chemical Society.
XPS analysis combined with an argon sputtering treatment could be mance from water splitting is also improved after hydrogenation
used to remove the top layers of TiO2 under ultra-vacuum [31]. The of TiO2 catalyst [62,73] and Ti3+ doping [6,10,60,107]. Besides, Fang
locations of Ti2p3/2 and Ti2p1/2 usually show a blue shift because et al. reported the CO2 photoreduction for selective CH4 evolution of
of the introduction of Ti3+ species, and oxygen vacancies can also TiO2-x materials under solar light irradiation [108]. Except for facil-
be evidenced in the O1 s XPS spectra. EPR is efficient for testing itating the separation of photogenerated electrons and holes, the
the Ti oxidation states and loss of O on the surface and in the oxygen vacancies enhance the trapping of CO2 molecules [109] and
bulk of TiO2 . The g-factors, which are independent of microwave promote the formation of CO− 2 species through a charge-transfer
frequency of EPR, are usually used for identifying the compounds process [110]. Furthermore, PEC performance of TiO2-x was studied,
instead of field resonance. The signal with g = 2.02 corresponds to including photocurrent density [39,43,111], power conversion effi-
O−2 , which comes from the reduction of surface adsorbed O2 by ciency (PCE) [56], incident photon-to-current conversion efficiency
surface vacancies [99]. EPR spectra with g⊥ = 1.992 and g// = 1.962 (IPCE), electrochemical impedance spectroscopy (EIS) Nyquist plots
were usually reported as the typical symbol of Ti3+ centers in the [43,50,56,111], lithium-ion batteries (LIBs) [20,112,113], lithium-
lattice of anatase TiO2 [100–104]. Besides, g-signals with g⊥ = 1.976 ion capacitor (LIC) [114], sodium-ion batteries (SIBs) [23,115] and
and g// = 1.945 have also been reported for rutile TiO2 [42,51], cor- oxygen-reduction reaction (ORR) tests [68], etc. It is concluded that
responding to Ti3+ in the bulk or subsurface of TiO2 catalysts. In TiO2-x nanomaterials have shown significant potential in solving
addition, the oxygen vacancies can be displayed visually on STM problems related to energy and environment issues.
images. A combination of these characterization techniques can be
used for the identification of reduced TiO2 catalysts.
3. TiO2-x photocatalysts doped with non-metal elements
2.3. Applications of TiO2-x photocatalysts 3.1. Doping with nitrogen
Based on the special physical and chemical properties of Doping with non-metal elements is a traditional modification
TiO2-x photocatalyst, TiO2-x presents superior photocatalytic way for TiO2 material to improve its photocatalytic performance
and photoelectrochemical performance, including photocatalytic [116]. Early in 2001, Asahi et al. demonstrated the band gap narrow-
degradation of organic compounds, photocatalytic hydrogen gen- ing and enhanced reactivity under visible light for nitrogen-doped
eration from water splitting, CO2 photoreduction, rechargeable TiO2 catalyst [117]. Then Burda et al. increased the concentration of
batteries, DSSCs, etc. TiO2-x was reported to show enhanced nitrogen doping in TiO2 to 8% via direct amination of TiO2 nanopar-
photocatalytic degradation of methylene blue [26,45,48,105,106], ticles [118]. The introduction of N contributes to the narrowing
rhodamine B [7], methyl orange [13,21,46], 4-chlorophenol [46], of band gap of TiO2 , which is caused by the mixture of N2p and
reactive black 5 [38] and phenol [38,106], because of its enhanced O2p states [117]. However, Sakthivel et al. demonstrated that the
solar light absorption, narrowed band gap and improved separation valence band edge upon nitrogen doping did not change [119].
of electron and hole pairs. The photocatalytic H2 production perfor- Batzill et al. also did not observe any band gap narrowing, although
localized N2p states just above the valance band induced by N dop- process, followed by NaBH4 reduction treatment to introduce N and
ing was found [120]. But Irie et al. ascribed the band gap narrowing Ti3+ into TiO2 , respectively [128]. Su et al. reported the preparation
as the formation of an isolated narrow band above the valence band of TiO2-x with N doping using urea as the reductant [55]. When urea
[121]. As concluded by Kuznetsov et al., the orbital mixing of O2p and amorphous TiO2 were annealed at high temperature under
and N2p is impossible [122], and the calculated band gap energies N2 atmosphere, carbon nitride formed on the surface of TiO2 at
were underestimated in Asahi et al.’s work [117]. The enhanced around 300 ◦ C, and then the formed C3 N4 decomposed when the
visible absorption of N-doped TiO2 should be attributed to the temperature reached 700 ◦ C. The decomposition of C3 N4 leads to
formation of midgap states inside the band gap, which was con- the formation of high-reducing carbon and nitrogen species, which
firmed by Di Valentin via experiment and DFT calculations [123]. can be used to reduce Ti4+ into Ti3+ at high temperature. Finally,
For reduced TiO2 catalyst, it is hoped that the disorder structure will Ti3+ doped porous TiO2 was obtained and nitrogen was doped into
contribute to the upshift of valence band maximum, and Ti3+ and the lattice of TiO2 , which can be used as gas-sensing materials for
oxygen vacancy (Ov ) doping will introduce impurity states below CO detection [55].
the conduction band. Therefore, further doping with non-metal ele- Zhang et al. reported nitrogen-doped black hydrogenated
ments such as nitrogen would be an ideal way to continue the band TiO2 with a flower-like hierarchical architecture [129]. Tripoly-
gap modification engineering of TiO2 . cyanamide was used in the nitrogenation process of TiO2 as the
Hoang et al. reported reduced TiO2 nanowire arrays with nitro- nitrogen source and also structure-directing agent. Then hydro-
gen doped modification [124]. The hydrogenation and nitridation genation was achieved by heating at high temperature under H2
were achieved by annealing TiO2 both under H2 and NH3 gas flows. flow. Hydrogenation of TiO2 is responsible for the generation of
The substitutional Ti3+ and N were confirmed by EPR and XPS in high concentration of Ov and small amount of Ti3+ , and it results
Hoang’s work [124]. Considering the bandgap modification of Ti3+ into the increase of VBM but decrease of CBM. Sayed et al. employed
and N doping, it is believed that the interaction between Ti3+ and heating treatment with ethanolamine and solvothermal chemical
N is responsible for the solar light absorption edge extension and reduction using diethylene glycol for the nitridation and reduction
high water photo-oxidation performance of TiO2 under visible light of TiO2 samples [130]. Band gap narrowing induced by Ti3+ and N
irradiation. Chen et al. reported that heating TiO2 in NH3 gas would doping was raised by Sayed.
result in the doping of nitrogen and also formation of oxygen vacan- The incorporation of hydrogen and/or removal of oxygen show a
cies [125]. Similar work has already been studied by Irie et al. significant effect on the introduction of nitrogen species in reduced
early in 2003, and oxygen vacancies were detected. However, the TiO2 . After hydrogenation, N-doped TiO2 shows a broader and blue
authors ascribed it as single nitrogen doping in the bulk of TiO2 shift of N 1s species in XPS spectra, and Hoang et al. ascribed
[121]. Besides, the facilitation of Ti3+ and oxygen vacancies forma- this shift to the formation of lower oxidation states of substitu-
tion caused by nitrogen doping was confirmed by DFT calculations tional N introduced by electrons transfer from Ti3+ [124]. In general,
[120]. substitutional N is located at lower bonding energy position than
The obtained Ti3+ species induced by N doping via thermal interstitial N species in XPS [131,132]. Cheng et al. observed both
treatment are usually located at the surface. Except for ther- interstitial N (Ti O N) and substitute N (N Ti O) species in N1s
mal treatment, Li et al. successfully synthesized nitrogen doped XPS spectra [53]. Moreover, Zhang et al. demonstrated that N
TiO2-x samples through dielectric barrier discharger (DBD) plasma doping concentration (Ti O N bond in XPS) decreased after post-
method [126]. It is one of non-thermal plasmas with a high electron hydrogenation [129]. This phenomenon was also observed by Fang
temperature but low bulk gas temperature (room temperature). et al. and Zhou et al., the authors reported the decrease of Ti O N
After DBD plasma treatment, disorder layers were generated on but the increase of anionic N− on the samples after vacuum acti-
the surface of TiO2 catalyst, and the dopant could be controlled vation [13,28]. And the total nitrogen doping percentage remains
by changing the working gases of plasma (Fig. 6). The generation of changeless after vacuum activation process [28]. It indicates that
surface Ti3+ and substituted N doping was identified by XPS and EPR during vacuum thermal treatment, nitrogen atoms are favorable to
techniques, implying that reduction and nitridation of TiO2 could migrate from the surface to deeper layer of TiO2 , bonding with tita-
be both achieved by the NH3 plasma treatment [126]. nium atoms and occupying the position of oxygen vacancies which
Except for thermal treatment under gas flow, nitrogen doped are introduced by vacuum activation [13].
TiO2-x can also be obtained by vacuum activation or reduced by The interaction between Ti3+ and nitrogen under thermal
nitrogen-rich precursors. Fang et al. synthesized N doped TiO2-x vacuum treatment can be described as follows (Fig. 7). Firstly, nitro-
via a simple one-step vacuum activation process [13]. As reported gen doping introduces some chemically absorbed nitrogen atoms
by Xing et al., vacuum process will introduce [Ov :2Ti3+ ]0 impurity which are bonded with oxygen atoms on the surface, and it also
states just below CBM, and the oxygen vacancies and Ti3+ species introduces several oxygen vacancies on the surface layers of TiO2
were confirmed by XPS and EPR spectra [27]. Fang et al. found that catalyst [122,123]. After thermal vacuum treatment, the oxygen
this method can simultaneously further introduce N doping species atoms which were bonded with titanium atoms are departed. Di
into deep layers of TiO2 [13]. The preparation of reduced TiO2 and Valentin et al. reported that the formation cost of oxygen vacancies
doping of nitrogen can be achieved at the same time in the vacuum is reduced in the presence of nitrogen doping [123]. As a result,
activation process. Zhou et al. demonstrated that vacuum activa- plenty of Ti3+ and oxygen vacancies are obtained both on surface
tion method results into the increase of Ti-N in XPS and facilitates and deeper layers of N-doped TiO2 [27]. In the presence of oxygen
nitrogen doping into the lattice of TiO2 [28]. vacancies, the nitrogen atoms chemically absorbed on the surface
Cheng et al. prepared reduced TiO2 doped with nitrogen via a would migrate into deep layers of TiO2 , favorable for the forma-
simple one-step solution reduction process [53]. Hydrazine hydrate tion of bulk N species (Nb − ) based on electron transfer form Ti3+ to
solution was used as nitrogen source during the annealing treat- paramagnetic bulk N (Nb • ) [133]. The nitrogen atoms would take
ment, leading to the formation of nitrogen doping. Besides, Ti4+ the place of oxygen vacancies and bond with titanium, or stay in
species could also be reduced by hydrazine hydrate, leading to the the interstitial sites. These N complex species could contribute to
formation of Ti3+ impurity doping states just below the conduction the formation of nitrogen impurity states in the bandgap of TiO2
band. Li et al. reported 3D hierarchical structure TiO2-x samples [132]. Finally, in the one-step vacuum treatment, Ti3+ production
with nitrogen doping [127]. Diethylentriamine was used as the and nitrogen migration could be achieved simultaneously, resulting
nitrogen resource during the hydrothermal process. In Liu et al.’s into the bandgap narrowing of TiO2 catalyst.
work, urea was used as the nitrogen resource in the hydrothermal
Fig. 6. Proposed mechanism for the formation of disorder layers on the surface of TiO2 via DBD plasma process with different working gases (Ar, H2 and NH3 ). Ti3+ and oxygen
vacancies are generated after Ar or H2 plasma treatment, while N and Ti3+ are both doped into TiO2 catalysts using NH3 as the working gases. Reprinted with permission
from ref. [126], Copyright 2014 Wiley-VCH.
Fig. 7. Proposed mechanism of Ti3+ and N co-doping in TiO2 photocatalyst by vacuum activation process. The module was cleaved on the (101) surface of anatase TiO2 .
Reprinted with permission from ref. [13]. Copyright 2015 Elsevier.
The synergistic effect between Ti3+ and nitrogen dopant introduced by molten aluminum reduction in an evacuated two-
species is the key factor for the enhancement of photocatalytic zone furnace. At the same time, a large number of oxygen vacancies
performance of N-TiO2-x under visible light irradiation. The pho- were generated in the shell during this process. Then the S2−
togenerated electrons will be excited from nitrogen doping levels anions occupied the place where oxygen vacancies located, further
above the valence band directly to the Ti3+ impurity states just narrowing the bandgap of TiO2-x and enhancing the visible-light
below conduction band [134], extending the absorption edge to absorption. Similar like that of nitrogen doped TiO2-x , the bandgap
the visible light region [13]. Besides, the introduction of Ti3+ and narrowing of S-doped TiO2-x was achieved by the introduction of
oxygen vacancies facilitates the separation of photogenerated elec- S3p orbitals and impurity states caused by Ti3+ , making it possi-
trons and holes. As the result, reduced TiO2 materials doped with ble to extend absorption edge from UV region to visible and even
nitrogen present superior activities than the pristine TiO2 such near-infrared region [10].
as enhanced photocatalytic and photoelectrocatalytic degradation Feng et al. reported the formation of disordered surface layers,
of organic compounds [13,53], improved water photooxidation however, induced by boron doping [135]. In general, surface Ti3+
performance [124], increase of photocatalytic hydrogen evolution species are not stable and likely to be oxidized by the oxygen in
rate under AM 1.5 illumination [129], and CO detection with fast air or water under solar light irradiation. In Feng et al.’s work, the
response/recovery at room temperature [55]. concentration of Ti3+ reaches as high as 87.5% of the total Ti on the
surface of the boron-induced catalyst, calculated from XPS spec-
tra [135]. Interstitial B specie (B-O-Ti) is observed in the B-doped
3.2. Doping with boron, sulfur, fluorine or iodine TiO2-x , and it favors the formation of surface Ti3+ species and struc-
tural disorder layers on the surface of catalyst. The generation of
Except for nitrogen, other non-metal elements were also intro- Ti3+ impurity states and lattice disordered layers account for the
duced into reduced TiO2 photocatalysts, such as boron, sulfur, bandgap narrowing of TiO2 and enhanced mobility of photogener-
fluorine and iodine. ated electrons, which finally improves its solar-light photocatalytic
Yang et al. reported sulfur-doped TiO2-x with a core-shell water splitting for hydrogen production.
nano-structure via aluminum reduction followed by post-thermal
treatment under H2 S atmosphere [10]. The disordered shell was
Fig. 8. (a) Schematic illustration of the synthesis of core-shell structured TiO2-x samples and its further doping with nonmetal elements. (b) Core-shell structure of the
reduced TiO2 catalysts by HRTEM. (c) UV-DRS spectra of reduced TiO2 samples with nonmetal (H, N, S, I) doping. Reprinted with the permission from ref. [138], Copyright
2014 Royal Society of Chemistry.
The bandgap narrowing of B-doped TiO2-x was ascribed to the est photocatalytic H2 generation and photodegradation of methyl
formation of Ti3+ impurity states and disordered surface layers orange under visible irradiation [138].
[135]. Two kinds of mid-gap states were observed in the calcu-
lated DOS analysis, and the one below CBM was ascribed to Ti3+
4. Metal-based TiO2-x materials
doping while the one above VBM was mainly attributed to disor-
der structure, respectively. The interstitial B atoms contribute to
4.1. Noble-metal-based TiO2-x materials
the formation and stabilization of disorder layers and Ti3+ species
by coupling with neighboring Ti and O atoms, supported by DOS
It is reported that low concentration of Ti3+ facilitates the for-
calculation [135]. In addition, the generation of band tail above
mation of localized oxygen vacancies and inhibit electron mobility
the valence band is usually found on hydrogenated TiO2 , owing
[45,94]. These localized defect sites act as recombination centers for
to structural disorder on the surface of TiO2 [40,89,136]. However,
photogenerated electron-hole pairs and thus restrain the photocat-
Mo et al. demonstrated that hydrogen defects showed little influ-
alytic activities of TiO2 samples. Noble metal nanoparticle, such as
ence on the positions of VB or CB, and they attributed the up-shift
Au, Pt and Pd are usually used as the co-catalyst over the TiO2 (M-
of valence band to hybridization of H and O2p orbits [9].
TiO2 ), promoting the activities by surface plasmon resonance (SPR)
The doping of F atoms on TiO2-x samples was reported by Xing
and the separation of charge pairs [139].
et al. via vacuum activation process with a mixture of TiO2 /MCF and
Pan et al. synthesized gold grafted TiO2-x nanoparticles and
NH4 F [137]. Reduction of TiO2 and doping of F were achieved in the
studied the noble metal loading process on oxygen-defective TiO2
vacuum thermal treatment at the same time. Similar like nitro-
photocatalyst [140]. The spontaneous and fast loading of gold on
gen doping on TiO2-x catalysts via vacuum activation process, the F
TiO2 samples was achieved by the strong binding with oxygen
atoms occupy the place of oxygen vacancies rather than lattice oxy-
vacancies. The electrons located on the oxygen vacancy states of
gen due to their strong electrophilicity, leading to the formation of
TiO2 will be captured by gold ions, and then reduce the ions to gold
paramagnetic Ti3+ -F. The lifetime of electrons will be prolonged by
substances. The priority of gold binding with defect-rich TiO2 sur-
the obtained lattice Ti3+ -F levels. However, while traditional calci-
face was confirmed by theoretical calculations [141], and the charge
nation techniques are employed to the doping of reduced TiO2 , only
transfer from reduced TiO2 to Au was also evidenced by Jiang et al.
Ti4+ -F and surface Ti3+ are generated because of the replacement of
[142]. Besides, Lian et al. synthesized reduced TiO2 grafted with Pt
lattice oxygen atoms by F atoms.
which starts from metallic Ti foil [143]. The Pt loading was real-
Lin et al. investigated the effect of various nonmetal incorpo-
ized through reduction of Pt ions by Ti3+ species, evidenced by the
ration in reduced TiO2 samples, such as H, N, S and I [138]. The
decrease of Ti3+ signals. Therefore, in this case, additional reduc-
core-shell structured TiO2 photocatalyst with amorphous oxygen-
ing agents, surfactants or post-thermal treatment are not necessary
deficient TiO2 shells was synthesized first by molten Al in an
during the preparation process for the loading of noble metal ions
evacuated two-zone furnace (Fig. 8b). Then nonmetal corporations
on the reduced TiO2 catalysts.
were achieved by hydrogen plasma and thermal treatment with
It is reported that the loading of Au promotes the formation
NH3 , S, and I2 gases, respectively (Fig. 8a). The content of oxy-
of oxygen vacancies in the interface of Au and TiO2 [59], espe-
gen vacancies decreased after nonmetal incorporation, implying
cially under UV or X-ray irradiation (Fig. 9) [144]. These oxygen
the filling of oxygen vacancies by these elements. Among all these
defects induced by gold loading are usually low-concentrated,
reduced TiO2 doped with nonmetal elements, TiO2-x doped with
and mainly located on the surface of catalyst. This phenomenon
N shows the largest solar light absorption (Fig. 8c), and also high-
could be explained by the electron trapping effect of noble met-
Compared to other noble metals, Ag is cheaper and easier to

be synthesized [149]. The synthesis of Ag2 O/TiO2-x composite was
reported and the existence of Ag2 O accelerated the charges separa-
tion and transference [150,151]. Li et al. designed a dual Z-scheme
system for Ag2 O modified TiO2-x nanocrystals with {001} and {101}
facets exposure [151]. Based on the dual Z-scheme system theory,
the photogenerated electrons in the CB of Ag2 O and holes in the VB
of {101}-TiO2 could be retained, resulting into the strong oxidation
and reduction capability of the catalyst.
Self-doped TiO2 decorated with Ag/AgCl or Ag/Ag2 O compos-
ites were designed [149,152]. Cui et al. prepared Ag-Ag2 O/TiO2-x
nanophotocatalyst using KBH4 as the reductant [149]. KBH4 solu-
tion contributes the formation of Ti3+ species and reduction of Ag+
Fig. 9. Illustration of Ti3+ formation on gold deposited TiO2 materials under UV to Ag0 nanocrystalline. Finally, Ag-Ag2 O/TiO2-x nanomaterial was
and soft X-ray radiation. Reprinted with permission from ref. [144], Copyright 2015 successfully fabricated. During the preparation of Ag/AgCl modi-
American Chemical Society. fied TiO2-x hollow sphere photocatalyst, Yin et al. chose NaBH4 as
the reductant for the chemical reduction of Ti(IV) species, followed
by photo-induced reduction of AgCl to Ag nanoparticles [152]. The
synergistic effect between SPR effect of Ag0 and band gap narrow-
ing by Ti3+ doping promotes solar light absorption and efficient
electron-hole separation, improving photocatalytic activities under
visible light irradiation.
4.2. Non-noble-metal-based TiO2-x materials
Recently, using Cu species as co-catalyst for TiO2 has attracted

plenty of attentions. Noble metals such as Rh, Pt, Ag, Au and Pd
were used for metal incorporation to improve the photocatalytic
activities of TiO2 previously, because of their high activities and sta-
Fig. 10. (a) Charge transfer on Pd loaded pristine TiO2 samples in oxygen reduction bility. However, due to the high cost of noble metals, copper begins
reaction (ORR) process. (b) Charge transfer between Ti3+ impurity states and Pd to show the potential to substitute noble metals as co-catalyst for
atoms on Pd loaded TiO2-x samples in ORR process. Reprinted with permission from TiO2 because of its low-cost and considerable activities [153].
ref. [147]. Copyright 2016 American Chemical Society.
Nanosized metallic Cu is not stable and easy to oxidize to Cu2 O
or CuO while exposure to air or oxygen molecules. In order to
als. The effect of electron-rich platinum on TiO2-x samples was prevent the oxidation of Cu nanoparticles, Zhao et al. coated Cu
firstly evidenced by low-temperature EPR early in 1988 by Bon- with reduced TiO2 by thermal treatment under vacuum [154]. The
neviot et al.[145]. In the EPR spectra, the g tensor at g⊥ = 1.969 metallic Cu promotes the generation of oxygen vacancies of TiO2
and g// = 1.936 was reported on the Pt/TiO2-x material induced by during the preparation process, and finally facilitates the charge
hydrogenation through heating at high temperature. This signal separation of photogenerated electrons and holes caused by elec-
was ascribed as Ti3+ in the metal-support interface on the pres- tron transfer between Cu and TiO2 .
ence of platinum on TiO2-x samples. In addition, Albuquerque et al. To achieve high quantum efficiency of Cu/TiO2 , energy level
reported that the doping of Ce also facilitates oxygen vacancy for- matching is presented, and Kumar et al. proposed that the electron
mation on anatase TiO2 by DFT calculation [146]. transfer from Ti3+ doping level to Cu co-catalyst (Cu2+ ) accounts
The loading of noble metal on reduced TiO2 samples usu- for the improved activities of the catalyst [155]. Liu et al. demon-
ally leads to an electron-rich noble-metal surface, and it was strated that the grafting of Cu(II) oxide amorphous nanoclusters on
also observed on Pd- [147] or Pt-grafted [143] TiO2-x materials. reduced TiO2 showed a interfacial charge transfer (IFCT) from VB
The loaded noble metals, which act as active sites, could trap of TiO2 to Cu2+ nanoclusters, leading to a multi-electron oxygen
electrons and protons easily. The electron transfer between Ti3+ reduction process, as illustrated in Fig. 11 [93].
and noble metal promotes the strong metal-support interaction In addition, it was also reported that Cu+ species is more active
(SMSI), resulting into the enhanced activity of the catalyst, e.g. the than Cu2+ and Cu [156–158], and the formation of Cu+ species or
charge transfer between Pd and Ti3+ species enhances the oxygen- Cu+ /Cu0 is essential for high activities of the catalysts [159]. Liu et al.
reduction reaction of Pd-TiO2-x [147]. Yuan et al. reported that a reported that after thermal treatment of Cu/TiO2 under inert gases
localized electron transfer could be achieved between Pd surface (e.g., N2 , Ar, He), the Cu2+ would trap electrons induced by oxygen
atoms and Ti3+ impurity states [147], leading to the electron-rich vacancies and convert to Cu+ species, while at reductive atmo-
Pd surface, as illustrated in Fig. 10. The subsequent decreased sphere (e.g., H2 ), the partial obtained Cu+ would further be reduced
adsorption of O2 caused by charge transfer would promote the to Cu [156]. Similar mechanism was reported, and Chen et al. iden-
ORR performance of Pd-TiO2-x catalysts. Lian et al. also reported tified the formation of Cu+ by XPS, X-ray absorption near edge
the formation of Pt-O bond induced by in-situ reduction of Pt4+ structure (XANES), EPR and EXAFS [153]. A proposed charge trans-
ions on TiO2-x , and it facilitated the electron transfer from the bulk fer reaction was raised as follows: Cu2+ + Ti3+ → Cu+ + Ti4+ . Then
to the surface of TiO2 , benefiting for excellent performance for the further thermal treatment at H2 atmosphere would reduce
photocatalytic H2 evolution [143]. Zheng et al. reported Pd-MgNix the obtained Cu+ to Cu nanoparticles. The mixture of Cu and Cu+
nanospheres which act as co-catalyst with black-TiO2 [148]. Pd and species contributes to the high activity of Cu/TiO2 in CO oxida-
MgNix alloy are demonstrated to be electron and hole collectors, tion (Fig. 12) [153]. It is demonstrated that the formation of oxygen
respectively, working as the reduction and oxidation sites in the vacancies and Ti3+ is essential for the generation of the high-active
photocatalysis process and avoiding surface charge recombination. Cu+ species.
platform for charge transfer while combining with other semi-

conductors, such as TiO2-x @MoS2 photocatalysts with core-shell
structure [128]. Liu et al. combined MoS2 and black TiO2 together to
form 3D mesoporous structural composite [60]. The sandwich-like
nanosheets exhibited high photodegradation rate of methyl orange,
due to the active S atoms, narrowed band gap by Ti3+ formation and
excellent charge transfer between MoS2 and TiO2-x .
To extend the optical absorption of TiO2 to the visible region,
CdS is a good candidate for TiO2 coupling because of its narrow
band gap and suitable band alignment with TiO2 . Zhang et al.
fabricated CdS decorated TiO2-x nanotube arrays by cathodic polar-
ization followed by chemical deposition [165]. CdS is beneficial for
the incident photon-to-charge carrier generation efficiency (IPCE),
while Ti3+ contributes to the enhanced solar light absorption and
improved change transport of TiO2 catalyst. Ji et al. reported that
the formed Ti3+ provided a transport route for photoexcited elec-
trons between these two composites of the CdSe quantum dots
Fig. 11. Proposed charge transfer on Cu(II) oxide grafted TiO2-x catalyst under visible grafted TiO2 samples [166]. Ma et al. employed Ag3 PO4 quantum
light irradiation. Reprinted with permission from ref. [93]. Copyright 2011 American
Chemical Society.
dots as the photosensitizer of TiO2-x for high photocatalytic effi-
ciency [167]. The improved charge transfer process was achieved
by Ag-O-Ti bonds between Ag3 PO4 and TiO2-x .
In addition, Liu et al. ascribed the enhancement of CO2 photore- Ti3 C2 , a representative of exfoliated transition metal carbides
duction for CH4 and CO evolution to the synergistic effect between materials (MXenes) [168,169], have attracted plenty of attentions
Cu+ and Vo /Ti3+ species: enhanced CO2 adsorption and subsequent owing to the high mobility of carriers. The hole trapping effect of
charge transfer promoted by surface oxygen defects, and electron- 2D Ti3 C2 OHx facilitates the separation of photoexcited carriers on
hole pairs separation induced by Cu+ /Cu0 couples [156]. Surface TiO2-x samples, reported by Peng et al. [170]. Other metal-based-
oxygen defects or Ti3+ promotes the formation of CO2 − from cap- materials have been used for coupling with TiO2-x , such as SrTiO3-x
ture of CO2 by electrons, while the Cu+ helps to the subsequent [171] and BiVO4 [172]. Zhu et al. reported that the generation of
dissociation of the obtained CO2 − to CO molecules even in the dark Ti3+ promotes the electron transfer from CB of BiVO4 to Ti3+ impu-
[110]. rity states of TiO2-x , while the electron transfer to CB of pure TiO2
Reduced TiO2 grafted or doped with iron-group metal (e.g., Fe, is difficult because of the energy barrier between BiVO4 and TiO2
Co and Ni) are also reported. Fe(III) nanoclusters, acted as electron [172].
trapping centers, could efficiently promote the electron transfer
from oxygen vacancy states of TiO2-x to the adsorbed molecules, 5. Carbon-based TiO2-x materials
and the recombination of electron-hole pairs in TiO2-x are sup-
pressed [160]. Khan et al. reported that doping of Fe ions into TiO2 Carbon is one of the most fascinating elements in the periodic
lattice created impurity energy levels of Fe2+ /Fe3+ and Fe3+ /Fe4+ . table. It is the base of lives all over the earth. The atoms of carbon can
These Fe3+ 3d states in addition to Ti3+ doping states favor the elec- be bonded in different ways. The best-known forms of carbon are
tron transition and contribute to narrowing of TiO2 band gap [161]. graphite, diamond and amorphous carbon. In addition, fullerene,
Liu et al. synthesized cobalt doped TiO2-x samples by a simple vac- carbon nanotube and graphene are newly found materials in recent
uum activation method [162]. Similar like the effect of noble metal decades. Based on the various properties of carbon-based materi-
doping on TiO2-x catalysts [59,144], the introduction of Co also pro- als, the combination of carbon and TiO2-x will contribute to new
motes the formation of Ti3+ and oxygen vacancies in TiO2 [162]. In features and enhanced performance.
addition, Ni catalyst is usually used in the CO2 hydrogenation reac-
tion for CH4 evolution [163]. The synergistic effect of Ni2+ and Ti3+ 5.1. Graphene-based composite materials
on the visible-light absorption and charge separation was therefore
studied by Zhang et al. [61]. Graphene has been representative of 2D materials since
Novoselov et al. extracted graphene from a piece of graphite in 2004
4.3. Metal-compounds-based TiO2-x materials [173]. Graphene is only one single atomic layer of carbon, packed
in a hexagonal lattice. Gein and Novoselov regard it as a basic block
MoS2 is a typical layered structural metal sulfide, consisted for building all other graphitic materials: it can be wrapped up into
of stacked atoms layers (S-Mo-S) by van der Waals forces. Few- 0D fullerenes, rolled into 1D carbon nanotubes and stacked into 3D
layered or single-layered MoS2 materials are useful in applications graphite [174]. Although graphene is a form of carbon, the proper-
of electronics and energy storage [164]. MoS2 could provide a ties are completely new. The use in composite materials is probably
Fig. 12. Proposed mechanism of Cu+ /Cu formation in Cu/TiO2-x catalysts and its activity for CO oxidation. Reprinted with permission from ref. [153], Copyright 2012 American
Chemical Society.
Fig. 13. (a) SEM image of {001}-{101} exposed TiO2-x catalyst wrapped with graphene. The image showed that the TiO2 single crystals were wrapped with a thin layer of
graphene. Reprinted with permission from ref. [175], Copyright 2014 Wiley-VCH. (b) TEM image of TiO2-x /graphene heterostructure. The reduced TiO2 catalysts prepared
by LAL process dispersed on the sheet of graphene homogeneously, indicating the strong contact between TiO2 and graphene. Reprinted with permission from ref. [16],
Copyright 2016 American Chemical Society.
the most immediate application for graphene. Benefiting from its

high conductivity property and unique structure, graphene-based
composite materials could achieve special supporting structure and
enhanced photogenerated electron-hole separation of TiO2 .
Wang et al. synthesized reduced graphene oxide (RGO)
wrapped TiO2 nanocrystals (NCs) with Ti3+ and oxygen vacan-
cies via hydrothermal treatment followed by thermal annealing
under vacuum (Fig. 13a) [175]. By treating TiO2 NCs with 3-
aminopropyltriethoxysilane (APTES), amine group was introduced
on the surface of TiO2 , and made it positively charged. Then the neg-
atively charged graphene oxide sheets were wrapped on TiO2 easily
through electrostatic attraction interaction [175]. With the help of
HRTEM, the final TiO2 NCs/RGO sample presents a unique core-
Fig. 14. Schematic illustration of the charge transfer on TiO2-x /boron doped
shell structure, which is responsible for the formation of Ti3+ and
graphene composite. Reprinted with permission from ref. [106], Copyright 2014
Ov . As a result, the generation of Ti3+ and Ov will introduce impurity Nature Publishing Group.
states below the conduction band, extending the absorption edge
of solar light to the visible region, and the photogenerated electrons
can transfer from reduced TiO2 to graphene and its recombination
with holes will be inhibited.
Xing et al. prepared reduced TiO2 /graphene composite material
via a simple one-step hydrothermal method [106]. The final mate- introduction of Ti3+ doping at the same time [16,104,176]. Xing
rials consist of TiO2 nanorods with exposed {100} and {010} facets, et al. have reported a vacuum activation method for the synthesis
and boron doped graphene sheets. NaBH4 was used as the reducing of Ti3+ self-doping TiO2 materials [27]. This facile approach could
agent and also boron dopant source during this process. Hydrogen be used for the reduction of graphene oxide. In the work reported
release is achieved by the hydrolysis of NaBH4 , which can be used by Qiu et al., the doping of Ti3+ , reduction of graphene oxide, and
during the preparation of reduced TiO2 , as previously reported by the loading of TiO2-x samples on the reduced graphene oxide were
Xing et al. [57] Since then, other approaches for preparing reduced achieved at the same time by one-step vacuum activation process
TiO2 materials were reported by using NaBH4 as the reducing agent [104]. Other reduced-metal-oxide/graphene materials could also
[7,12,23,58–62,128]. be prepared by the same method.
The charge transfer of TiO2-x /graphene composite under solar Li et al. employed a one-step laser ablation in liquid (LAL)
light irradiation is discussed in details, as illustrated in Fig. 14 [106]. method without any chemical reduction agent for the synthesis of
Under solar light irradiation, the photogenerated electrons transfer TiO2-x /graphene oxide heterostructure (Fig. 13b) [16]. Under laser
from valence band to the impurity level introduced by Ti3+ doping. irradiation, oxygen atoms would depart from the lattice of TiO2 ,
Because the surface energy of exposed {001} and {100} facets are leading to the formation of oxygen vacancies and Ti O C bond
higher than that of {101} facets, the electrons tend to transfer from with graphene oxide. The reduction of Ti4+ and loading of TiO2 on
{001} or {100} facets to {101} facets. Finally, the enriched elec- graphene could be achieved at the same time.
trons in TiO2 transfer to graphene through Ti O C bonds in the In general, surface hydroxylation of TiO2 would introduce sev-
interface of TiO2 and graphene materials. In this process, graphene eral surface defects on TiO2 , such as Ti3+ , oxygen vacancies and
significantly accelerates electron transfer and avoids recombina- Ti OH bond. Cao et al. reported that hydroxylation would con-
tion of the photogenerated electron and hole pairs because of its tribute to the interaction between TiO2 and graphene [176]. By a
high electronic conductivity. simple UV-microwave method, the surface hydroxylation of TiO2
The reduction of graphene oxide often requires complex devices, and the composition with graphene were achieved, resulting into
time-consuming conditions, or toxic chemicals. In order to avoid the expanded light absorption and improved charge transfer rate.
high toxicity and the following second pollution, several new meth- In addition, TiO2 photocatalyst modified by hydroxyl groups was
ods are used for the reduction of graphene oxide and also the reported to exhibit efficient photocatalytic reduction of Cr(VI) to
Cr(III) [177].
5.2. Other carbon-based composite materials
Zhang et al. synthesized TiO2-x and carbon nanotubes (CNTs)

composite material, used as highly efficient counter electrode for
ZnO-based dye-sensitized solar cells [56]. The black reduced TiO2
was prepared via a simple sol-gel method, using carbamide as
the reductant. Based on the notable electrocatalytic activities of
TiO2-x and excellent hole-transfer property of carbon nanotubes,
TiO2-x /CNTs composite material can be regarded as an alternative
to the traditional Pt electrode. Except for carbon materials such as
graphene and CNTs with high charge-transfer properties, simple
carbon coating on the surface of TiO2 could also be used for the
enhanced photocatalytic performance because of its stabilization
of the obtained Ti3+ [107]. The coating carbon works as a barrier,
which could prevent H2 O and O2 from diffusing into the surface
of TiO2 and avoid direct exposure of the surface Ti3+ species. In
other literature, coke carbon and graphite-like carbon induced by
Fig. 15. Schematic illustration of charge transfer on reduced TiO2 catalysts with
vacuum activation process act as photosensitizer, leading to the {001} and {101} co-exposure under solar light irradiation, and its application of
enhancement of solar light absorption and photoinduced electrons photocatalytic CO2 reduction for CH4 and CO evolution. Reprinted with permission
migration [178,179]. from ref. [108], Copyright 2017 Royal Society of Chemistry.
exposure, mesoporous TiO2-x , core-shell or yolk-shell structured

5.3. Carbon-compound-based composite materials
TiO2-x , TiO2-x inverse-opals, etc. Besides, special facets exposure of
TiO2 make significant changes to the physical and chemical prop-
Recently, graphitic C3 N4 (g-C3 N4 ), a novel-metal-free mate-
erties of TiO2 catalysts.
rial with special layered structure, has gained massive attentions
because of its narrow band gap (2.7 eV) and high thermal and chem-
6.1. TiO2-x with special facets exposure
ical stability [180,181]. g-C3 N4 can be prepared by pyrolysis of
nitrogen-rich precursors such as melamine [182]. Lu et al. prepared
The facets exposure effect is an important factor for TiO2 pho-
Ti3+ doped TiO2 with exposed {001}-{101} facets and graphitic
tocatalysts, related to physical and chemical properties of the
C3 N4 separately, and then TiO2-x /g-C3 N4 composites were obtained
catalyst. Anatase TiO2 nanoparticles with exposed high-surface-
by ultrasonic waves [183]. Li et al. synthesized TiO2 /g-C3 N4 het-
energy {001} facets are reported to show higher photocatalytic
erojunctions from a mixture of H2 Ti3 O7 and melamine by a simple
performance than the TiO2 with traditional {101} facets expo-
one-step calcination process [184]. Strong bonding between TiO2
sure [187]. TiO2 nanocrystals with exposed {001} facets decorated
and g-C3 N4 was formed during the preparation, and Ti3+ and oxy-
with Pd were reported to exhibit highly photocatalytic and selec-
gen vacancies were also generated at the same time. Liao et al.
tive alcohol oxidations under UV light irradiation [188]. Cao et al.
reported a heating followed by an electrochemical reduction step
reported the superiorly photocatalytic performance for degrada-
for the synthesis of TiO2-x nanotube arrays/g-C3 N4 material [185].
tion of phenol and rhodamine B on TiO2 -{001} single crystals than
The self-doping of Ti3+ into TiO2 was achieved by electrochemical
the commercial P25 catalyst [189]. However, the relatively wide
reduction process, which has been proved to be an efficient way to
band gap limits its light absorption to UV region. Therefore, it is nec-
prepare reduced TiO2 in previous works [31,33].
essary to introduce self-doping into the pristine TiO2 samples with
The separation of photogenerated electron-hole pairs and pro-
special facets. And it is also important to investigate the reduced
longed charge life induced by the heterojunction structure could be
surface of TiO2 , including formation, surface energy, light absorp-
confirmed by photoluminescence (PL). In general, the photoexcited
tion, molecule adsorption, charge transfer, etc.
carriers among heterojunctions could transfer either band to band
Single large {101} facets only result in adjacent trapping sites
or Z-scheme. Li et al. ascribed the charge migration in TiO2-x /g-C3 N4
for the carriers and high electron-hole recombination rate, while
composite as electron transfer from VB of g-C3 N4 to VB of TiO2 and
co-exposure of {001} and {101} facets contribute to charge separa-
hole transfer from CB of TiO2 to that of g-C3 N4 , when under visible
tion [190]. Chen et al. demonstrated the providing of hole-trapping
light irradiation [184]. Such kind of charge transfer leads to the sep-
site by {001} facets, and the acceleration of hole migration to
aration of electrons and holes, and prolong charges lives. However,
{001} facets induced by the electrostatic effect of surface F anions
Liao et al. regarded the charge transfer in TiO2 /g-C3 N4 composite as
[191]. It is also reported that {001} and {101} facets work as
a Z-scheme process under UV light irradiation along with the for-
hole and electron collectors, respectively [192]. In a dual {001}-
mation of hydroxyl radicals [185]. The photogenerated electrons
{101} anatase TiO2 system, the electrons are likely to migrate from
transfer from CB of TiO2 to VB of g-C3 N4 , while the holes remain
{001} facets to {101} facets while the holes prefer to move from
staying in the VB of TiO2 . Finally, the wide optical absorption of
{101} facets to {010} facets [193,194], due to their different surface
g-C3 N4 and efficient separation of photogenerated electron-hole
energy (0.45 J/m2 for (101) surface and 0.98 J/m2 for (001) surface)
pairs between TiO2 and g-C3 N4 heterojunctions contribute to the
[195]. According to our previous work, the TiO2-x samples with
enhanced photodegradation of organic pollutions, water splitting
co-exposed {001}-{101} facets show enhanced photocatalytic CO2
hydrogen production and photoelectrocatalytic activities.
reduction activities and improved CH4 evolution selectivity, owing
to the enhanced solar light absorption introduced by Ti3+ and inhi-
6. TiO2-x with special morphology bition of electron-hole recombination rate induced by special facets
exposure [108], illustrated in Fig. 15.
The morphology of TiO2-x samples is one of the key factors Chen et al. employed hydrogenation treatments on anatase
for determining the performance of the catalysts [186]. Until TiO2 -{001}, TiO2 -{100} and TiO2 -{101}, respectively, to investi-
now, plenty of morphologies have been reported, such as TiO2-x gate the different properties of these reduced surfaces [196]. The
nanotube arrays (NTAs), TiO2-x nanosheets with special facets hydrogenated TiO2 -{001} shows the highest concentration of Ti3+
species and F1 color centers among these reduced nanocrystals. tubes with inner and outer surface promote deep light penetra-
And the photocatalytic performance of TiO2 -{001} increased after tion and electron diffusion on the catalyst (SEM and TEM images
hydrogenation treatment, while that of TiO2 -{100} and TiO2 -{101} of TiO2-x nanotubes are shown in Fig. 17). The authors demon-
displayed less changes [196]. strated that the Ti3+ species could work as co-catalyst instead of
In order to introduce {001} facets into TiO2 photocatalyst, noble-metals for high photocatalytic hydrogen evolution, both for
hydrofluoric acid was usually used as structure-directing agent, high-pressure H2 treated TiO2 [206] and implanted TiO2 samples
because [001] is energetically preferable for fluorine-terminated [97]. However, amorphous layers around the surface of TiO2 , which
surfaces [197]. Si et al. reported the fabrication of Ti3+ doped TiO2 is usually obtained after hydrogenation or Al reduction [4,10], were
nanosheets with dominant {001} facets using zinc as the reduc- observed both for non-implanted and implanted samples, reported
tant [198]. Zn powder contributes to not only the formation of Ti3+ by Liu et al. [97]. After implantation, the amount of amorphous
species but also the stabilization of the formed Ti3+ , confirmed by layer will become higher. Cui et al. reported that the Al-reduced
other literatures [29,68,69]. As a halogen element, although the sur- black TiO2 nanotube arrays could be used as photoanode of pho-
face terminated effect of Cl− is weaker than F− , chloride can also be toelectrochemical cells for high water-splitting efficiency [71]. The
used to serve as surface capping and structural shaping reagent. Pei improved charge transfer and separation induced by nanotubes and
et al. synthesized {001}-TiO2-x in a F-free system, and the catalyst enhanced visible light absorption caused by Ti3+ doping contribute
shaping and surface energy reduction were probably controlled by to the final improvement of photocatalytic or PEC performance.
Cl− anions (Fig. 16a) [68]. Zhu et al. reported that Ti3+ self-doping TiO2 nanotubes showed
Cai et al. fabricated Ti3+ self-doped TiO2 with {001} facets enhanced field emission (FE) properties compared to the pristine
by hydrothermal treatment of tetrabutyl titanate, Ti powder and one, for the TiO2-x nanotubes obtained by hydrogenation [207]
hydrofluoric acid at 200 ◦ C [41]. Ti powder was used as the reduc- or cathodic reduction process [33]. Zhou et al. also introduced
tant in the acid solution. However, Wang et al. reported that Ti3+ species into TiO2 nanotube arrays by cathodic polarization
hydrothermal treatment at higher temperature (240 ◦ C) on tetra- treatment, in order to improve the electrochemical response of
butyl titanate with the presence of HF aqueous solution could TiO2 NTAs used as electrode material for supercapacitors, due to
directly promote the formation of Ti3+ [199]. The formation of Ti3+ the decrease of charge-transport resistance and large surface area
was caused by the substitution of fluoride atoms. Besides, hydro- [208]. Compared to other chemical doping methods, the electro-
genation of the F-modified TiO2 sample can realize the doping chemical reduction treatment facilitates self-doping of Ti3+ into
of Ti3+ into the high-percentage {001}-TiO2 samples [48]. Except TiO2 catalysts, without introduction of heteroelements or struc-
for these thermal techniques, a non-thermal dielectric barrier dis- tural disturbance [31].
charge plasma treatment was introduced to promote the formation
of Ti3+ and disorder layers in TiO2 [126]. By changing the working 6.3. TiO2-x with ordered structures
gases, other elements such as N could also be incorporated into the
lattice of {001}-TiO2 . To meet the requirement for high photocatalytic performance
For rutile TiO2 samples, DFT calculations shows that the removal of the catalyst, synthesis of TiO2 samples with well-defined struc-
of a neutral bridging oxygen atoms on rutile TiO2 (110) surface pro- ture and high surface area is considered. Wen et al. synthesized
motes the generation of two unpaired electrons which are localized reduced mesoporous TiO2 photocatalyst by self-assembly method
at the 3d orbitals of neighboring 5-coordinated Ti atoms [200]. using F127 as the soft template agent [209]. The generation of Ti3+
And Wang et al. reported that the positively charged bridging oxy- was introduced by the partial oxidation of TiCl3 , with abundant oxy-
gen vacancy (BOV+ ) is the easiest to form compared with neutral gen vacancies formed in the bulk of TiO2 . The mesoporous structure
BOV and dication BOV2+ [201]. Therefore, the main point vacancies and self-doping of Ti3+ account for the enhanced photocatalytic
on rutile TiO2 (110) surface is positively charged bridging oxygen activities of the catalysts. Templated based approach is efficient
vacancy. Zuo et al. [6] and Pei et al.[202] synthesized reduced TiO2 for the synthesis of defined-structural TiO2 samples, however, the
with {111} and {110} facets co-exposure starting from Ti pow- introduction of uniform structure is sometimes difficult and also it
der and TiH2 , respectively (Fig. 16b). The formed {111} and {110} is not easy to remove the template agent. Hu et al. reported meso-
facets act as hole and electron collectors, respectively, which results porous black TiO2 hollow spheres via a template-free hydrothermal
into the separation of photogenerated carriers [203]. Compared to method (Fig. 18a) [50]. Self-reduction was achieved by thermal
unregularly shaped TiO2 nanoparticles, these reduced TiO2 with treatment at H2 atmosphere, and the thermostable hollow struc-
special exposed facets could achieve improved water splitting effi- ture could be maintained up to 900 ◦ C. The authors demonstrated
ciency, benefitting from the extended solar light response by Ti3+ that the reduction of mesoporous TiO2 hollow spheres leads to the
and inhibited electron-hole recombination by dual-facets [6,202]. change of built-in electric field and surface band bending, mak-
ing the electrons much easier to escape from TiO2 to co-catalysts
[50]. As the result, the electron transfer from TiO2 surface to
6.2. TiO2-x nanotube arrays the co-catalysts is promoted and that reducing the photogener-
ated electron-hole recombination. In addition, the utilization of
The unidirectional architecture of TiO2 nanotube arrays pro- solar light is enhanced because of the reflection of light within
vides inner and outer surface, allowing the photocatalyst with the hollow structure. Tang et al. reported that the hollow micro-
high surface area and better electron transfer efficiency. In general, sphere structure of TiO2 can greatly improve the photocatalytic
anodization process is often used to grow TiO2 nanotube arrays performance [210]. Therefore, the unique hollow porous TiO2
starting with Ti foils. Zhang et al. and Kang et al. treated TiO2 nan- structure (Fig. 18b) is demonstrated to present excellent lithium
otube arrays with liquid phase reduction process using NaBH4 as storage performance, making this material a super anode for LIBs
the reductant [204,205]. The reduction of Ti4+ was facilitated by [18]. The proposed formula of reversible Li+ insertion-extraction
the atomic hydrogen released by NaBH4 [7,57]. Surface oxygen of the hollow TiO2 porous materials is shown as follows [18]:
vacancies induced by NaBH4 contribute to the band gap narrow- TiO2−x + yLi+ + ye− ↔ Liy TiO2−x .
ing, and also serve as charge carrier trappers, decreasing charge Except for hollow sphere structure, the multiple reflection of
recombination centers [205]. light could be also realized within the core-shell [211] or yolk-
Liu et al. employed high-energy proton ion-implantation on shell [212] structure of TiO2-x , to make more efficient use of solar
TiO2 NTAs to introduce Ti3+ species into the catalyst [97]. The long light. Other well-shaped structure such as nanocages are reported
Fig. 16. (a) TEM images of {001}-TiO2-x single crystals reduced by Zn powder during the preparation. Inset is the corresponding fast-Fourier transform pattern of the catalyst.
The lattice fringe spacing of 0.35 and 0.47 nm correspond to the {101} and {002} facets, respectively. Reprinted with permission from ref. [68], Copyright 2015 Nature
Publishing Group. (b) TEM image of rutile TiO2 single crystal with co-exposed {111} and {110} facets. Inset is the oriented [110] selected area electron diffraction (SAED)
pattern of this catalyst. Reprinted with permission from ref. [6]. Copyright 2012 Wiley-VCH.
Fig. 17. SEM images of TiO2-x nanotubes reduced by high-energy proton ion-implantation from top (a) and side (c) view, respectively. Reprinted with permission from ref.
[97], Copyright 2015 American Chemical Society. Top (b) and side (d) view TEM of the TiO2-x nanotube arrays prepared by Al reduction process. Reprinted with permission
from ref. [71], Copyright 2014 Royal Society of Chemistry.
(Fig. 18c) [213]. Light trapping effect could be realized on black in situ H2 reduction of the blank TiO2 inverse opals [214]. The field
TiO2 with nanocage structure, to enhance solar light harvesting. emission scanning electron microscopy (FE-SEM) image of TiO2-x
The special structure will promote multiply scatter of solar light inverse opals is displayed in Fig. 18d. Finally, the synthetic effect
and provide enough path length and residence time for the light between inverse structure and hydrogen corporation accounts for
within the nanocages. And Zhu et al. proposed that the black colored its improvement of photodegradation of methylene blue.
TiO2-x catalyst could localize the temperature increase just at the
air-water interface rather than heating the bulk of water, making
this catalyst an efficient material for solar desalination [213]. 7. Summary and outlook
Qi et al. combined physical (slow light effect of photonic crys-
tals) and chemical routes (self-doping of Ti3+ ) for the improvement The modification methods of TiO2-x material have been dis-
of photocatalytic performance [215]. The TiO2 inverse opals were cussed in this review, for the further improvement of photocatalytic
synthesized using polystyrene sphere (PS) arrays as the hard tem- performance of TiO2 photocatalysts. Nitrogen was proved to be an
plates, and Ti3+ was introduced by vacuum activation process. The efficient non-metal element for the doping of TiO2 samples. The
obtained highly ordered inverse opal structure helps to enhance the synergistic effect between N and Ti3+ species is investigated during
light absorption (slow light effect), while the doping of Ti3+ species the formation of themselves, as well as in the photocatalysis pro-
shift the absorption edge of TiO2 to the visible light region, as illus- cess. Except for nitrogen, doping with other non-metal elements
trated in Fig. 19. Xin et al. reported reduced TiO2 inverse opals by were also discussed, such as boron, sulfur, fluorine and iodine.
Noble metals (Au, Pt, Pd and Ag) are grafted on the surface of
Fig. 18. (a) SEM image of the mesoporous black TiO2 hollow sphere treated by H2 thermal reduction. Reprinted with permission from ref. [50], Copyright 2016 Royal Society
of Chemistry. (b) TEM image of the hollow TiO2-x porous sphere after calcination at H2 atmosphere. Reprinted with permission from ref. [18], Copyright 2015 Springer. (c)
SEM image of the black TiO2 nanocages reduced by Al. Reprinted with permission from ref. [213], Copyright 2016 American Chemical Society. (d) FE-SEM of black TiO2 inverse
opals. Reprinted with permission from ref. [214], Copyright 2015 Royal Society of Chemistry.
TiO2-x , core-shell or yolk-shell structured TiO2-x , TiO2-x inverse-

opals, are reported.
However, there are still some challenging issues left to solve
and new challenges to face on TiO2-x catalysts. For example, the
proposed mechanism for the electron transfer between dopants
and the reduced TiO2 surface should be evidenced through a more
provable way. And how these defective sites in the bulk of TiO2-x
make an effect to the surface compounds requires deeper investi-
gations. It is hoped that this review will encourage new approaches
for preparation and modification of TiO2-x photocatalysts, and the
understanding of this kind of material will provide new view for
designing other defective materials.
Fig. 19. Schematic illustration of slow light effect (physical enhancement) and Ti3+ Notes
doping effect (chemical enhancement) of recued TiO2 inverse opals. Reprinted with
permission from ref. [215], Copyright 2014 Elsevier.
The authors declare no conflict of interests.
Acknowledgements
TiO2-x samples, act as co-catalyst because of the electron-rich sites.
The SPR effect of noble metal provides TiO2-x material a new path This work has been supported by National Nature Sci-
for electron transfer. Except for noble metals, the grafting of Cu, ence Foundation of China (21577036, 21377038, 21237003 and
iron-group metal (Fe, Co and Ni) and metal compounds are stud- 21677048), the National Basic Research Program of China (973 Pro-
ied. Based on the high conductivity property and unique structure, gram, 2013CB632403), State Key Research Development Program
graphene, carbon nanotubes and g-C3 N4 are introduced in TiO2-x of China (2016YFA0204200), “Chenguang Program” supported
compositing, which lead to efficient charges separation and trans- by Shanghai Education Development Foundation and Shanghai
fer properties. Special facets exposure makes a significant effect on Municipal Education Commission (14CG30), the Science and Tech-
the active sites formation and electron transfer of the catalyst, espe- nology Commission of Shanghai Municipality (16JC1401400) and
cially the dual-exposure of anatase {001}-{101} facets and rutile the Fundamental Research Funds for the Central Universities
{111}-{110} facets. In addition, TiO2-x with ordered structures such (222201717003). W. Fang thanks the China Scholarship Council
as TiO2-x nanotube arrays (NTAs), TiO2-x nanosheets, mesoporous (CSC, file No. 201406740019) for the doctoral fellowship.
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Journal of Photochemistry and Photobiology C: Photochemistry Reviews 32 (2017) 21–39

Contents lists available at ScienceDirect

Journal of Photochemistry and Photobiology C:

Modiﬁcations on reduced titanium dioxide photocatalysts: A review

6. TiO2-x with special morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

Recently, reduced TiO2 (TiO2-x ) materials have received much

at high temperature and high H2 pressure, Lu et al. developed a

2.2. Properties and characterizations of TiO2-x photocatalysts

Chen et al. reported that the disorder lattice introduced mid-

2.3. Applications of TiO2-x photocatalysts 3.1. Doping with nitrogen

Compared to other noble metals, Ag is cheaper and easier to

4.2. Non-noble-metal-based TiO2-x materials

Recently, using Cu species as co-catalyst for TiO2 has attracted

platform for charge transfer while combining with other semi-

the most immediate application for graphene. Beneﬁting from its

5.2. Other carbon-based composite materials

Zhang et al. synthesized TiO2-x and carbon nanotubes (CNTs)

exposure, mesoporous TiO2-x , core-shell or yolk-shell structured

TiO2-x , core-shell or yolk-shell structured TiO2-x , TiO2-x inverse-

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