Green Chemistry Letters and Reviews

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Modification strategies of TiO2 for potential

applications in photocatalysis: a critical review

M. Humayun, F. Raziq, A. Khan & W. Luo

To cite this article: M. Humayun, F. Raziq, A. Khan & W. Luo (2018) Modification strategies of
TiO2 for potential applications in photocatalysis: a critical review, Green Chemistry Letters and
Reviews, 11:2, 86-102, DOI: 10.1080/17518253.2018.1440324

To link to this article: https://doi.org/10.1080/17518253.2018.1440324

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GREEN CHEMISTRY LETTERS AND REVIEWS, 2018
VOL. 11, NO. 2, 86–102
https://doi.org/10.1080/17518253.2018.1440324

Modification strategies of TiO2 for potential applications in photocatalysis:

a critical review
M. Humayuna, F. Raziqb, A. Khanc and W. Luoa
a
Engineering Research Center for Functional Ceramics of the Ministry of Education, School of Optical and Electronic Information, Huazhong
University of Science and Technology, Wuhan, People’s Republic of China; bSchool of Physics and Institute of Fundamental and Frontier of
Sciences, University of Electronic Science and Technology of China, Chengdu, People’s Republic of China; cDepartment of Chemistry, Abdul Wali
Khan University, Mardan, KP, Pakistan

ABSTRACT ARTICLE HISTORY

TiO2 has received tremendous attention owing to its potential applications in the field of Received 25 December 2017
photocatalysis for solar fuel production and environmental remediation. This review mainly Accepted 9 February 2018
describes various modification strategies and potential applications of TiO2 in efficient
photocatalysis. In past few years, various strategies have been developed to improve the KEYWORDS
TiO2; modification strategies;
photocatalytic performance of TiO2, including noble metal deposition, elemental doping,
CO2 conversion; water
inorganic acids modification, heterojunctions with other semiconductors, dye sensitization and splitting; pollutants
metal ion implantation. The enhanced photocatalytic activities of TiO2-based material for CO2 degradation
conversion, water splitting and pollutants degradation are highlighted in this review.

1. Introduction
and environmental friendly merits (2–6). Naturally, TiO2
Semiconductor photocatalytic technology has attracted exists in three polymorphs such as rutile, anatase and
tremendous attention for effective utilization of solar brookite (7). Among these, anatase phase has been
energy in water reduction to produce hydrogen, carbon proven to be the most efficient photocatalyst, owing to
dioxide conversion to chemical fuels and pollutant degra- its high photoactivity, cheapness, stability and negative
dation for environmental remediation (1). In past few conduction band potential (8). It is widely investigated
years, TiO2 has been extensively studied as a potential in photocatalysis and as electrode material (9). Due to
photocatalyst for CO2 conversion, water splitting and the high stability and redox properties of anatase TiO2,
degradation of hazardous contaminants in both it has been used in various fields, such as solar cells,
aqueous and gaseous system owing to its low cost, high water and air purification, cancer therapy and self-clean-
stability, non-toxicity, biologically inertness, redox ability ing of antibacterial materials (10,11). The presence of

CONTACT W. Luo luowei@mail.hust.edu.cn

© 2018 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
 GREEN CHEMISTRY LETTERS AND REVIEWS 87

high-density surface hydroxyl groups slow down the the band gap energy (Eg) of semiconductors. Thus, under
recombination of photogenerated charge carriers. The solar irradiation, the electrons are excited from the
highly specific surface area and anatase crystallinity valence band (VB) to its conduction band (CB) and
greatly influence the photocatalytic performance of initiate reduction reactions on the catalyst surface. On
TiO2. It is widely accepted that photocatalytic reactions the other hand, the holes left in the VB take part in oxi-
mainly take place on the surface of photocatalysts and dation reactions. When the electron–hole pairs are not
the adsorption of pollutants in advance is one of the used in photocatalytic reactions, they recombine very
most important steps in photocatalytic reactions. Thus, fast and release energy in the form of heat. The basic
the large surface area is generally favorable to principles for redox reactions in semiconductor photoca-
enhance photocatalytic activity during photocatalysis talysts are shown in Figure 1(A). First, photogenerated
(12,13). However, the large intrinsic band gap (Eg = electron–hole pairs are produced. Second, the elec-
3.2 eV), fast recombination of photogenerated charges tron–hole pairs are separated and diffused to the elec-
and limited utilization of solar-light (ca. 4%) greatly trode surface. Third, redox reactions take place on the
limits the practical applications of anatase TiO2. photocatalyst surfaces (22). Among the semiconductor
Further, at high temperature (500–600°C) treatment, oxide photocatalysts, TiO2 an n-type semiconductor
anatase phase transforms into rutile phase and resulting shows optical absorption in UV-region (λ < 400 nm) of
in the decrease photocatalytic activities under normal solar spectrum. Its CB level (−0.3 eV) is more negative
conditions (14). To overcome the above-mentioned and suitable for the redox potential of H+/H2 (0 eV),
shortfalls, extensive research is underway to develop while its VB level (2.9 eV) is more positive than the stan-
new routes to modify TiO2 by doping metal and non- dard redox potential of O2/H2O (1.23 eV) vs. normal
metal elements, coupling other semiconductor materials hydrogen electrode (NHE) as depicted in Figure 1(B).
and surface modification with inorganic acids (15–17). It When TiO2 is irradiated under solar-light, electron–hole
has been investigated that doping elements such as S, pairs are produced. The electrons in the CB reduce H+
C, N and B could greatly extend the absorption capacity ions to evolve H2 and the holes in the VB oxidize H2O
of TiO2 from UV to visible region. These elements could to form O2 (23). Similarly, TiO2 is also a potential candi-
easily substitute the oxygen atoms from the lattice of date for both CO2 conversion to chemical fuels and pol-
TiO2 and decrease its band gap by contributing their lutant oxidation to inorganic minerals. However, the
p-orbitals (18–21). This alters the electronic properties wide band gap and fast recombination of photogener-
of TiO2 and results in the enhanced reaction rates for ated charge carrier’s (electron–hole pairs) still greatly
photocatalytic processes. Similarly, the heterojunctions limits its practical applications. To overcome these short-
with noble metals and other semiconductors also play falls, various attempts have been made. Among them,
a vital role in the enhanced photocatalytic activities of doping metal and non-metal elements to extend its
TiO2. Besides, modifications with inorganic acids are optical absorption and enhance charge carriers separ-
much meaningful to improve the photocatalytic activi- ation, fabricating heterojunctions with other semicon-
ties of TiO2. ductors to improve charge transfer and separation,
In this review, we have summarized various modifi- surface modification with inorganic acids, noble metal
cation strategies of TiO2 by doping metals and non- deposition, metal ion implantation, and dye sensitization
metals, by constructing heterojunctions with noble are widely investigated (24).
metals and semiconductor oxides and modification
with inorganic acids. Further, the photocatalytic mechan-
isms for water splitting, CO2 reduction and pollutants
degradation have been explained elaborately. Although
a number of review articles give deep insight into the
structure modification and catalytic performances of
TiO2 photocatalyst. This review attempted to provide
detail knowledge on the structure modification, photo-
catalytic mechanisms and applications of TiO2 in
photocatalysis. Figure 1. (A) Photogenerated charge carrier’s in semiconductors.
Eph represent energy of the photon used. A means electron
acceptor and D means electron donor. (B) Schematic illustration
2. TiO2 photocatalysis for the band gap structure showing the CB and VB positions of
TiO2 and the redox potentials vs. NHE. Adapted from references
Semiconductor oxide photocatalysts could absorb solar- (23) and (24) with permissions. Copyright 2015 and 2012, Royal
light, when the energy of the incident photons matches Society of Chemistry.
88 M. HUMAYUN ET AL.

3. Modification strategies of TiO2 depicted in Figure 3(A). This greatly extended the
optical absorption of TiO2 from UV to visible region. It
3.1. Doping metal and non-metal elements
was found that the incorporation of electrons deficient
It is widely accepted that the lattice structure and surface S atoms into the crystal lattice of TiO2 has effectively cap-
composition greatly affect the functionalities and effi- tured the photoinduced electrons and reduced charge
ciency of nanomaterials. Many researchers found that carrier’s recombination. Further, S-doping generated
introducing electronically active secondary species into surface oxygen vacancies, which acted as trapping
the crystal lattice of nanomaterials greatly alter its center for the photogenerated electrons and reduced
optical absorption and suppress the charge carrier’s the recombination of electron–hole pairs. The synergistic
recombination. In 2014, Hou et al. (25) reported the effect of efficiently reduced charge carrier’s recombina-
hydrothermal synthesis of N-doped TiO2 nanotubes, tion and extended visible-light absorption resulted in
which were immersed in deionized water and various the enhanced visible-light photocatalytic performance
concentration ammonia solution. They investigated of S-doped TiO2 for methyl orange (MO) degradation.
that the molar ratio between deionized water and Wu et al. (28) reported the synthesis of C-doped TiO2
ammonia aqueous solution had a great effect on the by a facile solvothermal method. It has been demon-
morphology of TiO2 nanotubes. They found that the strated that the incorporation of carbon atoms into the
samples immersed in ammonia solution have higher crystal lattice of TiO2 substituted oxygen atoms and
absorption than that immersed in water. Further, the resulted in the generation of oxygen vacancies. The
band gap was effectively reduced from 3.2 to 2.84 eV, band gap was considerably reduced from 3.2 to
after doping nitrogen and facilitated the photogener- 2.39 eV, and the optical absorption was greatly altered.
ated carrier’s separation. This resulted in the dramatically This resulted in the enhanced visible-light photocatalytic
enhanced visible-light activity of N-doped TiO2 nano- activities of TiO2 for nitric oxide (NO) and methyl orange
tubes for methyl orange (MO) degradation. The sche- (MO) oxidation, which is much superior to P25 and N-
matic band gap structure of TiO2 and N-doped TiO2 is TiO2 photocatalysts. The schematic band gap structure
displayed in Figure 2(A). Recently, McManamon et al. is shown in Figure 3(B).
(26) reported the sol–gel synthesis of S-doped TiO2 nano- Sood et al. (29) reported the synthesis of Fe-doped TiO2
particles. They investigated that S occupy some intersti- by ultrasonic-assisted hydrothermal method. It was inves-
tial sites in the crystal lattice, which results in the tigated that the incorporation of Fe into the crystal lattice
generation of surface states between the VB and CB of of TiO2 favored the substitution of Ti, as both have
TiO2. It is noticed that the incorporation of S into the approximately the same ionic size. From UV-visible
crystal lattice dramatically reduced the band gap of absorption spectra, it was observed that Fe doping
TiO2 from 3.2 to 1.7 eV and facilitated visible-light extended the absorption of TiO2 from UV to visible
absorption as shown in Figure 2(B). It was found that region. The band gap was effectively reduced from 3.2
after doping S, the visible-light activity of TiO2 for mala- to 2.9 eV that resulted in the enhanced visible-light
chite green degradation was greatly enhanced. photocatalytic activity for paranitrophenol degradation.
Bakar et al. (27) reported the synthesis of S-doped TiO2 The schematic mechanism for pollutant degradation by
photocatalysts by template-free oxidant peroxide route Fe-doped TiO2 photocatalyst is depicted in Figure 4(A).
followed by crystallization through hydrothermal tech- Roy et al. (30) reported the synthesis of Cu-doped TiO2
nique. It was investigated that doping S into the crystal by facile hydrothermal method. They demonstrated that
lattice of TiO2 substituted oxygen atoms by sulfur the band gap of TiO2 was significantly reduced from
anions and resulted in the narrowed band gap as 3.2 eV to 2.06 eV. Further, the intermediate surface
states were produced between the VB and CB of Cu-

Figure 2. Schematic illustration of the energy band structures (A) Figure 3. Schematic illustration of the band gaps and photoca-
TiO2 and N-doped TiO2, (B) TiO2 and S-doped TiO2. Adapted from talytic processes on S-doped TiO2 (A), and C-doped TiO2 (B).
references (25) and (26) with permissions. Copyright 2014 and Adapted from references (27) and (28) with permissions. Copy-
2015, Elsevier Ltd. right 2016, Royal Society of Chemistry. and 2013, Elsevier Ltd.
 GREEN CHEMISTRY LETTERS AND REVIEWS 89

Figure 4. Schematic illustration of the band gaps structure and

photocatalytic processes (A) in Fe-doped TiO2 and (B) Cu-
doped TiO2. Adapted from references (29) and (30) with per-
missions. Copyright 2015, Elsevier Ltd. and 2014, American
Chemical Society.
Figure 5. Schematic illustration for the possible reaction mech-
anism of photocatalytic CO2 reduction with H2O: (A) photocata-
doped TiO2 and the transitions in visible-light was
lytic CO2 conversion and redox reactions over In-doped TiO2
explained on the basis of d-orbital splitting of transition and (B) photogenerated charge carrier’s recombination and sep-
metals as depicted in Figure 4(B). They suggested that aration. Adapted from reference (31) with permission. Copyright
the VB of TiO2 is composed of Ti−O 2σ, Ti−O 2π, and O 2015, Elsevier Ltd.
2π molecular orbitals. Similarly its conduction band
bottom consists of Ti−Ti σ, Ti−Ti σ*, Ti−Ti π, Ti−Ti π*, activities. Naturally, it is accepted that the surface modi-
and Ti−O π* molecular orbitals while the CB top has Ti fication with inorganic acids greatly promotes the
−O σ* molecular orbitals. The energy level of π* orbitals adsorption of O2 on the photocatalyst surface, which is
in Cu-doped TiO2 shifted toward the VB maxima and much crucial for photocatalytic activities (32). He et al.
increased the atomic number of transition metal. As a (33) reported the hydrothermal synthesis of sulfuric
result, the energy levels of σ*(1) and σ*(2) were shifted acid modified TiO2 nanosheets. They investigated that
up and downward and resulted in the narrow energy H2SO4 modified TiO2 with {0 0 1} and {1 0 1} facets
gap. The σ*(1) and σ*(2) molecular orbitals of Cu-TiO2 exhibit superior photocatalytic activity for CO2 conver-
were found to be located near to the water and peroxides sion to CH4 and H2O oxidation under visible-light
oxidation potentials. Hence, they directly interact with the irradiation. These enhanced activities were attributed
σ orbitals of the intermediate products thereby reducing to the promoted surface OH groups, the generated
the over potential of oxygen evolution reactions. oxygen vacancies and improved visible-light absorption.
Tahir et al. (31) reported the synthesis of In-doped Further, it was investigated that the surface protonation
TiO2 nanoparticles by sol–gel method. It was found resulted from acid modification improved the photogen-
that the absorption band edge of In-doped TiO2 was erated charge carrier’s lifetime of TiO2 nanosheets and
slightly shifted toward lower wavelength direction and also prevailed the limitation of unfavorable side length
resulted in the enlarge band gap. Further, the incorpor- for photogenerated charge carrier’s migration. Moreover,
ation of Indium into the crystal lattice of TiO2 has signifi- the photocatalyst showed high stability during the
cantly increased the surface active sites and also photocatalytic conversion of CO2. The mechanism of
suppressed the photogenerated charge carrier’s recom- CO2 reduction and water oxidation over bulk anatase
bination. As a result, the photocatalytic activity for CO2 TiO2 and sulfuric acid modified TiO2 nanosheets is
reduction under UV-light was obviously increased. The depicted in Figure 6(A,B).
main product during CO2 reduction over TiO2 photocata-
lyst was CO, while Indium-doping remarkably enhanced
the CH4 yield. The photocatalytic processes and charge
carriers recombination and separation in TiO2 and In-
doped TiO2 photocatalyst is depicted in Figure 5(A,B).

3.2. Modification with inorganic acids

It has been demonstrated that surface modification with
inorganic acids can greatly alter the surface carried
charge properties of TiO2 photocatalyst in neutral
Figure 6. Schematic illustration for the energy band gap of the
water. The newly introduced surface groups could bulk (A) and sulfuric acid modified anatase TiO2 and the relevant
greatly promote the separation of photogenerated redox potentials for CO2 and H2O (B). Adapted from reference
charge carriers, leading to the enhanced photocatalytic (33) with permission. Copyright 2016, Elsevier Ltd.
90 M. HUMAYUN ET AL.

Cao et al. (34) reported the surface modification of TiO2

nanoparticles by simple post-treatment with monometal-
lic sodium orthophosphate solution. It was found that
phosphate modification has greatly promoted the
adsorption of O2 on the surface of TiO2 photocatalyst.
The enhanced adsorption of O2 was attributed to the sub-
stitution of –Ti–OH with –Ti–O–P–OH groups. As a result,
the photogenerated electrons were effectively captured
by the surface promoted O2, and the activities for photo-
catalytic degradation of pollutants were significantly
improved. The surface forms of un-modified and phos-
phate-modified TiO2 are depicted in Figure 7(A,B). Figure 8. Schematic illustration for photoelectrochemical (PEC)
water oxidation by cobalt (II) phosphate-modified TiO2.
Liu et al. (35) reported the cobalt phosphate-modified Adapted from reference (35) with permission. Copyright 2013,
TiO2 films, which were prepared by the post-treatment of American Chemical Society.
TiO2 films with monometallic sodium orthophosphate
solution followed by cobalt nitrate solution. They
demonstrated that the photoelectrochemical water oxi-
dation of TiO2 photocatalyst was greatly enhanced
after modification with cobalt phosphate. This enhanced
activity was attributed to the role of Co (II) ions linked
with the surface of TiO2 through phosphate groups. It
was confirmed that the surface linked cobalt (II) ions
could effectively capture the photogenerated holes
and generate high valence Co ions, which further
induce oxidation reaction with H2O molecules and
return to its original oxidation state. The schematic
mechanism for the holes captured by Co (II) and the Figure 9. Schematic illustration for the surface structure of
improved photoelectrochemical (PEC) water oxidation unmodified (A) and HF modified TiO2 in atmosphere and water
of TiO2 after modification with Co (II) phosphate is (B). Adapted from reference (36) with permission. Copyright
depicted in Figure 8. 2013, American Chemical Society.
Luan et al. (36) reported the synthesis of hydrofluoric
acid controlled 001-facet TiO2 nanoparticles by hydro- −Ti:F−H bond greatly enhanced the adsorption of O2 on
thermal method. They observed that the 001-facet TiO2 the surface of TiO2. Hence, the photogenerated electrons
exhibit exceptional photoactivities for pollutants degra- were effectively captured by the adsorbed O2 and charge
dation as compared to the unmodified TiO2. The carrier’s separation was improved.
enhanced photoactivities were attributed to the residual
HF linked to the TiO2 surface via coordination bond
between Ti4+ and F- as depicted in Figure 9. The resultant
3.3. Constructing heterojunctions
The utilization of solar energy in a cost-effective manner
is a mean of meeting the global energy demand and
environmental remediation. Hence, it is highly desirable
to convert solar-light into an energy storage medium
(37). The photocatalytic water splitting to produce H2
and O2, CO2 conversion to chemical fuels and pollutant
degradation under direct solar irradiation are the main
issues of scientific research nowadays. The direct water
splitting and CO2 reduction can be achieved using a
single semiconductor. However, the proper redox poten-
tials and effective absorption of visible-light are both the
Figure 7. Schematic for the surface forms of un-modified (A) and fundamentals of photocatalytic processes (38). In
phosphate-modified TiO2 (B). Adapted from reference (34) with general, the semiconductor photocatalyst should have
permission. Copyright 2012, Royal Society of Chemistry. a wide band gap with proper VB and CB positions to
 GREEN CHEMISTRY LETTERS AND REVIEWS 91

provide effective separation of photogenerated charges, 3.3.1. Noble-metals-TiO2 heterojunctions

transfer energetic electrons and high stability toward Recently, it has been investigated that incorporation of
photocorrosion. Semiconductor TiO2 fulfill all these noble metals into the crystal lattice of wide band gap
requirements, but unfortunately the low quantum yield semiconductors such as TiO2 have significantly improved
limits its practical application. This is because; TiO2 the photocatalytic activity of TiO2 in visible-light region
could absorb only UV-light, which accounts for ca. 4% due to surface plasmon resonance (SPR) effect of noble
of solar spectrum (39). To overcome this shortfall, con- metals. It has been demonstrated that the surface
structing heterojunctions with noble metals and other plasmon resonance effect mainly arises from the collec-
semiconductor oxides with wide and narrow band tive oscillations of electrons on surfaces of noble metal,
gaps are widely employed. Constructing heterojunctions and these energetic electrons transfer into the conduc-
could effectively improve the optical absorption, charge tion band of the coupled semiconductor due to the
carrier’s separation and stability of TiO2 photocatalyst. Schottky barrier. Schottky barrier between noble metals
Therefore, it is highly desirable to choose suitable photo- and semiconductor oxides arises via Fermi levels equili-
catalysts for coupling, in order to improve the stability brium, as a result built-in electric field is formed at the
and efficiency of TiO2 photocatalyst. Photocatalysts interface which favors separation of photogenerated
with large surface area exhibit more active sites, which charges as depicted in Figure 10 (40,41).
is much crucial for photocatalytic reactions. Besides, Ismail et al. (42) reported the synthesis of Pt/TiO2
the proper band gap and band edge alignment is also nanocomposites by photodeposition and in-situ
a key point because the relative energy level at interface methods. TEM images of Pt/TiO2 nanocomposites
junction also reveals the charge separation direction and (Figure 11(A)), prepared via photodeposition method
transportation. Based on the above consideration, the revealed that the pt nanoparticles with average diameter
heterojunctions are categorized into two classes; noble- of ∼3 nm are uniformly dispersed on the surface of TiO2
metals-TiO2 heterojunctions and semiconductor oxides- nanoparticles. On the other hand, the TEM images of Pt/
TiO2 heterojunctions. TiO2 nanocomposites obtained via in-situ method

Figure 10. Equilibrium position of Semiconductor-Metal nanocomposites with Redox Couple (A) before and (B) after UV-Irradiation.
Schematic illustration of photogenerated charge transfer and separation in semiconductor-metal heterojunctions (C) under UV-light
and (D) under visible-light irradiation. Adapted from references (40) and (41) with permissions. Copyright 2004, American Chemical
Society and 2013, Royal Society of Chemistry.
92 M. HUMAYUN ET AL.

Figure 11. TEM images of mesoporous Pt/TiO2 nanocomposites calcined at 450°C for 4 h: PtTiO2-3 (A) and in situ prepared PtTiO2-1 (B).
HRTEM image of PtTiO2-3 (C), Dark-field TEM image of mesoporous PtTiO2-1 nanocomposites (D) and PtTiO2-3 nanocomposites (E).
Schematic for the photocatalytic degradation of dichloroacetic acid over Pt/TiO2 nanocomposites (F). Adapted from reference (42)
with permission. Copyright 2011, American Chemical Society.

(Figure 11(B)), showed that the Pt nanoparticles with with d-spacing (d = 0.35 nm) and (200) direction lattice
average diameter of ∼15 nm are in close contact with fringes with d-spacing (d = 0.23 nm) for TiO2 and Au,
TiO2 nanoparticles. HRTEM image of Pt/TiO2 nanocompo- respectively. The activity of the as-prepared nanocompo-
site is shown in Figure 11(C), while the dark-field TEM sites was evaluated for photocatalytic water splitting in
image of mesoporous Pt/TiO2 nanocomposite and Pt/ the presence of electron donor (ascorbic acid), under
TiO2 nanocomposite is shown in Figure 11(D and E). visible light as shown in Figure 12(C). All the samples
The photocatalytic activity of both type nanocomposites showed excellent photocatalytic activity for H2 evolution,
was evaluated for degradation of dichloroacetic acid which were attributed to the surface Plasmon resonance
(DCA). The result showed that the photocatalytic activity effect of Au nanoparticles. To study the SPR effect of Au
of TiO2 for DCA degradation was significantly enhanced nanoparticles, they performed controlled wavelengths
by the addition of Pt islands and directly associated irradiation (500 ± 20 nm) experiments. It was confirmed
with the particle size of Pt. The activity of the nanocom- that the surface plasmon excited hot electrons transfers
posites prepared via photodeposition method was much from Au nanoparticles to the CB of TiO2; as a result, the
higher than that of nanocomposites prepared by the in- visible-light photocatalytic activity of TiO2 for water
situ method, even higher than the commercially avail- reduction was significantly enhanced. The schematic
able TiO2 (P25). This enhanced activity was attributed mechanism for hydrogen evolution over Au-TiO2 nano-
to the well-dispersed small-sized (3 nm) Pt nanoparticles composite is depicted in Figure 12(D).
on the surface of TiO2. They demonstrated that when Pt/ Dong Yang et al. (44) reported the synthesis of Ag/
TiO2 nanocomposites are irradiated with photons having TiO2 nanocomposites by two different methods. Firstly,
energy higher than the band gap of TiO2, photogener- they prepared Ag/TiO2 heterojunctions by simple ultra-
ated electrons from the valance band are excited to sonic treatment and stirring of AgNO3 and TiO2 nano-
the conduction band of TiO2 leaving the holes in the tubes (TNT) with the aid of 3-(3, 4 Dihydroxyphenyl)
valance band. The closely contact Pt nanoparticles act propionic acid (DiHPP), which acts both as a linker and
as electrons sink to promote the reduction of oxygen reducer. Secondly, they followed photochemical
on their surfaces and the holes in the valance band reduction method for the synthesis of Ag/TiO2 hetero-
migrate to the surface of photocatalysts for oxidation junctions without adding DiHPP. In the prepared Ag/
of organic pollutants as depicted in Figure 11(F). TNT composite, about 3.8 nm in diameter of Ag nano-
Jun Fang et al. (43) reported the synthesis of Au-TiO2 crystals were uniformly dispersed over the TiO2 nano-
nanocomposites by a co-polymer assisted sol–gel tubes (TNT) surface and formed the heterojunction
method. From TEM micrograph (Figure 12(A)), it was con- structure with TiO2 nanotubes (TNT). They demonstrated
firmed that Au and TiO2 nanoparticles are in close that the DiHPP first links to the TiO2 nanotubes (TNT)
contact with each other. HRTEM image (Figure 12(B)), surface through the bidentate chelation of catechol
showed well resolved (101) direction lattice fringes group with Ti4+ and then acts as both an anchor and a
 GREEN CHEMISTRY LETTERS AND REVIEWS 93

Figure 12. TEM image (A) HRTEM image (B), photocatalytic H2 production under visible light (λ > 420 nm) irradiation (C), and schematic mech-
anism for hydrogen evolution (D) of Au-TiO2 nanocomposites. Adapted from reference (43) with permission. Copyright 2012, Elsevier Ltd.

reducer to in situ nucleate and grow Ag nanocrystals on activity, which can almost degrade 100% rhodamine B
the TiO2 nanotubes (TNT) surface. By adjusting the (RhB) within 2 h. This excellent performance can be
AgNO3 concentration, the loading amount of Ag nano- attributed to the local electric field caused by the
crystals on the TiO2 nanotubes (TNT) surface can be con- surface plasmon resonance (SPR) of Ag nanocrystals
trolled easily, and the visible-light absorption ability of and the high adsorption capability of TiO2 nanotubes
Ag/TNT heterojunctions enhances with increasing the (TNT) with the large specific surface area. The TEM and
Ag loading amount. Moreover, their photocatalytic HRTEM images and the mechanism for photogenerated
activity was evaluated by the degradation capability of charge transfer and the photocatalytic degradation of
rhodamine B (RhB) under visible light. The Ag/TNT het- RhB over Ag/TNT heterojunctions under visible-light
erojunctions exhibit the high visible-light photocatalytic irradiation are shown in Figure 13.

Figure 13. TEM micrograph of TNT (A), TEM image of Ag/TNT heterojunction (B), HRTEM image (C), and TEM image of Ag/TNT nano-
composites synthesized without DiHPP (D). Schematic mechanism for charge transfer phenomenon and the photocatalytic degradation
of RhB over Ag/TNT heterojunctions under visible light (E). Adapted from reference (44) with permission. Copyright 2015, American
Chemical Society.
94 M. HUMAYUN ET AL.

3.3.2. Semiconductors-TiO2 heterojunctions charge carrier’s separation efficiency because of the for-
In semiconductors-TiO2 heterojunctions, both the com- mation of heterojunction between them (46). Recently,
ponents can be excited by photons to generate charge some researchers (47–49) found that the photoelectro-
carriers (electron–hole pairs). The charge transfer direc- chemical performance of TiO2 photoanodes could be
tion would mainly depend on the relative VB and CB obviously improved by constructing heterojunction
position of both semiconductors. Primarily, the hetero- with ZnO. Zha et al. (50) reported TiO2/ZnO nanocompo-
junctions between TiO2 and other semiconductors are sites prepared via solvothermal method. They demon-
categorized into three types as shown in Figure 14. In strated that the as-prepared nanocomposites exhibit
Type-I heterojunction, the two semiconductors should exceptional photocatalytic activity (97% in 30 min) for
be either n-type or p-type. Suppose the two semiconduc- methyl orange (MO) degradation under UV light; which
tors are represented by A and B. The CB of B should be is attributed to the hierarchical nanostructure with a
higher and its valance band should be lower than that large surface area. The SEM images (Figure 15(A,B)) and
of A. Therefore, both the electrons and holes would TEM image (Figure 15(C)) of the heterojunctions show
transfer to semiconductor A. In type-II heterojunctions, multi-layers of fan blades like morphology with an
the photogenerated electrons would transfer from B to average length of 2.5–3 mm. The HRTEM image (Figure
A, while the photogenerated holes would transfer from 15(D)) reveals that the lattice fringes with d-spacing
A to B. Such type of heterojunction is much beneficial, 0.28 nm in (101) planes correspond to anatase TiO2,
because of the effectively separation of electron–hole while the later at (100) planes are attributed to hexago-
pairs. Type-III heterojunction is similar to type-II except nal wurtzite ZnO. The photocatalytic mechanism over
for the more prominent difference in VB and CB pos- TiO2/ZnO heterojunctions is shown in Figure 15(E). As
itions, which requires a huge driving force for photogen- the energy band gap of ZnO is 3.37 eV, hence, its con-
erated charge transfer. duction band (CB) and valence band (VB) potential is a
little bit more negative than that of TiO2. When TiO2/
ZnO nanocomposite is irradiated by photon energy to
3.3.2.1. Heterojunctions with wide band gap semicon-
surpass its band gap energy, the photogenerated elec-
ductors. Since the first report on solar-driven photoelec-
trons from its VB are excited to the CB, which then trans-
trochemical (PEC) energy conversion by TiO2
fer to the CB of TiO2 due to the potential difference
semiconductor photoelectrode in 1972, TiO2 has been
between them. Simultaneously, the holes from the VB
widely investigated and regarded as one of the most
of TiO2 transfer thermodynamically to the VB of ZnO.
promising candidates for water splitting, owing to its
This results in the enhanced photoactivities of TiO2.
low cost, high stability, strong optical absorption and
Recent reports (51–53) show that SrTiO3 (3.4 eV) could
suitable band edge positions (45). However, TiO2 nor-
effectively improve the charge separation and photo-
mally suffers from the intrinsic drawback of photocorro-
electrochemical performance of TiO2 by shifting its
sion, which reduces its photoactivity and photostability.
Fermi level to more negative potential in the formed
To solve this issue, research has been proliferated to
SrTiO3/TiO2 heterojunction. Guo et al. (54) reported
improve the photostability and photocatalytic properties
SrTiO3/TiO2 nanosheet heterojunctions prepared via
of nanosized TiO2 by coupling with ZnO. It has been well-
hydrothermal method. They demonstrated that the as-
established to remarkably enhance the photogenerated
prepared SrTiO3/TiO2 heterojunction exhibit porous
structure with a high surface area. It was found that
the material exhibit enhanced charge carriers separation,
which is significant for dye sensitized solar cells (DSSCs).
The photoelectric conversion efficiency and short-circuit
current density of DSSCs based on SrTiO3/TiO2 hetero-
junctions were obviously enhanced as compared to the
pure TiO2 nanosheets. The short-circuit current density
of 12.55 mA cm−2 and photoelectric conversion effi-
ciency of 7.42% was observed for DSSCs based on the
SrTiO3/TiO2 heterojunctions under solar illumination.
The photogenerated charge transfer and separation in
SrTiO3/TiO2 heterojunction under UV-light irradiation is
Figure 14. Band gap structures and migration of the charges in
three type combination systems of TiO2 with other semiconduc- shown in Figure 16.
tors. Adapted from reference (41) with permission. Copyright It is widely accepted that TiO2 exhibit fast recombina-
2013, Royal Society of Chemistry. tion of photogenerated charge carrier’s which leads to
 GREEN CHEMISTRY LETTERS AND REVIEWS 95

Figure 15. SEM images (A, B), TEM image (C) and HRTEM image (D) of fan blades. Schematic diagram illustrating p–n junction and
charge transfer and separation mechanism in TiO2/ZnO heterojunctions under UV light irradiation (E). Adapted from reference (50)
with permission. Copyright 2015, Royal Society of Chemistry.

the low photocatalytic efficiency. In order to overcome Fermi energy level of TiO2 is higher than that of SnO2,
this shortfall, recent studies (55–58) reveal that photo- hence the photogenerated electrons of TiO2 easily trans-
generated charge separation and catalytic activities of fer to SnO2 and the photogenerated holes of SnO2 trans-
TiO2 can be obviously improved after coupling nanocrys- fer to the VB of TiO2. Therefore, the efficient charge
talline SnO2. Wang et al. (59) reported hierarchical SnO2/ separation will increase the lifetime of charge carriers
TiO2 heterojunctions. They demonstrated that under UV and then enhance photocatalytic activity. On the other
light irradiation, the nanocomposites exhibit enhanced hand, in a single component system, most of the
photocatalytic activities for Rhodamine B (RhB) degra- charges quickly recombine without doing any photoche-
dation as compared to the bare TiO2 nanofibres. This mical process and only a few charges take place in
enhanced photoactivity was attributed to the UV-light photocatalytic reactions. This results in the low photoca-
excited electrons transfer from the CB of TiO2 to the CB talytic activity. As can be seen from Figure 17(B), the PL
of SnO2. To well understand the charge transfer mechan- emission spectrum of TiO2 (TS0) is much intense com-
ism and the enhanced photoactivities, they proposed a pared to that of SnO2/TiO2 nanocomposite (TS1). This
schematic mechanism as shown in Figure 17(A). The indicates that the charge recombination is greatly inhib-
band gap and work function of anatase TiO2 is 3.2 and ited in the SnO2/TiO2 nanocomposite. This resulted in the
4.2 eV, respectively. Its electron affinity is approximately enhanced photoactivity for RhB degradation.
4.2 eV. On the other hand, the band gap and work func-
tion of rutile SnO2 are 3.5 and 4.4 eV, respectively. Its
electron affinity is 0.5 eV higher than that of TiO2. The 3.3.2.2. Heterojunctions with narrow band gap semi-
conductors. Hematite (a-Fe2O3) a narrow band gap
(∼2.1 eV) semiconductor oxide has attracted tremendous
attention owing to its potential applications as a low-cost,
high stability, natural abundance, non-toxicity, visible-

Figure 16. Schematic diagram illustrating the energy band gaps Figure 17. (A) Schematic diagram showing the energy band
and photogenerated charge transfer and separation phenom- structure and electron–hole pair separation in the SnO2/TiO2 het-
enon in SrTiO3/TiO2 heterojunction under UV light irradiation. erostructure. (B) PL emission spectra of TS0 and TS1. Adapted
Adapted from references (54) with permission. Copyright 2015, from reference (59) with permission. Copyright 2009, American
Royal Society of Chemistry. Chemical Society.
96 M. HUMAYUN ET AL.

light responsive and electrode material for photoelectro- observed that TiO2 nanoparticles exhibit an average par-
chemical (PEC) water splitting (60,61). The theoretical ticle size of about 130 nm. Moreover, the In2O3–TiO2 het-
solar-to-chemical energy conversion efficiency for Fe2O3 erojunction was confirmed by HRTEM image (Figure 19
is reported to be 16% (62). Coupling a-Fe2O3 to semicon- (B)). The lattice fringes at (101) plane with d-spacing
ductor TiO2 has seldom been reported, however, recently 0.31 nm were attributed to anatase TiO2, while the
Li et al. (63) reported the branch-shaped a-Fe2O3/TiO2 fringes at (222) plane with d-spacing 0.29 nm were attrib-
nanocomposites, which were prepared by a combine uted to In2O3. From selected area electron diffraction
electrospinning and hydrothermal approach. The nano- (SAED) patterns (Figure 19(C)), it was confirmed that
composites consist of 3D porous TiO2 nano-fibers the nanoparticles exhibit polycrystalline structure. The
(diameter ∼ 70 nm) and the coupled a-Fe2O3 nanorods visible-light photocatalytic activity of the fabricated
(length ∼ 100–200 nm). The nanocomposites exhibit nanocomposites was evaluated for RhB degradation. It
large surface area (∼ 42.8 m2 g−1). They investigated was investigated that the nanocomposites exhibit
that the resultant nanocomposites exhibit excellent superior photocatalytic activity for RhB degradation as
visible-light photocatalytic activities for degradation of compared to the TiO2 and In2O3 alone. From photocata-
organic dyes, methylene blue (MB), including Congo red lytic stability recycle test, it was confirmed that the
(CR), methyl orange (MO) and eosin red (ER). These photocatalyst exhibit high stability. The photocatalytic
enhanced activities were attributed to the large surface mechanism for In2O3–TiO2 nanocomposites was
area, extended visible-light absorption and improved designed as shown in Figure 19(D). The VB and CB pos-
photogenerated charge separation. They proposed a ition of TiO2 stand at 2.8 and −0.4 eV, respectively vs.
charge transfer and separation mechanism, which is NHE. Similarly, the VB and CB of In2O3 located at 2.17
shown in Figure 18. They demonstrated that under and −0.63 eV vs. NHE. When heterojunction is formed
visible-light (400 cutoff) irradiation, the excited high- between In2O3 and TiO2, and irradiated under visible
level energy electrons from the valance band (VB) of light, the photogenerated electrons from the VB of
Fe2O3 would transfer thermodynamically to the conduc- In2O3 would transfer to the CB of TiO2. This will reduce
tion band (CB) of TiO2, and react with molecular oxygen the recombination of electron–hole pairs. Consequently,
(O2) to produce the superoxide anion (O·− 2 ) and hydrogen the improved charge separation would enhance the
peroxide (H2O2). While the photogenerated holes in the interfacial charge transfer to the adsorbed substrates,
VB of Fe2O3 will react with hydroxyl species on the catalyst leading to a superior photocatalytic activity of In2O3–
surface and produce the highly reactive hydroxyl radicals TiO2 nanocomposites for RhB degradation.
(.OH), which are responsible for the oxidation of organic
dye pollutants.
Mu et al. (64) reported the synthesis of In2O3–TiO2
nanocomposites via electrospinning and solvothermal
techniques. They investigated that the In2O3 nanoparti-
cles with an average particle size of about 30 nm were
successfully grown onto the surface of TiO2 as confirmed
by means of TEM analysis (Figure 19(A)). Further, it was

Figure 19. TEM image (A), HRTEM image (B), SAED patterns (C),
Figure 18. Schematic for band gap structures and visible-light and schematic diagram energy band structure and charge separ-
induced charge carrier transfer and separation in a-Fe2O3/TiO2 ation (D) of In2O3–TiO2 nanocomposites. Adapted from reference
nanocomposites. Adapted from reference (63) with permission. (64) with permission. Copyright 2012, American Chemical
Copyright 2016, Royal Society of Chemistry. Society.
 GREEN CHEMISTRY LETTERS AND REVIEWS 97

CdS is a visible-light responsive n-type semiconductor,

which has been widely investigated among narrow band
gap semiconductors. It has been regarded as an attractive
material owing to its high efficiency for water reduction to
evolve hydrogen. The narrow band gap (∼2.4 eV) with suf-
ficient negative conduction band position for the
reduction potential of protons made this material more
valuable for practical applications (65). However, the
poor stability, particle agglomeration and high recombi-
nation rates of photogenerated charges still greatly
impair its practical use for large-scale water splitting
(66,67). Therefore, the fabrication of CdS-TiO2 nanocom-
posites has been attempted to diminish recombination,
improve its surface area and to stabilize the material. Liu
et al. (68) reported One-dimensional (1D) CdS@TiO2 core Figure 20. Schematic diagram for the energy band gaps and the
−shell nanocomposites (CSNs) prepared via two-step possible reaction mechanism for the selective oxidation of alco-
solvothermal method. The visible-light photocatalytic hols to the corresponding aldehydes over 1D CdS@TiO2 CSNs
activities of the as-prepared 1D CdS@TiO2 CSNs nano- under visible-light. Adapted from reference (68) with permission.
composites were evaluated for selective oxidation of alco- Copyright 2012, American Chemical Society.
hols to aldehydes. It was investigated that the
nanocomposites exhibit obviously enhanced visible- are transported to the interfacial electron acceptors
light activity for both conversion and yield as compared (e.g. H2O, I− +
3 , H , O2, etc.) and induce various redox reac-
to bare CdS NWs, which is attributed to the prolonged life- tions as depicted in Figure 21. In this way, the effective
time of photogenerated charge carriers after coupling solar energy utilization and interfacial charge transfer
TiO2. Moreover, it is noticed that the photogenerated from the excited dye to the conduction band of TiO2
holes from CdS core can be stuck by the TiO2 shell, as con- should be the key parameters to accomplish a high
firmed by means of controlled radical trapping exper- level of photo-conversion efficiency (69).
iments and the selective reduction of heavy-metal ions, Choi et al. (69) reported the synthesis of organic dye-
Cr(VI), over 1D CdS@TiO2 CSNs. Hence, it is concluded sensitized TiO2 particles for H2 evolution from H2O and 4-
that the reaction mechanism of visible-light catalytic oxi- chlorophenol and Cr(VI)) pollutants oxidation under
dation of alcohols over 1D CdS@TiO2 CSNs is actually visible-light (λ > 420 nm). They investigated the effect
different from that over 1D CdS NWs. It is demonstrated of various anchoring groups. For this, they prepared
that under visible-light irradiation (λ = 520 ± 15 nm), the Ru-free organic dyes of donor–acceptor configuration
excited electrons from the valence band (VB) of CdS with different numbers (n = 1, 2, and 3) of carboxylate-
NWs in the 1D CdS@TiO2 CSNs would transfer thermody-
namically to the TiO2 shell. Simultaneously, the holes in
the valance band of CdS NWs would stuck by the TiO2
shell. As a result, the lifetime of charge carriers will
prolong. The photogenerated electrons react with mol-
ecular oxygen and produce superoxide radicals (O·− 2 ),
which oxidize the alcohols to the corresponding alde-
hydes (Figure 20).

3.4. Dye-sensitized TiO2

Sensitization of TiO2 with organic dyes is a promising and Figure 21. Schematic of the visible-light induced H2 evolution
extremely effective technique used for renewable solar and pollutant oxidation on organic dye-sensitized TiO2 in
H2 production, electricity generation, and various water. (1) Photo-excitation and relaxation of organic dye, (2) elec-
organic pollutants oxidation. In this technique, the dye trons injection to the conduction band of TiO2 (or Pt/TiO2), (3) H2
molecules anchored on TiO2 are excited with solar production, (4) oxidation of dye, (5) regeneration of dye, (6) oxi-
dation of the electron donors (ED), (7) and (9): reduction of Cr(VI)
photons to generate highly excited electrons which
to Cr(III), (8): reduction of the dissolved O2 to superoxide anion,
then transfer to the conduction band of TiO2. Sub- (10) oxidation of the superoxide anion. Adapted from reference
sequently, the electrons in the conduction band of TiO2 (69) with permission. Copyright 2012, Elsevier Ltd.
98 M. HUMAYUN ET AL.

anchoring groups which were referred as D1, D2 and D3, quantum efficiency (AQE ∼44%) compared to their analo-
respectively. They found that all the three kinds of dyes gous simple architecture dye molecules. Further, they
are effective for H2 production in the presence of elec- noticed that the additional donating-groups such as dibu-
tron donors such as tri-ethanol-amine (TEOA) and ethyl- toxyphenyl and dihexylcyclopentyl p-conjugated-bridge
ene-diamine-tetra-acetic acid (EDTA) with the orders: units provide exceptional surface protection through
D3–D2 > D1 (TEOA) and D3 > D2–D1 (EDTA). From FTIR steric hindrance. This leads to the high photocatalytic
analysis, it was confirmed that D1 and D3 are probably activity. The mechanism of H2 evolution over the dye-sen-
anchored on the surface of TiO2 mainly by means of sitized TiO2-Pt photocatalyst is shown in Figure 23. The
bidentate modes with a single and double carboxylates, HOMO and LUMO positions of the dye attribute to the
respectively. Further, they investigated that D2 is formal redox potentials and the formal excited state oxi-
anchored with single and double carboxylates, depend- dation potential, respectively. In H2 evolution process,
ing on the competing electron donors. They demon- first, the dye molecules are excited from the ground
strated that the carboxylates number is less important state to the excited state by the absorption of incident-
in the sensitized pollutant oxidation because of the photon flux, due to the intra-molecular p–p* transition.
different photochemical conditions and reaction path- Second, the excited electrons immediately transfer to
ways. The tri-branched organic dye molecules with the conduction band of TiO2 before quenching by emis-
mono-, di-, and tri-carboxylate anchoring groups (sensi- sion and subsequent formation of the oxidized state
tizers D1, D2 and D3, respectively are depicted in dye. Third, the transferred electrons to the conduction
Figure 22. band of TiO2 are transported toward the co-catalyst Pt
Tiwari et al. (70) reported a series of donor-based site. Fourth, these electrons reduce H2O molecules at Pt
triphenylamine (TPA) dyes in sensitized visible-light H2 site. Finally, the oxidized dyes reduce to its ground state
generation over TiO2-Pt photocatalysts. First, different by accepting electrons from the oxidized sacrificial elec-
dyes such as 4-(diphenylamino) phenylcyanoacrylic acid tron donors. Hence, the reduction of the oxidized dye
(DN-F01), 5-[4-(diphenylamino)phenyl]thiophene-2-cya- and the regenerated by sacrificial electron donors
noacrylic acid (DN-F02), and 3-(5-(4-(diphenylamino)styryl) resolve the efficiency of H2 evolution.
thiophen-2-yl)-2-cyanoacrylic acid (DN-F03), (E)-3-(5-(4-(bis Lee et al. (71) reported the fabrication of phenothia-
(20,40-dibutoxy-[1,10-biphenyl]-4-yl)amino)phenyl) thio- zine-based organic dyes/TiO2-Pt composites with sys-
phen-2-yl)-2-cyanoacrylic acid (DN-F04) and 3-(6-(4-(bis tematic alkyl-chains and two-anchoring groups. They
(20,40-dibutoxy-[1,10-biphenyl]-4-yl)amino)phenyl)-4,4- demonstrated that the composite showed excellent
dihexyl-4H-cyclopenta[1,2-b:5,4-b0] dithiophen-2-yl)-2- visible-light photoactivities for H2O splitting. Further,
cyanoacrylic acid (DN-F05) were adsorbed on the they investigated that the phenothiazine dyes with
surface of TiO2-Pt, and the resultant photocatalysts were longer alkyl-chains exhibit high stability during photoca-
subjected for H2 evolution under visible-light in the pres- talytic processes. Their stability was attributed to the cat-
ence of sacrificial electron donor triethanolamine (TEOA). ionic radical produced by one electron oxidation. They
They investigated that the extended visible-light absorp-
tion and the enhanced interfacial charge transfer from
excited dye molecules to the conduction band of TiO2
are much significant in DN-F05-TiO2. They found that
the DN-F05 dye-sensitized TiO2-Pt photocatalyst display
superior turnover number (1864) and noticeable

Figure 22. The structural representation of tri-branched organic

dye molecules with mono-, di-, and tri-carboxylate anchoring Figure 23. Proposed mechanism for the efficient visible-light H2
groups (sensitizers D1, D2, and D3). Adapted from reference evolution over dye-sensitized TiO2 photocatalyst. Adapted from
(69) with permission. Copyright 2012, Elsevier Ltd. reference (70) with permission. Copyright 2015, Elsevier Ltd.
 GREEN CHEMISTRY LETTERS AND REVIEWS 99

demonstrated that the two-anchoring groups can be molecules were transferred to the conduction band
introduced at position 3 and 7 of the phenothiazine (CB) of TiO2 which then initiated interfacial chemical
dyes. However, the multi-anchoring groups can greatly reaction. The schematic of visible-light induced H2 evol-
improve the photostability of the photocatalysts during ution over dye-sensitized TiO2 is depicted in Figure 25.
photocatalytic processes. They demonstrated that the
phenothiazine-based dyes with a directly connected
anchoring group exhibit enhance visible-light harvesting 3.5. Metal ion-implanted TiO2
efficiencies compared to the common donor–acceptor The metal ion implantation is another strategy used to
sort of dyes with additional p-conjugated bridges. The modify the electronic structure of semiconductors. In
alkyl groups on nitrogen can induce orientation of dyes this technique, the metal ions are accelerated in the elec-
on TiO2, which may possibly result in the efficient elec- tronic field and injected to the target (sample) as the ion
tron transfer from the excited dye molecules to the con- beam. These metal ions interact with the sample surfaces
duction band of TiO2. This results in the improved in different ways depending on their kinetic energy.
photoactivities of the composites for H2O splitting. The Further, the metal ions are highly accelerated to have
schematic of phenothiazine-based dyes (P1–P5) with enough kinetic energy (50–200 keV) and then implanted
two anchoring groups is depicted in Figure 24. into the semiconductors bulk (73). Yamashita et al. (73)
Bae et al. (72) reported the synthesis of a variety of Ru- reported the synthesis of (V+, Mn+, Fe+) metal ion-
bipyridyl with di-, tetra-, and hexa-carboxylate function- implanted TiO2 photocatalysts. They investigated that
alities (C2, C4 and C6) and with di-, tetra-, and hexa-phos- at high energy acceleration and subsequent annealing
phonate anchoring groups (P2, P4 and P6) sensitized of these metal ion-implanted TiO2 photocatalysts in O2
TiO2 samples for visible-light catalytic H2 evolution in at 725 K, the absorption spectra was remarkably shifted
aqueous suspension containing an electron donating toward visible-light region. The resultant photocatalysts
agent (EDTA). They investigated that the efficiencies of showed exceptional photocatalytic activity for 2-propa-
C and P sensitizers depend on the number and type of nol (diluted in H2O) degradation under visible-light
anchoring groups. The adsorption of P sensitizers on irradiation. They confirmed by means of XAFS analysis
TiO2 surface was strong enough not to be hindered by that the implanted metal ions are sited at Ti4+ lattice
EDTA, whereas the adsorption of C sensitizers was signifi- positions in TiO2 after annealing. They demonstrated
cantly inhibited. Thus, the P-TiO2 exhibited exceptional that the substitution of Ti ions in TiO2 matrix with the
visible-light activity for H2 evolution compared to that implanted metal ions is much important to modify TiO2
of the C-TiO2. Among the six different kinds of sensitizers, for visible-light photocatalytic activities. Takeuchi et al.
P2 was the most active for H2 evolution. (74) reported the synthesis of transition metal ions (Cr
When the Ru-bipyridyl-TiO2 samples were irradiated and V) implanted TiO2 thin film photocatalysts by an
under visible-light, the excited electrons of dye advanced metal ion-implantation technique. They
observed that the absorption spectra of the resultant
thin film photocatalysts were remarkably shifted toward
visible-light region. As a result, the photocatalysts

Figure 25. The electron pathways are represented by various

numbers: (1) electron transfer from the excited sensitizer to
the conduction band of TiO2; (2) back-electron transfer to the oxi-
dized sensitizer (RuIIILx); (3) the migration and trapping of elec-
Figure 24. Schematic of the phenothiazine-based dyes/TiO2-Pt trons in Pt deposits; (4) the interfacial transfer of electron to H2O
composites for efficient visible-light-driven H2O splitting. (or H+) on Pt; (5) the regeneration of sensitizer by an electron
Adapted from reference (71) with permission. Copyright 2012, donor (D) (i.e. EDTA). Adapted from reference (72) with per-
Royal Society of Chemistry. mission. Copyright 2006, American Chemical Society.
100 M. HUMAYUN ET AL.

showed significant visible-light catalytic decomposition Funding

of NOx into N2 and O2 environment at 275 K. Zhou et al.
The work was financially supported by the National Natural
(75) reported the fabrication of V+ ion-implanted P25 Science Foundation of China under [grant no. 11574106,
TiO2 photocatalysts by an ion implantation method. 61771448 and 51635007], the China Postdoctoral Science Foun-
They investigated that the materials exhibited remarkably dation under [grant no. 2017M622404], and the Fundamental
enhanced visible-light catalytic activity for the degra- Research Projects of Shenzhen City [JCYJ20150831202835225].
dation of formic acid. From HRTEM micrographs, they
have confirmed that the V ions exist in the form of
Notes on contributors
VO2(T) in the P25 TiO2 matrix. Based on the photolumines-
cence spectra, they suggested that the enhanced visible- M. Humayun received his PhD degree in Chemistry &
light activity of the V+ ion-implanted P25 TiO2 photocata- Materials Science from Heilongjiang University China in
2017. He received the distinguished PhD scholar award
lyst for formic acid degradation is also attributed to
(30000 RMB) from the Chinese Government in 2016. Fur-
improved charge separation. Lam et al. (76) reported the thermore, he received the outstanding graduate award
synthesis of chromium (Cr) ion-implanted TiO2 thin from Heilongjiang University in 2017. Currently, he is
films. They investigated that the visible-light catalytic working in Prof. Luo Wei group as a postdoc researcher
activity of the resultant Cr/TiO2 photocatalyst for degra- in the School of Optical & Electronics Information, Huaz-
dation of gaseous formaldehyde was considerably hong University of Science & Technology (HUST) China,
under the China postdoc research program. He received
enhanced. Wang et al. (77) reported the fabrication of the China Postdoctoral Science Foundation project grant
Sn ion-implanted TiO2 thin films by an ion implantation in 2017 (Grant no. 2017M622404). His current research
technique. They used different doses of Sn ion implan- interests include the design of visible-light-driven nanopho-
tation for surface modification of TiO2. They demon- tocatalysts for solar fuel production and environmental
strated that the Sn4+ ions substitute Ti lattice site in TiO2 purification.
matrix. They investigated that TiO2 with an optimum F. Raziq received his PhD degree in Chemistry & Materials
dose of implanted Sn ions exhibited enhanced photoac- Science from Heilongjiang University, in 2017. He received
the distinguished PhD scholar award (30000 RMB) from the
tivity for Rhodamine B (RhB) degradation. The enhanced
Chinese Government in 2016. Currently, he is working as a
photoactivity was attributed to the extended light postdoc researcher in Prof. Liang Qiao group Institute of Funda-
absorption from ultraviolet to visible region and mental and Frontier of Sciences, University of Electronic Science
enhanced charge separation as a result of Sn4+ introduced and Technology of China, under the China postdoc research
electron and holes trapping states near the conduction program. His current research interests include synthesis of
band bottom and valance band top of TiO2. visible-light responsive materials for CO2 conversion and
water splitting.
A. Khan received his PhD degree in Physical Chemistry from
4. Conclusions Quaid-I-Azam University, Islamabad, Pakistan, in 2010. He
joined the Department of Chemistry Abdul Wali Khan Univer-
In this review, we have described various modification sity Mardan Pakistan as an Assistant Professor in 2011. His
strategies of TiO2 and their applications in photocatalysis. research interests include Polymer Science, Colloids & Surfac-
We have discussed basic concepts related to surface tants, and Materials Chemistry.
modification including metal nanoparticles deposition, W. Luo received his PhD degree in Electronic Science and
inorganic acids modification, elemental doping, hetero- Technology from Huazhong University of Science & Tech-
junctions with other semiconductors, dye sensitization nology China, in 2009. From 2009 to 2012, he worked as
a postdoc researcher in the School of Optical & Electronics
and metal ion implantation. Further, this review empha- Information, Huazhong University of Science & Technology
sizes the basic mechanisms for photophysical and photo- (HUST) China. From 2012 to 2016, he worked as a Lecturer
chemical processes and the physical concepts suitable in the School of Optical & Electronics Information, (HUST),
for material properties interpretation and structural China. From 2014 to 2016, he worked as a postdoc
property correlations. This review would help us to syn- researcher in the United States University of Michigan
(ANA). From 2016 till date, he is working as an Associate
thesize low-cost TiO2-based material and also help us
Professor in the School of Optical & Electronics Infor-
to deeply understand the photophysical and photoche- mation, (HUST), China. His current research interests
mical processes involved during the photocatalytic CO2 include SAW sensors and low-dimensional semiconductor
conversion, water splitting, and pollutants degradation sensing materials.
over TiO2-based materials.

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