Fuel 303 (2021) 121207

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

Latest progress on the key operating parameters affecting the

photocatalytic activity of TiO2-based photocatalysts for hydrogen fuel
production: A comprehensive review
Mohammed Ismael
Institute of Chemistry, Technical Chemistry, Carl von Ossietzky University Oldenburg, Carl-von-Ossietzky-Str. 9-11, 26129 Oldenburg, Germany

A R T I C L E I N F O A B S T R A C T

Keywords: Photocatalytic hydrogen generation via water splitting is a sustainable, renewable, and promising technology to
TiO2-based photocatalysis produce green and clean hydrogen fuel by disassociating water into H2 and O2 using TiO2 photocatalyst, and
Hydrogen production sunlight with negligible impact on the environment, which can fulfill the future requirements of energy. TiO2-
Energy conversion
based photocatalysts are one of the most effective and widely used photocatalysts for photocatalytic hydrogen
Parameters affect the activity of TiO2-based
production due to their high photostability, abundance, high efficiency, non-toxicity, and low cost. However,
photocatalyst
TiO2 as a common photocatalyst cannot be easily applied to photocatalysis due to its wide bandgap energy that
can only be activated under UV light, which occupies around 2–5% of the solar spectrum and the higher
recombination rate of the photogenerated charge carriers before migrating to the surface to split water that
restricted its photocatalytic performance. For that, factors such as surface area, particle size, and calcination
temperature that affect the photocatalytic activity of TiO2 were highlighted. Additionally, the rational strategies
such as doping, composite structure, dyes sensitization, defects engineering, and others that are used in
enhancing their activities are described in detail. Importantly, the investigation showed that various parameters
such as pH, sacrificial reagent, light intensity, catalyst, cocatalyst loading and catalyst deactivation, have great
effects on photocatalytic hydrogen production over TiO2-based photocatalysts. Through reviewing the important
state-of-the-art advances on this topic, this comprehensive review may provide new opportunities for designing
and constructing highly effective TiO2-based photocatalysts for other applications in photocatalysis.

1. Introduction
Energy crisis and environmental problems have become more severe
over recent years due to the decreasing availability of nonrenewable
fossil fuels resources, and the greenhouse effect as a result of the un­
controlled CO2 emission and releasing of large quantities of air pollution
gases annually, which cause severe health problems for humans and
global climate change. Recently, oil remains the world’s primary fuel,
comprising 32.9% of global energy demand, followed by coal (29.2%)
and natural gas (23.8%) in 2015 [1]. It is of the utmost urgency to
identify carbon–neutral alternative energy sources to tackle this issue
[2]. Among various renewable energies, solar energy is the most abun­
dant and providing about 120,000 TW annually to the Earth. Therefore,
the conversion of solar energy into chemical energy (hydrogen energy)
can be a powerful approach to mitigate the future energy crisis and
environmental pollutions [3–5]. Another process called photoreduction
of carbon dioxide or artificial photosynthesis focused on synthesizing
hydrocarbon molecules such as CH4, CH3OH, and CO from CO2 which
acts as the natural photosynthesis in green plants (Fig. 1(a&b)) [6],
wherein sunlight absorbed by chlorophyll in plants promotes starch and
oxygen production from carbon dioxide and water. Furthermore, Pho­
togenerated charge carriers formed upon excitation of the photocatalyst
by the absorption of solar energy can also be used to induce the pho­
todegradation reaction of different organic pollutants and dyes in the
marine environment (Fig. 1c) [6]. In addition to solar energy, to produce
hydrogen, water should be required as the second element in photo­
catalytic water splitting. Hydrogen production using this green tech­
nology is, therefore, a fully environmentally friendly process using
renewable and non-toxic photocatalysts, solar energy, and water. In
contrast, it doesn’t produce any harmful or dangerous atmospher­
ic gases or pollution. Therefore, this green technology will be expected
to cover the need for energy demand shortly.
Hydrogen can be a promising choice for future energy demand
because it is storable, renewable, a green source of energy with no CO2

E-mail address: mohammed.ismael@uni-oldenburg.de.

https://doi.org/10.1016/j.fuel.2021.121207
Received 7 April 2021; Received in revised form 29 May 2021; Accepted 3 June 2021
Available online 13 July 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
M. Ismael Fuel 303 (2021) 121207

emissions and can easily be used in fuel cells for the generation of and photocatalyst is the most attractive and renewable approach among
electricity. Hydrogen has higher energy content per unit of weight all the traditional hydrogen production technologies. Fig. 2 [15] dis­
(120.7 kJ/g), compared to any of the known nonrenewable hydrocarbon plays a schematic diagram using sunlight, photocatalyst, and water to
fuels and is considered to be the major energy source for the future [7,8]. produce photocatalytic hydrogen in the hydrogen energy system.
Furthermore, Hydrogen is a gas at ambient conditions that can be used
like gasoline as a transport fuel [9]. It can be easily stored as pressurized
1.1. TiO2 photocatalyst
gas and liquid compounds and easily distributable through the pipeline
[10]. Currently, the main hydrogen storage technologies are classified
Titanium dioxide (TiO2) or titania is a very well-known and
into the physical and chemical methods; compressed, liquefied are
researched material due to its high photostability, photocatalytic ac­
related to the physical methods, whereas solid-state and chemical
tivity, non-toxicity, and availability [16]. Up to now, TiO2 nanoparticles
hydrogen storage technologies are chemical methods of hydrogen stor­
have been applied in photocatalytic hydrogen production via water-
age. Although both methods are widely used in hydrogen storage tech­
splitting [17,18], degradation of organic pollutants in the wastewater
nologies, still they are facing some challenges, for example, in
[19,20], photocatalytic self-cleaning [21], bacterial disinfection
compressed hydrogen storage, high energy, and high-pressure tank
[22,23], photo-induced super hydrophilicity [24,25] as well as in pho­
require for this method. These storage tanks are manufactured from
tovoltaics [26,27], and photosynthesis [28]. TiO2 crystallizes in three
carbon nanofibers, which is very expensive. High energy and super
common phases; anatase, rutile, and brookite phases (Fig. 3) [29].
insulation tank are demanded the liquefaction of hydrogen, which is not
Anatase type TiO2 has a tetragonal crystal structure each octahedron
easy to eliminate all heat by the insulation that leads to losing some
shares corners to form (0 0 1) planes and is used mainly in photo­
hydrogen to keep the pressure in the tank at a safe level. Solid-state
catalysis. Rutile type TiO2 also has a tetragonal crystal structure consists
storage materials refer to the storage of hydrogen in metal hydrides
of edge-sharing octahedrons forming the (0 0 1) planes and is mainly
are allocated into two: reversible hydrides and physisorption (porous)
used as a white pigment in paint. Brookite type TiO2 has an ortho­
materials. Reversible hydrides need relatively high temperatures
rhombic crystalline structure that is made up of both corner and edge-
(>100 ◦ C) to operate, and they suffer from reversibility issues. Besides,
sharing octahedral. Anatase TiO2 is more favorable than rutile and
reversible hydrides suffer from degradation over cycles. Additionally,
brookite as it has better performance for photocatalytic H2 production
during hydrogen discharging from hydrides, it’s possible that some toxic
[30] due to the faster charge carrier separation, higher kinetic stability,
gases (NH3) can be produced, which can be detrimental to the operation
and suitable bandgap energy [31].
of a fuel cell. Porous materials operate at cryogenic temperatures (77 K)
to store a significant amount of hydrogen, and their drawback is the cost
associated with cooling. The problem is that high-surface-area porous
materials tend to have low material densities and therefore only modest
volumetric hydrogen storage capacities. For the chemical hydrogen
storage, no onboard regeneration is possible and a heat management
system is required, and the regeneration itself is a costly process. Thus,
energy-efficient and inexpensive regeneration processes have to be
developed. However, most annual hydrogen production (44.5 million
tons) is used for the production of ammonia (NH3) and methanol
(CH3OH), and a very small amount of it is used for energy purposes
[11,12]. Many clean and sustainable solutions to synthesize hydrogen
and avoid using fossil fuel as the key source of energy have been
established in recent years. For instance, Naseri et al. [13] reviewed the
advantages and disadvantages of the current nonrenewable methods
used for hydrogen production. Nowadays, 95% of global hydrogen
production comes from nonrenewable fossil fuel [14]; photocatalytic Fig. 2. Schematic diagram of photocatalytic hydrogen generation using sun­
hydrogen production via water splitting using renewable solar energy light, photocatalyst, and water in the hydrogen generation system [15].

Fig. 1. (a) Natural green plant photosynthesis in comparison with (b) Artificial photosynthesis through water splitting and CO2 reduction, and (c) Photodegradation
of aqueous organic pollutants into harmless inorganic compounds over photocatalyst under solar energy [6]. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)

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Fig. 3. Crystal structure of the three common polymorphs of titania (anatase,
rutile, and brookite) [29].
Titanium dioxide usually exists as an n-type semiconductor (elec­
trons are the majority charge carrier) [32]. Crystalline TiO2 and TiO2
nanoparticles (<10 nm) show higher photocatalytic activity perfor­
mance than amorphous due to the reduction of the photoexcited
electron-hole recombination and quantum size effect, respectively
[33–35]. However, titania still has drawbacks for broad-scale photo­
catalysis that attributed to the large bandgap energy, which cannot be
excited under visible irradiation that occupies 46% of the solar spectrum
as well as fast charge carriers recombination [36,37]. Nevertheless, TiO2
nanomaterials remain the most studied nanomaterials for hydrogen
generation is shown in Fig. 4 [38].
To enhance the performance of photocatalytic activities particularly
for visible light irradiation, numerous methods have been developed to
increase the photocatalytic efficiency, such as metal and nonmetal ion
doping, noble metal loading, semiconductors coupling to TiO2, and dye
sensitization, which will be discussed in more details in the second part.
1.2. Photocatalytic and photoelectrochemical water splitting
H2 is an ideal clean fuel of the future because it can be produced from
renewable energy sources and causes no pollution, thus the whole pro­
duction process is green and renewable [39,40]. Photocatalytic
Fig. 4. Statistical distribution of published papers for photocatalytic H2 pro­
duction over different photocatalytic materials [38].
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Fuel 303 (2021) 121207
hydrogen production via water-splitting using renewable sources, such
as water and solar energy is widely accepted as a possible solution to
solve the global energy crisis [41] since the feasibility of producing H2
using UV light in a photoelectrochemical cell was first illustrated by
Japanese scientists Fujishima and Honda in the year 1972 using the
semiconductor material titanium dioxide (TiO2) (Fig. 5a) [42], but the
development of high efficient photocatalysts for solar energy induced
hydrogen production via water splitting still have some challenges and
is, thus often mentioned as a “holy grail” in photocatalysis [43,44].
Especially, most oxide and mixed oxide photocatalysts are able to split
water are only active under UV irradiation, which occupies around 4%
of the total solar energy. Therefore, it is very important to search for
photocatalysts that are active under sunlight energy, efficient, thermal
and chemical stability, low-cost, and non-toxic. To date, various semi­
conductors have been explored to split water under light irradiation
with suitable cocatalysts loaded on the surface; such as metal oxide,
nitride, and sulfide [45–47]. Unfortunately, the relatively low quantum
yield efficiency and high expensive noble metal-containing materials
(cocatalyst) of these systems make them unfavorable for practical usage.
In typical photocatalysis processes, semiconductor photocatalysts,
such as TiO2, ZnO, and ZnS, are initially activated by incoming photons
provided by either ultraviolet (UV) or visible-light irradiation. When
sufficient photochemical energy is applied, electrons can be excited
from the VB to the CB of the semiconductors, leaving positively charged
holes in the VB. After that, electrons and holes should be separated and
transferred to the surface of the photocatalyst to initiate the redox re­
actions to produce H2 (Eqn: (1)) and O2 (Eqn: (2)), respectively.
Photoreduction: 4H + 4e_ → 2H2, E0 = 0 V vs. NHE (1)
Photooxidation: H2O + 2 h → O2 + 2H + 4e , E = 1.23 V vs. NHE (2)
+ + _ 0
A schematic diagram of the fundamental principle of photocatalytic
water splitting is shown in Fig. 5b [48]. However, photocatalyst should
lower bandgap energy (3.0 e.V > Eg > 1.23 eV) to be active under visible
light irradiation. For thermodynamic reasons the CB has to be more
negative than H+/H2 0 V, whereas the VB has to be more positive than
O2/H2O 1.23 V. Overpotentials due to kinetic limitations require band
positions for the CB more negative than about − 0.3 V and the VB more
positive than about 1.5 V. On the other hand, photoelectrochemical
water splitting (PEC) follows the same principle described by Fujishima
and Honda. In Principle, the photoelectrochemical cell has two elec­
trodes, TiO2 and Pt electrodes. Under light irradiation of TiO2, electron
and hole pairs are generated, the holes oxide water at TiO2 electrode,
whereas, the photogenerated are transferred to the Pt electrode to
reduce water to hydrogen gas [49]. In the PEC technique, the photo­
active semiconductor (photocatalyst) should be attached to the
conductive substrate, which acts as electrode and a small bias was
applied to achieve the water splitting. Additionally, the charge separa­
tion of this technique was attained at the semiconductor/liquid inter­
face. The advantage of this techniques compared to the photocatalytic
system is that no need for gas separation because the generated oxygen
and hydrogen are formed on different electrodes.
Fig. 6 [50] shows the bandgaps and the VB and CB positions of the
three commonly known polymorphs of TiO2: anatase (tetragonal), rutile
(tetragonal, the most thermodynamically stable phase), and brookite
(orthorhombic) relative to the redox potential of water at pH = 7. As
presented in Fig. 6, the low activity of the rutile TiO2 is mainly assigned
to the position of the flat band potential, which locates at almost a
similar level to the reduction potential of the proton, whereas that of
anatase TiO2 is shifted negatively by ca. 0.2 eV (Fig. 6). Thus, the
electrons of the conduction band energy of anatase TiO2 would be higher
than that for rutile TiO2. A more cathodic conduction band potential
energetically favors proton/water reduction to hydrogen, explaining the
higher activity of the former toward hydrogen production. Furthermore,
it is important to arrange the photocatalytic system e.g. by the addition
of suitable cocatalysts, such that the photo-induced charges are
M. Ismael Fuel 303 (2021) 121207

Fig. 5. (a) Schematic diagram of photo-electrochemical hydrogen production by Fujishima and Honda using TiO2 and Pt electrodes [42], and (b) Fundamental
principle of semiconductor-based photocatalytic hydrogen production [48].

2. Factors affecting the photocatalytic activity of photocatalysts

and modification techniques used to improve the efficiency of
TiO2-Based photocatalysts

2.1. Factors affecting the photocatalytic activity of photocatalysts

2.1.1. Surface area and particle size of the photocatalysts

The photocatalytic activity of a catalyst is highly correlated to the
specific surface area and the particle size of the catalyst because a
catalyst with a higher specific surface area and small particle size pos­
sesses more surface active sites and possibly promotes the interfacial
charge separation [64,65]. It has been reported that TiO2 nanoparticles
exhibit higher photocatalytic activity performance compared to the TiO2
microparticles that ascribed to the small diameter, in which the charge
required the minimal effort to reach the surface and initiate the redox
reaction [66]. Therefore, with decreasing in particle size, the travel
distance needs for the photogenerated charge carriers is reduced, thus,
reducing the charge recombination. However, achieving a high specific
surface area with a smaller particle size photocatalyst is heavily
dependent on the temperature used in the synthesis process, which is
why applying the sol–gel approach to the photocatalysts synthesis is
considered a promising route to obtain materials with these character­
istics compared to the solid-state reaction. Several studies have reported
Fig. 6. Band structure of the three commonly known polymorphs of TiO2 at
that photocatalysts in the form of nanoparticles are more effective than
pH = 7 related to the water redox reaction potentials [50].
bulk powders [67,68]. For instance, Chiarello et al. [69] designed and
prepared a set of Au-modified TiO2 photocatalysts by flame spray py­
separated efficiently in order to suppress bulk/surface electron/hole
rolysis, accompanied by remarkably enhanced performance for
recombination as much as possible.
hydrogen production under visible light irradiation. The Au deposited
Previous studies were carried out on some narrow bandgap semi­
on TiO2 surfaces in the Au-TiO2 is beneficial for enlarging the surface
conductors such as CdS [51,52] and WO3 [53,54] with band gaps around
area and improving crystallinity, which can strengthen the charge sep­
2.4 eV. However, the fact that serious photocorrosion was observed for
aration in space. Porosity has a great influence on enlarging the specific
CdS and that WO3 is like Fe2O3 (bandgap of 2.2 eV) not able to form H2
surface area of the photocatalyst. For instance, nanocrystalline TiO2 ­
directly, limits their applicability [55]. In addition, several studies were
particles on porous hosts (SBA-15 and ZSM-15) were fabricated via a
reported on common metal oxides, such as TiO2 [56], ZnO [57], and
sol–gel impregnation method by Jiang et al. [70]. The porous TiO2
ZrO2 [58] for hydrogen production activity, but their large bandgap
particles (TiO2/ZSM-5 and TiO2/SBA-15) show a significantly enhanced
energy leads to them being inefficient in sunlight. To overcome these
photocatalytic performance for hydrogen production under full arc
obstacles, many efforts have been made to develop new visible-light-
(Fig. 7a&b), which could be ascribed to the smaller TiO2 particle size
driven photocatalysts with high water-splitting activity [59,60].
and higher surface area providing by the porous structure of the ob­
Several common approaches [61,62] have been adopted (1) metal or/
tained photocatalyst.
and nonmetal ions doping for bandgap narrowing; (2) developing solid
For instance, Xu et al. [71] constructed (CuO-TNT, TNT: nanotubes)
solutions to control the band structure; (3) dye sensitization to make UV-
by introducing highly dispersed CuO into TiO2 nanotube by hydro­
light-active photocatalysts harvest visible light; (4) developing novel
thermal method or wet impregnation process. Results showed that the
single-phase Vis-active photocatalysts through bandgap engineering.
visible-light performance of H2 production for CuO-TNT photocatalyst is
Binary metal compounds, such as BiVO4 [63], have emerged very
significantly improved compared to a single semiconductor. The tubular
recently as the state-of-the-art solar absorber material with a bandgap
structure, large BET surface area, and high dispersion of copper com­
similar to that of Fe2O3.
ponents are responsible for the higher H2 production. El-Maghrabi et al.
[72] reported a simple method for the synthesis of mesoporous

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M. Ismael Fuel 303 (2021) 121207

Fig. 7. Hydrogen evolution of various porous TiO2 based samples under a 300 W Xe lamp illumination in the presence of 2 wt% Pt nanoparticles as cocatalyst, and
methanol as a sacrificial reagent of (a) Pure TiO2 and TiO2/ZSM-5, (b) Pure TiO2 and TiO2/SBA-15 [70].

core–shell CdS@TiO2 photocatalysts for enhanced H2 evolution under
solar irradiation in the presence of a sacrificial agent and Pt as cocatalyst
(Fig. 8a). The mesoporous core–shell structure of the synthesized pho­
tocatalyst leads to an increase in the specific surface area, which facil­
itates the charge transport and separation confirmed by photocurrent
and electrochemical impedance measurements (Fig. 8b&c) and inhibit
charge recombination in visible light (Fig. 8d).
Sreethawong et al. [73] investigated N-doped mesoporous-
assembled TiO2 and N-doped nanocrystals in photocatalytic H2 pro­
duction. The results indicated that the mesoporous structure of the
photocatalyst is responsible for enhancing the photocatalytic activity by
increasing the specific surface area. Meanwhile, Martha et al. [74]
fabricated a series of novel V2O5/N, S-TiO2 composite photocatalysts by
a solid-state reaction route. The photocatalytic applications of the
composite materials were evaluated for visible-light hydrogen produc­
tion and direct sunlight phenol degradation. V2O5/N, S–TiO2 activated
at 500 ◦ C showed the highest activity for the two photocatalytic re­
actions that mainly ascribed to the enhancement of the surface area and
charge separation. In another interesting study, Chaugule et al. [75]
significantly obtained a novel catalyst system composed of Sm and Ni
oxide doped titanium oxide nanofiber with enhanced photocatalytic
activities for visible fuel production using NaBH4. The enhancement
could be attributed to the higher surface area and pore size of Sm-Ni
oxide of the doped TiO2 nanofiber (Fig. 9a&b) [75].
Rungjaroentawon et al. [76] used Eosin Y-sensitized mesoporous-
assembled TiO2–SiO2 photocatalyst for hydrogen production. Mixed
oxide photocatalysts were synthesized via the sol–gel method using the
structure-directing agent. Results indicated that the 97:3 TiO2 to SiO2

Fig. 8. (a) Activities of visible-light H2 production for the CT-50 photocatalyst and 0.1, 0.5 and 1 wt% Pt (b) Photoelectrochemical performance and (c) Electro­
chemical impedance spectra of CTs, and (d) Schematic representation of the charge separation mechanism and photocatalytic hydrogen production using core–shell
CdS@TiO2/Pt photocatalysts [72].

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M. Ismael
Fig. 9. (a) Hydrogen production with 0.6 wt% NaBH4 at 25 ◦ C, and (b) Pore size distribution curve of nickel doped, SmO doped, Sm-Ni oxide doped TiO2 [75].
ratio exhibited the highest activity, which can be ascribed to the high
surface area and small crystalline size. Moreover, Parayil et al. [77]
successfully obtained TiO2 aerogel using the high-temperature sol–gel
method. The photocatalytic activity of the TiO2 aerogel was investigated
for hydrogen production. Among all prepared photocatalysts, TiO2-6 h
shows superior activity without using Pt due to increased surface area
and reduces particle size. Furthermore, particle size and surface area of
nano-TiO2 powders can also be affected by precursor concentration, and
calcination temperature [78]. Puskelova et al. [79] also successfully
obtained TiO2/Pt aerogel nanocomposites by a combined sol–gel-su­
percritical drying strategy, and firstly utilized this nanocomposite in
visible-light photocatalytic H2-production containing aqueous ethanol
solution. The highest activity was obtained for the photocatalyst with
smaller particle sizes (Fig. 10a) and a high specific surface area
(Fig. 10b).
In another study, Qiu et al. [80] prepared TiO2 hierarchical/nano­
wires junction using a combined hydrothermal and calcination method
for the determination of hydrogen production in the presence of Pt as a
cocatalyst. Photocatalyst calcined at 450 loads 0.5 wt% Pt exhibited the
highest photocatalytic hydrogen activity (Fig. 11a) that attributed to the
large surface area (Fig. 11b).
Monoclinic phase and anatase phase composite loaded with CuNi
alloy nanoparticles in the presence of ammonia borate was used as
photocatalyst and tested for hydrogen production reported by Wang
et al. [81]. Photocatalyst was synthesized using combined hydrothermal
and impregnation methods. The highest photocatalytic hydrogen pro­
duction was obtained for a photocatalyst calcined at 700 ◦ C (Fig. 12a&b)
Fig. 10. (a) Comparison of different Pt sizes for hydrogen production over 1% Pt-TiO2 composite in presence of ethanol (1) 5.75 (2) 6 and (3) 6.5 nm, and (b) N2
adsorption/desorption isotherm for surface area determination of 1% TiO2-Pt-5.75 nm aerogel [79].
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Fuel 303 (2021) 121207
containing 36% Cu and 64% Ni, which was mainly assigned to the role of
CuNi alloy nanoparticles in enhancing charge separation efficiency
(Fig. 12c) as well as for the high surface area (Fig. 12d).
In another study, Liu et al. [82] studied the influence of particle size
on the photocatalytic hydrogen production of Ba/SrTiO3 cores/TiO2
shell heterostructure prepared using the facile sol–gel method. The
maximum hydrogen production activity was observed for the photo­
catalyst calcined at 600 ◦ C with 100–150 nm thick in presence of 1 wt%
Pt as cocatalyst. The work of Chen et al. [83] for example, demonstrated
that Nanorod-like TiO2 photocatalysts were successfully achieved by
simple hydrothermal and ion-exchange methods, showing highly
effective visible-light performance concerning bare TiO2 (P25) that
ascribed to the high surface area and better crystallinity. Furthermore,
Yang et al. [84] successfully constructed a core–shell structure con­
taining carbon-doped TiO2 and metallic TiC. The photocatalytic activity
of the core–shell photocatalyst was tested for hydrogen production in
presence of aqueous methanol as a sacrificial reagent. Results have
clearly shown that the core–shell structure exhibited higher photo­
catalytic performance compared to pure TiO2, which may be assigned to
the large surface area and efficient charge transfer.
2.1.2. Calcination temperature
Calcination temperatures have a prominent effect on the prepared
photocatalysts morphology, surface area, pore-volume, crystallinity,
crystallite size, and phase structure, and these influences have also
impacted their evolutionary photocatalytic behavior. Wu et al. [85]
studied the effect of the thermal treatment on the photocatalytic activity
M. Ismael Fuel 303 (2021) 121207

Fig. 11. (a) Comparison of H2 production rate for different calcination temperatures, and (b) N2 adsorption–desorption isothermal curves for specific surface area
determination of photocatalysts [80].

Fig. 12. (a) Hydrogen evolution rate under different light conditions, (b) different calcination temperatures, (c) The proposed mechanism for efficient charge
separation and hydrogen production, and (d) N2 adsorption–desorption isotherms of the different photocatalysts with (the most active) and without CuNi alloys
nanoparticles [81].

of the well-crystallized titania nanorods thin film toward degradation of
RhB. Their study showed that the highest activity of the thin film was
achieved when the film was thermally treated at 450 ◦ C. At higher
thermal treatment, the photocatalytic activity was decreased due to the
reduced specific surface area. It has been observed that the anatase
phase of TiO2 obtained at lower temperature shows better photo­
catalytic hydrogen production activity than the rutile one [86]. Thus,
the synthesis method and calcination temperature should be optimized
to obtain the high active anatase phase of TiO2. For instance, Naik et al.
[87] prepared free-template mesoporous Bi2O3/TiO2-xNx nano­
composites via simple co-precipitation technique at different calcination
temperatures for hydrogen production under visible light irradiation.
Inspiringly, the photocatalyst sample calcined at 400 ◦ C showed the
highest activity, which can be assigned to the enlargement of the surface
area and high crystallinity. Similarly, Parida et al. [88] prepared hier­
archical and fibrous meso-macroporous N-doped TiO2 without using
templates at different calcination temperatures (300–800 ◦ C). The result
indicated that the photocatalyst calcined at 400 ◦ C presents the highest
hydrogen production activity (Fig. 13a). Moreover, the crystalline
anatase phase (Fig. 13b), optimized visible light absorption (Fig. 13c),
and the improvement of the charge separation provided by the special
morphology and porosity of the catalyst (Fig. 13d), are the key factors
for the enhanced photocatalytic activity. Besides, calcination tempera­
ture, crystallinity, surface area are strongly affected hydrogen produc­
tion activity. Herein, the sample calcined at 400 ◦ C has good crystallinity
compared to that calcined at 300 ◦ C, it has a high surface area and pure

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Fig. 13. (a) H2 evolution over different N-doped TiO2 photocatalysts, (b) X-ray diffraction patterns of N-doped TiO2 photocatalysts calcined at various temperatures,
(c) Diffuse reflectance spectra of N-doped TiO2 photocatalyst calcined at different temperatures, and (d) Photoluminescence (PL) spectra of NTP-300 and NTP-
400 [88].

phase titania compared to that photocatalysts calcined at the higher
temperature (500–800 ◦ C). Thus, it shows the highest activity.
To investigate the effect of calcination temperature on the
morphology of the obtained photocatalyst, Wei et al. [89] loaded Pt
nanoparticles (using H2PtCl6 as a precursor for the cocatalyst, Pt
oxidation number is 4 + ) over TiO2 microspheres by impregnation re­
action combined hydrothermal method. The highest photocatalytic
hydrogen production was obtained for the photocatalyst loaded with
1.2 wt% Pt and calcined at 500 ◦ C (Fig. 14a&b).
The sol–gel process was used by Wu et al. [90] to decorate Pd-
calcined black TiO2 nanoparticles in an argon atmosphere. The
photocatalyst obtained was checked at various calcination temperatures
for hydrogen production. For the photocatalyst calcined at 400 ◦ C, the
maximum behavior was recorded. (Fig. 15a&b). Also, the highest ac­
tivity was attributed to the enhancement of light absorption
(Fig. 15c&d).
Long et al. [91] fabricated CdS/TiO2 composites by wetness
impregnation at different calcination temperatures (300–500 ◦ C) for the
determination of hydrogen production activity. Photocatalyst calcined
at 500 ◦ C presents the highest activity due to the excellent crystallinity.
In order to investigate the influence of calcination temperature on the
phase formation of titania, Qiu et al. [92] showed that mixed-phase

Fig. 14. (a) Hydrogen generation rate of Pt loaded TiO2 microspheres with different Pt loading amounts and (b) Hydrogen generation rate of TiO2 microspheres
calcined at different temperatures [89].

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M. Ismael
Fig. 15. Hydrogen production rate of various Pd-TiO2 photocatalysts under the following light source irradiation: (a) UV-A and (b) UV-B, Kubelka-Munk function
spectra of synthesized (a) WTN (W: white) and (b) BTN (B: black) calcined at different temperatures for 2 h [90].
consisting of 67 wt% anatase and 33 wt% rutile exhibited superior
photocatalytic hydrogen production activity that attributed to the high
stability and good crystallinity.
In another study, Hui et al. [93] prepared nitrogen-doped SrTiO3/
TiO2 composite employing solid-state reaction and sol–gel method.
Photocatalytic hydrogen production of the obtained photocatalyst in
oxalic acid solution was evaluated under visible light at different
calcination temperatures (350–550 ◦ C). Photocatalyst calcined at 400 ◦ C
and loaded with 2 wt% Pt shows the highest activity. Moreover, Huang
et al. [94] studied the effect of post thermal temperature on photo­
catalytic hydrogen production of TiO2 film. Results showed that the TiO2
thin film calcined at 500 ◦ C exhibited higher hydrogen and oxygen
production activity as well as higher photocurrent intensity compared to
that calcined at 700 ◦ C. Photoelectrochemical cells consisting of TiO2 ­
nanotube photoanode and Pt/C cathode were constructed by Li and
coworkers [95]. TiO2 nanotube was calcined at different calcination
temperatures. The photocatalytic activities of photocatalysts were
assessed for hydrogen production in the photoelectrochemical cell. Re­
sults showed that the TiO2 nanotube photoanode showed the best ac­
tivity. Peng et al. [96] prepared Be2+ doped TiO2 photocatalysts using
combined impregnation and coprecipitation method. The highest
hydrogen production activity was obtained for the doped photocatalyst
calcined at 400 ◦ C for 1 h. at this calcination temperature, the doped
photocatalyst shows the best crystallinity. Li et al. [97] successfully
constructed a g-C3N4-TiO2 heterojunction for hydrogen production
under visible light irradiation. A g-C3N4-TiO2 heterojunction calcined at
600 ◦ C exhibited the highest activity. The composite formation between
the two semiconductors and the nanosheet structure of graphitic carbon
nitride facilitate charge transport and separation. Interestingly, Reddy
et al. [98] designed CaFe2O4/TiO2 composite using titania nanosheet
and low bandgap calcium ferrites. The photocatalytic activity of the
prepared samples was investigated for hydrogen production. 1% wt
9
Fuel 303 (2021) 121207
calcium ferrite over titania calcined at 400 ◦ C exhibited the highest
photocatalytic hydrogen activity (Fig. 16a&b).
Chang et al. [99] studied the hydrogen production activity of gold
doped-TiO2-MOx photocatalysts calcined at different calcination tem­
peratures. Importantly, Au/TiO2-Fe2O3 photocatalyst dried at 373 K in
the air without calcination showed the best hydrogen production ac­
tivity in the presence of methanol. In another study, Lee et al. [100]
synthesized TiO2/CuO composite nanofibers using the electrospinning
method. The photocatalytic activity of the composite was tested for
hydrogen production in an aqueous solution containing methanol as a
sacrificial reagent. Results show that 6 mol % Cu, calcined at 450 ◦ C
exhibited the highest activity. Recently, Vásquez et al. [101] hydro­
thermally synthesized a nanostructured material composed of Fe2O3 and
TiO2 oxides. After that, the samples were calcined at 400, 700, and
1000 ◦ C. Their findings showed that the sample calcined at 1000 ◦ C has
the highest activity attributed to the transformation of magnetite into
more active photocatalytically phases (hematite) driven by the changes
in surface morphology.
Besides, surface area and particle size, and calcination temperature,
bandgap energy of the photocatalyst are also a very important param­
eter that affects its light absorption. To make a photocatalyst visible-
light active, bandgap energy should be narrowed. Various bandgap en­
gineering techniques are developed by the researchers across the globe
mentioned in Section 2.2.1, 2.2.2, and 2.2.3. Besides, several approaches
used to enhance the charge separation efficiency of TiO2-based photo­
catalysts were described in details in sections 2.2.4., and 2.2.5. The
morphological architecture and the defect engineering tactics and their
influence on the photocatalytic performance of TiO2 were highlighted in
sections 2.2.6., and 2.2.7.
M. Ismael Fuel 303 (2021) 121207

Fig. 16. (a) Photocatalytic activity of 1 wt% CaFe2O4/TiO2 composite catalyst over different calcination temperatures, and (b) Photocatalytic activity of different
composite containing different wt% loadings of CaFe2O4 over TiO2 [98].

2.2. Modification techniques used to improve the efficiency of TiO2-Based
photocatalysts
Doping has been frequently applied to enhance the photocatalytic
activity of TiO2 catalysts by optimizing their optical properties by nar­
rowing their bandgap energy. Besides, dopants have a great influence on
the enhancement of the charge separation efficiency of the catalysts. The
applied dopants can be classified into three categories, metals, such as
transition metals, or nonmetals (like N, S, and C), and noble metals (such
as Au, Pd, and Pt). Commonly, noble metals such as Au and Ag have a
great ability to absorb visible light owing to the surface plasmon
resonance, but they are very expensive materials, which restrict their
application as efficient dopants in photocatalysis. Due to their low price
and availability, the transition metals can be an alternative to the noble
metals and also have the ability to enhance the photocatalytic activity.
However, their leakage activity contributes to the rapid deactivation of
the catalyst and produces a second source of contamination that allows
dissolved metals to be removed from treated water. Hence, doping with
nonmetals (mainly group P-block elements) has advantages compared to
the metal dopants. Besides the effective sensitization of TiO2 toward the
visible through narrowing of the bandgap energy, charge separation,
cheap, abundant and environmentally-friendly materials appear as

Fig. 17. The creation of impurity energy level in the forbidden band of semiconductor (a) Donor level, (b) Acceptor level formed by metal ion doping [104], and (c)
The mechanism of enhanced charge carrier separation and light absorption capacity of TiO2 through metal dopants [106].

10
M. Ismael
interesting landscapes. More details about these three categories of
dopants materials will be explained in more detail in the following
sections.
2.2.1. Metal ion doping
TiO2 doping by a heteroatom is an important means of extending
light absorption and influencing the band edge positions to boost the
photocatalytic efficiency of the photocatalyst. [102]. Recently, Ismael
et al. [103] reviewed the effect of dopants on enhancing the hydrogen
production activity of TiO2. In general, doping of transition metal cat­
ions decreases the bandgap of the semiconductor by creating an impu­
rity energy level (donor level or acceptor level) in the forbidden band of
TiO2 semiconductor making the photocatalysts visible light active
(Fig. 17a&b) [104] and may as well change the crystallinity of TiO2,
resulting in the creation some lattice defects, which diminish in elec­
tron/hole recombination centers [105]. Besides, the creation of donor or
acceptor level in the forbidden band of TiO2 and generation of gap state
through the interaction with the TiO2 VB state, which improves the
spectral response, enhanced charge separation efficiency can be also
achieved through the formation of Schottky barriers formed at the
semiconductor–metal interface or through the surface plasmon reso­
nance (SPR) of the noble metal or metal ions. Herein, the doped metal
can act as an electron sink site, trapping electrons from the CB of TiO2,
indicating improved charge separation efficiency. The overall effects of
metal dopants on enhanced light absorption and charge separation of
TiO2 are displayed in Fig. 17c [106]. Among different metals used as
dopants, copper (Cu) is the most promising metal dopant due to its
availability, and superior work function [106]. However, cation doping
amounts or concentrations should be carefully controlled to reach the
optimum. Otherwise, in the case of high dopant concentration acts as a
recombination center and may reduce the photocatalytic performance.
Therefore, regulation of the appropriate amount of dopant with
improved charge trapping and separation efficiency is very critical.
Fig. 18.
For instance, Ismael et al. [107] recently reported Ru doped TiO2 for
hydrogen production under visible light irradiation, their results show
that 0.1 wt% Ru is the optimum amount for the highest hydrogen ac­
tivity; increase amount of the Ru shows a decrease in the hydrogen
production activity. For another metal dopant, Singh et al. [108] tested
iron-doped TiO2 thin film for photoelectrochemical hydrogen produc­
tion. Doped thin films were successfully synthesized using the sol–gel
spin coating method. Compared to pure TiO2, the higher activity for the
obtained thin film was ascribed to the extension of light absorption to­
ward the visible region. Sun et al. [109] successfully manufactured
deposited metallic silver and nanoparticles Fe3+/TiO2 for hydrogen
production under visible light irradiation through the solvothermal
process. In all TiO2 tested photocatalysts, 4.5 wt% was optimum and
Fig. 18. (a) UV–vis absorption spectra of the prepared TiO2 containing different amounts of dopants (iron and silver), (b) charge transfer, separation, and hydrogen
production mechanism over Fe-Ag/TiO2 under light irradiation of λ > 400 nm [109].
11
Fuel 303 (2021) 121207
displayed the highest hydrogen production activity. Enhanced light
absorption and reduce charge recombination were responsible for its
higher photocatalytic performance are shown in Fig. (18(a&b)). Dholam
et al. [110] successfully fabricated Cr doped TiO2 thin film using the
different concentrations of Cr and different numbers of ITO/Cr-doped-
TiO2 layers via the RT magnetron sputtering method. Interestingly, a
thin film with the highest concentration of Cr and 6 layers thickness
shows the highest photocurrent and hydrogen production activity.
Another work related to the same group, Dholam et al. [111] synthe­
sized multilayer films ITO/V-doped TiO2 using the same method. 6 wt%
of V with 6 layers shows the highest activity toward hydrogen produc­
tion. Herein, enhanced light absorption by V ions and reduce charge
carrier recombination providing by the 6 layers thickness responsible for
the higher activity. Agegnehu et al. [112] hydrothermally prepared V-
doped TiO2/reduced graphene nanocomposite for hydrogen production
under visible light irradiation. Compared to pure TiO2, nanocomposites
exhibit higher photocatalytic activity due to the narrowing bandgap
energy and efficient charge separation offering by the graphene sheet
and the metal ion dopant. Cerium doped titania is synthesized through a
facile sol–gel method was studied by Bharatvaj and his co-workers
[113]. The photocatalytic activity of the prepared photocatalysts was
assessed to produce hydrogen in the sulfide solution. 0.4 wt% Ce3+–TiO2
shows the highest activity due to the reduction in the bandgap energy.
In another related study, Fan et al. [114] successfully deposited Ag
nanoparticles in Fe/TiO2 nanotubes via microwave-assisted chemical
reduction. Ag-Fe/TiO2 NTs showed higher visible light hydrogen pro­
duction performance, which attributed to better light absorption
behavior and high charge carriers separation. Cobalt also was used as a
dopant metal for the photocatalytic enhancement of TiO2 activity. For
instance, Sadanandam et al. [115] prepared Co/TiO2 photocatalysts by
impregnation method and tested for hydrogen production employing
glycerol as a sacrificial reagent. 1 wt% cobalt/TiO2 and 5% glycerol was
optimum and demonstrates the highest hydrogen evolution rate. Simi­
larly, Le et al. [116] used a simple physical absorption method to pre­
pare effective RhB dye-sensitized Co/TiO2 material for the overall
splitting of photocatalytic water under visible light. The catalyst RhB-
Co/ TiO2 effectively splits water into a 2:1 ratio of hydrogen and oxy­
gen (Fig. 19(a-c)). Coupling effects between the dye and the doped
photocatalyst is the key factor for enhancing the hydrogen production
activity compared to Co/TiO2 photocatalyst (Fig. 19(d)).
Furthermore, other transition metals such as Ni and Cu act as dopant
metals on TiO2. For instance, Jing et al. [117] successfully obtained Ni-
doped mesoporous TiO2 photocatalyst. The results also indicated that
the amount of hydrogen generation is strongly correlated to the con­
centration of Ni dopant and 1 wt% presents the highest hydrogen pro­
duction activity due to the efficient charge separation and narrow
bandgap energy. The bimetallic structure shows also an enhancement in
M. Ismael Fuel 303 (2021) 121207

Fig. 19. (a) H2 (b) O2 evolution as a function of reaction time over RhB-sensitized different photocatalysts (c) H2, O2 evolution and desorption of RhB dye as a
function of reaction time and (d) Charge separation mechanism and overall photocatalytic water-splitting over RhB-Co/TiO2 photocatalyst under visible light [116].

photocatalytic hydrogen production. For instance, Mohamed et al. [118]
studied the difference between monometallic and bimetallic doped ti­
tanium in photocatalytic action. In this analysis, the nanostructured
bimetallic copper/nickel doped TiO2 photocatalytic activity was con­
trasted with monometallic and also with undoped photocatalysts of
TiO2. The results indicated that 5% of CuNi-doped-TiO2 achieved the
highest photocurrent density (Fig. 20(a)), and photoconversion effi­
ciency (Fig. 20(b)) that was attributed to the efficient charge separation
provided by the two metal dopants.
Recently, Gogoi et al. [119] used a simple chemical reduction
method for the synthesis of Ag/TiO2 photocatalyst. Among different Ag-
doped TiO2, 1.5Ag/TiO2 exhibited the highest activity toward hydrogen
production in the presence of different sacrificial reagents (Ethanol, and
a mixture of Na2S and Na2SO3). The highest activity of 1.5Ag/TiO2 could
mainly be attributed to the existence of oxygen vacancies and the Ti - Ag
- O phase, reduction in the bandgap energy due to surface plasmonic
resonance (SPR), and efficient charge separation. In another interesting
work, Zeng et al. [120] constructed a novel, unassisted, hybrid tandem
photocatalytic fuel cell by adhering to a silicon solar cell to the back of a
highly-active silicon-doped TiO2 nanorod array. In this study, a silicon-

Fig. 20. (a) Photocurrent density, and (b) Conversion efficiency under visible light for monometallic and bimetallic compared to TiO2 photocatalysts [118].

12
M. Ismael
doped TiO2 nanorod array was hydrothermally synthesized and the
hybrid tandem photocatalytic fuel cell was tested for photo­
electrochemical hydrogen production from organic compound degra­
dation under solar light irradiation. Compared to conventional fuel cells,
hybrid tandem photocatalytic fuel cells have improved light absorption
and charge transfer, owing to the synergistic effect between silicon solar
cells and a highly-active silicon-doped TiO2 nanorod array, resulting in
enhancing the photocatalytic hydrogen production. Copper is also an
efficient dopant for TiO2 can increase its activity by narrowing the
bandgap energy and shifting the absorption edge toward the visible
region. For instance, Udayabhanu et al. [121] successfully deposited
CuO on Cu-TiO2 nanoparticles not only tested for hydrogen production
activity (10,453 mmol h1 g1 of the catalyst which is 21 fold higher than
pure TiO2 nanoparticles in the aqueous solution containing glycerol as a
sacrificial reagent), but also for the degradation of MB and photore­
duction of toxic Cr6+. The results investigated that 3% mol of CuO on Cu-
TiO2 nanoparticles showed the highest hydrogen production under
visible and solar light irradiation (Fig. 21a&b), which was mainly
ascribed to the enhanced light absorption through narrowing the
bandgap energy (Fig. 21c) and efficient charge separation (Fig. 21d).
Interestingly, Park et al. [122] investigated hydrogen production
from water by applying liquid plasma to the photocatalytic splitting of
water over Ag-doped TiO2. The photocatalytic hydrogen production was
enhanced for the doped TiO2 in the presence of methanol as an additive.
The enhanced activity was attributed to the wider visible light absorp­
tion of Ag-doped TiO2 as well as to the optical generating of OH radicals
and the role of methanol as an electron donor. Niobium (Nb) is one of
the most promising dopants which can enhance the photocatalytic
Fig. 21. (a) Comparison of the photocatalytic H2 production under solar light irradiation for a different amount of copper loading in 5 vol% Glycerol-water system,
(b) Hydrogen production activity of 3% mol CuO/Cu-TiO2 under visible and solar light irradiation, (c) Tauc plot, and (d) Photoluminescence of different CuO/Cu-
TiO2 photocatalysts [121].
13
Fuel 303 (2021) 121207
hydrogen production of TiO2 by modifying the surface structure and
crystalline structure of TiO2 and acts as an electron sink and inhibits the
recombination of electron-hole pairs. For that, Ravishankar et al. [123]
used an ionic liquid (IL) assisted hydrothermal method for the synthesis
of Nb/TiO2 nanoparticles at 140 ◦ C in one day. Their findings showed
that 0.3% Nb exhibited the highest visible-light photocatalytic hydrogen
production activity in an aqueous solution containing ethanol that may
be assigned to the synergistic effect between Nb and TiO2. Besides, Mn-
doped and Mo-doped TiO2 were also developed for enhanced photo­
catalysis [124–126]. Besides the mono-doping, co-doping (metal/metal
[127] or metal/non-metal [128]) of TiO2 with two metals is also a
promising method to enhance their photocatalytic activity performance
through reconstruct the conduction and valence band of TiO2 simulta­
neously reduce the bandgap energy, suppress the charge carrier
recombination and maintain the charge balance. For that, Lai et al.
[129] synthesized W, N co-doped TiO2 nanobelts films via a facile
method and tested for photodegradation under both UV and visible light
irradiation. Their investigation showed that the nanobelts structure
along with the co-doping effect assured an excellent performance of
TiO2.
2.2.2. Non-metal ion doping
Nonmetal ion doping (anion doping) is s novel and attractive
approach for shifting light absorption of TiO2 into the visible region by
an upward shift of its valence band without any effects on the CB of TiO2.
Unlike metal ion or cation doping, Nonmetal ion doping cannot for an
impurity energy level (donor level) in the forbidden band of the TiO2
semiconductor [130]. According to this process, the photocatalytic
M. Ismael
efficiency of the photocatalysts will be improved by reducing their
bandgap gap, which can only be accomplished by moving the valence
band upwards (Fig. 22) [131].
Various nonmetal ions, such as C, N, and S were commonly used to
dope TiO2. For instance, Luo et al. [132] reported that B and N dopants
enhance the photocatalytic hydrogen production activity of TiO2 in the
presence of oxygenated hydrocarbon and water. Similarly, Ramalingam
et al. [133] compared photocatalytic hydrogen production of Pd
deposited B, N-doped TiO2 photocatalyst to SrTiO3. Photocatalysts were
prepared via the sol–gel method. In another study, Pd/B9/N5-doped
TiO2 photocatalyst shows higher activity that may be attributed to the
higher stability of the deposited-doped photocatalyst. Yuan et al. [134]
successfully fabricated N-doped TiO2 by a simple heating method of the
precursors. The photocatalytic activity of the doped materials was tested
for hydrogen production. The results show that the phase transformation
(anatase to rutile), enhanced light absorption, and enlarged surface area
are responsible for higher hydrogen production. In another interesting
study, Ilie et al. [135] compared the photocatalytic hydrogen production
from sugar solution of TiO2/SiO2 photocatalyst modified by different
metal and nonmetal elements. Results showed that non-metals present
higher hydrogen production, which may be ascribed to less formation of
the recombination centers compared to the metal ions. S-doped porous
anatase TiO2 is synthesized through a facile thermal method by Xing and
his co-workers [136]. High hydrogen production activity was obtained
for the sample calcined at 700 ◦ C that assigned to higher crystallinity,
porous structure, and the role of the S atom in enhancing charge sepa­
ration. Sang et al. [137] studied the efficiency of photoelectrochemical
H2 evolution for the nanotubular N/C-TiO2 electrode. C doped-TiO2
showed higher activity than C-doped TiO2, which is mainly attributed to
the defect state, and more negative flat band potential caused by C.
Shaban et al. [138] synthesized carbon-doped TiO photoelectrodes by
flame oxidation for photoelectrochemical hydrogen production. This
modified CM-n-TiO2 photoelectrode is capable of producing hydrogen
by splitting water with a conversion efficiency of 9.02% under white
light. Results show that the higher hydrogen production efficiency of
CM-n-TiO2 photoelectrodes was assigned to narrow bandgap energy and
create new mid-band energy provided by carbon as anion dopant. In
another study, Liu et al. [139] synthesized carbonate-incorporated
TiO2 microspheres via the facile solvothermal method for visible-light
photocatalytic hydrogen production and degradation of MO, showing
highly effective visible-light performance with respect to bare TiO2 that
ascribed to the smaller pore size and high specific surface area. Simi­
larly, Zhou et al. [140] demonstrated that nanostructured C doped TiO2
thin film was successfully achieved by pulsed laser deposition, pre­
senting higher photocatalytic hydrogen generation performance and
photocurrent response than bare TiO2. Owing to its stability,
Fig. 22. Narrowing of the bandgap energy by the formation of new valance
band formation through non-metal doping process [131].
14
Fuel 303 (2021) 121207
comparable atomic size, low ionization energy, and efficient trapping
center, nitrogen was widely used as a nonmetal dopant for the photo­
catalytic hydrogen production performance of TiO2. For instance, Babu
et al. [141] prepared a rice grain morphology nitrogen-doped TiO2 and
the photocatalytic activity was assessed for hydrogen production under
visible light irradiation. Nitrogen-doped TiO2 showed higher hydrogen
production activity compared to that of pure TiO2 that may be ascribed
to the efficient charge separation and a higher specific surface area of
the doped photocatalyst. Wang et al. [142] mounted N-doped TiO2 film
by sputtering RF reactive magnetron in a gas mixture. The reduction of N
doped TiO2 bandgap energy was responsible for the enhancement of
hydrogen activity relative to bare TiO2. Likewise, Wang et al. [143]
deposited N-doped TiO2 film with preferred (2 1 1) orientation using the
same approach, the photocatalytic activity of the deposited film was
evaluated for hydrogen production. Herein, (2 1 1) facets show the
highest hydrogen evolution rate. Recently, Sun et al. [144] synthesized
Au/N-C/TiO2 photocatalysts by combining the pyrolysis of the Ti-
containing metal–organic framework and photoreduction. The photo­
catalytic activity of the novel Au/N-C/TiO2 photocatalysts was tested for
hydrogen production under simulated sun-light illumination for 1 h.
Importantly, the composition and interface sequence of the N-doped
carbon layer and Au nanoparticles were carefully engineered and
showed a great influence on the photocatalytic hydrogen production
activity. Their findings indicated that the photocatalytic H2 production
efficiency of N-C/Au/TiO2 is higher than that of Au/N-C/TiO2 due to the
synergistic effect that occurred with a controlled cocatalyst interface
(Fig. 23a-c). Furthermore, the improved light absorption of Au/N-C/
TiO2 photocatalyst is a second cause for the activity enhancement
(Fig. 23d).
Furthermore, Qin et al. [145] successfully engineered a novel CdS/
Ti3+/N-TiO2 using combined evaporation induced self-assembly (EISA)
and hydrothermal methods. Among different synthesized photo­
catalysts, 10%CdS/N-TiO2 exhibited the highest activity, which ascribed
to the broaden the absorption range of visible light provided by nitrogen
dopant and to the reduction of the activation barriers due to the pres­
ence of Ti3+ that act as a hydrogenation shell at the interface of TiO2.
Recently, 2D MXenes, consisting of transition metal cabide or nitride,
have shown excellent electrical performance and have been applied in
catalysts [146,147]. For instance, Kong et al [148] used a simple and
low-cost route for the first time synthesis of nanolayered photocatalyst
of N-doped TiO2 nanoparticles and N-doped C derived from layered N-
Mxene. The as-prepared N-TiO2/NC nanocomposite displayed higher
activity toward hydrogen production via water splitting under visible
light irradiation, which assigned to the enhanced visible light absorption
and efficient charge separation ability. Sulfur ion is also used as a
nonmetal dopant. For instance, Yang et al. [149] successfully con­
structed core–shell nanostructured S-doped rutile TiO2, the presence of
sulfur on the surface of the rutile TiO2 was investigated using X-ray
photoelectron spectroscopy (XPS) (Fig. 24(a)). As a result, sulfur-doped
titania boosts the photocatalytic hydrogen production rate assigned to
enhance light absorption (Fig. 24(b)).
In another study, Vorontsov et al. [150] showed that the doping of
TiO2 anatase by substitution of Ti with cationic sulfur S6+ and S4+ is
energetically unfavorable for the bulk and favorable for the surface.
Their results showed that the doped TiO2 with S4+ resulted in lattice
distortions comparable to that for S6+, resulting in the introduction of an
uncompensated charge for neighbor Ti atoms and induce visible light
absorption and visible light photocatalytic activity through narrowing
the bandgap energy. Furthermore, plots of frontier orbitals for S4+-
doped nanoparticle presented that holes and electrons have distinctly
different localizations which mean effective separation of photo­
generated charges and expected small rate of recombination. Moreover,
their findings showed that structural effects have a profound influence
on photocatalytic properties of S-doped TiO2. Fluorine anion was also
used in the literature as a dopant for the improvement of hydrogen
production activity of TiO2 [151]. Furthermore, Liu et al. [152] also
M. Ismael
Fig. 23. (a) Hydrogen production of different photocatalysts under simulated sunlight for 1 h, (b) Transient photocurrent response, (c) Electrochemical impedance
spectroscopy, and (d) Absorption spectra of different photocatalysts [143].
Fig. 24. (a) Core-shell S 2p XPS spectrum of R’-TiO2-S and R-TiO2, and (b) Visible-light driven photocatalytic H2 generation by R’-TiO2-S, R-TiO2-S, and R-
TiO2 [148].
stated that good bandgap narrowing, better distribution, and valence
band elevation can only be accomplished if the anion has less electro­
negativity than oxygen.
2.2.3. Noble metal/ cocatalyst loading
Various metal nanoparticles or cocatalysts, such as Pt [153], Pd
[154], Au [155], Cu [156], Rh, Ru [157] and Ag [158] are very active
cocatalysts for improving TiO2 photocatalysts by suppressing the
recombination of photogenerated electron-hole pairs. Noble metals are
commonly used as cocatalysts have lower Fermi energy levels than that
of TiO2. Thus, when they were loaded onto the surface of the TiO2
photocatalyst either by situ photodeposition or impregnation method,
the Schottky barrier can be formed at the interface between the two
(Fig. 25(a)) [159,160]. The photogenerated electrons are therefore
15
Fuel 303 (2021) 121207
passed through the Schottky barrier to the host photocatalysts surface
and captured by the cocatalyst, which serves as a hydrogen evolution
site. (Fig. 25(b)) [161]. Thus, electrons are efficiently separated from the
VB holes, resulting in improving hydrogen evolution activity. Further­
more, the work function of the metal plays a key role in controlling the
electron-hole separation [162]. Additionally, when noble metal such as
Au and Ag are decorated on the surface of TiO2, there is an additional
effect, the localized surface plasmon resonance (LSPR), which contrib­
utes to a strong absorption of the visible light and thus enhanced the
photocatalytic performance under the visible light illumination [163].
However, noble metals like gold (Au) and platinum (Pt) are the most
widely studied dopants for TiO2, owing to their superior work function
[106]. Recently, Beasley et al. [164] studied the influence of the work
function of the common noble/metal ions on the photocatalytic
M. Ismael
Fig. 25. (a) Schematic illustration of electron transfer through the Schottky barrier to the cocatalyst nanoparticle [158], (b) Charge separation mechanism confirmed
by the presence of cocatalyst [160].
hydrogen production over TiO2. Their findings investigated that the
hydrogen production activity is strongly correlated to the work function
of the metal ion and increased with the increasing the work function of
the metals. Different metals were used in this study such as Pt, Pd, Cu,
Ru, and Ag with their work functions are 5.93, 5.60, 5.10, 4.71, and
4.26 eV, respectively. Pt/TiO2 showed the highest activity for hydrogen
generation from water due to its larger work function and upward-bent
band causing the photoelectrons to be trapped in those metal sites that
are eventually consumed during water reduction, therefore, enhance the
charge separation efficiency. Whereas, other metals such as Ag, Ru, and
Cu were less effective towards hydrogen production due to downward-
bent band gaps that allow the photoelectrons to return to TiO2 from
the metal which leads to faster charge recombination. Generally, the
enhanced photocatalytic of TiO2 due to the presence of these cocatalysts
can be attributed to the role of the cocatalyst in trapping electrons and
thereafter enhanced the charge separation, surface plasma resonance
effect of the metal, creation of the new energy levels, and generation of
gap state due to the interaction between these metals and the VB of TiO2.
For instance, Yu et al. [165] hydrothermally synthesized Pt depos­
ited on TiO2 nanosheets with exposed (0 0 1) facets for hydrogen pro­
duction in ethanol solution using as a sacrificial reagent to trap holes.
2 wt% of loaded Pt nanoparticles displayed the highest photocatalytic
activity that may be ascribed to the efficient charge separation provided
by the cocatalyst. In another study related to the same cocatalyst, Zhu
et al. [166] used the simple sol–gel method to successfully grow Pt
deposited TiO2 hollow sphere. 1 wt% Pt charged TiO2 was optimum and
demonstrated the highest production rate of hydrogen and long-term
stability. In another study, Sosa et al. [167] synthesized a series of Pt
doped mesoporous titania using the sol–gel technique employ­
ing Pluronic F127 triblock-copolymer. 2.50 wt% was optimum and
shows the highest photocatalytic hydrogen production activity, due to
the efficient charge separation and narrowing the bandgap energy. Sun
et al. [168] successfully synthesized different molecular weights of
polyethylene glycol PEG-modified TiO2 photocatalyst via the sol–gel
method. Among different synthesized photocatalysts, Pt/PEG6000-
TiO2 demonstrated the highest hydrogen production activity that may
be assigned to the large surface area and efficient charge separation
providing by PEG and Pt nanoparticles, respectively. Tristantini et al.
[169] studied the role of nitrogen and platinum as dopants in enhancing
the photocatalytic hydrogen production over anatase TiO2 nanotubes in
the presence of glycerol. The photocatalytic activity of Pt-N-TiO2 was 13
times higher than the bare P25, which ascribed to the role of Pt to sta­
bilize N in the crystal lattice of TiO2 by minimizing N leaching into so­
lution. Furthermore, Pt nanoparticles can also trap electrons and
enhance the charge separation efficiency of N-TiO2. Yang et al. [170]
reported that both Pd/TiO2 and Pt/TiO2 anatase photocatalysts have
higher activities toward hydrogen production in the presence of ethanol
than Rh/TiO2, which ascribed to the poor contact between the metal
16
Fuel 303 (2021) 121207
particle (Rh) and the titanium oxide support. Furthermore, the forma­
tion of the surface ethoxide and hydroxyl formed by dissociative
adsorption at the interface between the Pt (or Pd) metal particles and
TiO2. Thus electrons of metal ion reduce the hydrogen atom in the hy­
droxyl, in the meantime, ethoxide species acts as a hole scavenger,
resulting in enhancing the charge separation of the photocatalytic and
improving the photocatalytic performance. Pd as a cocatalyst can also
enhance the photocatalytic hydrogen evolution activity of TiO2. For
instance, Ye et al. [171] sensitized TiO2 nanotube arrays by palladium
quantum dots. Compared with undoped TiO2, the photocatalytic activity
of Pd/TiO2 was sharply enhanced toward the production of hydrogen,
which may be attributed to the smooth charge separation provided by
the coupling effect between TiO2 nanotubes and Pd quantum dots. Au as
a noble metal cocatalyst was also reported in the literature as a prom­
ising metal in enhancing the hydrogen evolution activity of TiO2. Priebe
et al. [172] stated that the increased activity in the production of
hydrogen in an aqueous methanol solution of Au deposited TiO2 cata­
lysts depended on the formation of plasmonic Au particles and the ef­
ficiency of Au cocatalyst charge separation. Furthermore, Ortiz et al.
[173] compared the photocatalytic activities of undoped and doped
TiO2 synthesized via two different methods. The photocatalyst sample
prepared by the sol–gel/solvothermal/thermal exhibited the highest
activity for hydrogen evolution for 4 h was ascribed to the reduction of
the bandgap energy (Fig. 26(a&b)) and enlarged the specific surface
area (Fig. 26(c&d)). Although noble metals modified TiO2 are particu­
larly stable under light irradiation and effective for H2 production,
however, due to their high price, alternative low-cost transition metal
cocatalysts have to be investigated [174]. Ag2O also could be used as a
cocatalyst. For instance, Lalitha et al. [175] successfully deposited Ag
ion on TiO2 using the impregnation method. Among the different
amounts of Ag loading, 0.5 wt% shows the highest hydrogen evolution
activity in an aqueous solution containing methanol. Herein, Ag
deposited on the surface of TiO2 plays an important role in enhancing
the photocatalytic activity.
However, metallic Ag usually shows a far low H2-evolution rate due
to its serious capacitive property and poor H2-evolution activity for Ag-
modified photocatalysts compared to the common noble cocatalyst like
Pt. For that, Gao et al [176] boosted the photocatalytic hydrogen activity
performance of Ag by generating core–shell Ag@Ni cocatalysts. All the
as-synthesized Ag@Ni/TiO2 photocatalysts displayed a markedly
enhanced photocatalytic hydrogen evolution rate, which attributes to
the presence of both Ag and Ni metals, which act as an electron sink and
interfacial active hydrogen site, respectively. In another study, Wu et al.
[177] synthesized Ag/TiO2 NTs (NTs: nanotubes) photocatalysts using
the microwave-assisted chemical reduction method and tested their
activities for hydrogen production. Their results revealed that the Ag/
TiO2 NTs exhibited 3.3 times higher than pure TiO2, which mainly
attributed to the surface plasma resonance effect of Ag metals and the
M. Ismael Fuel 303 (2021) 121207

Fig. 26. UV–Vis-DRS for (a) TiO2-F (without metal) and (b) TiO2Ag-F, N2 adsorption–desorption isotherms of TiO2-F (without metal) and TiO2Ag-F. (F: second
method) [172].

Fig. 27. Hydrogen production (a) for different photocatalysts containing different amount of cocatalysts, (b) vs irradiation time, (c) absorption spectra, and (d) the
stability of the most active photocatalyst [179].

17
M. Ismael
role of Ag nanoparticles in restraining the charge recombination. Copper
nanoparticles are also could be used as an alternative to the expensive
noble metals-based systems due to their availability, cheap, and narrow
bandgap energies (1.4–2.3 eV) [178,179]. Ravi et al. [180] synthesized
CuO@NiO core–shell structures used a chemical reduction method. This
novel cocatalyst was deposited over TiO2 nanoparticles to enhance
hydrogen production generation. Among differently prepared photo­
catalysts, CNO1-10 T (10% wt TiO2) presented the highest activity
(Fig. 27(a&b)). Enhanced photocatalytic hydrogen production activity
was attributed to improved light absorption (Fig. 27c). Additionally, this
novel photocatalyst showed obvious stability after 3 days (Fig. 27d).
In another related study, Wang et al. [181] decorated CuO quantum
dots on TiO2 nanosheets with exposed {0 0 1} facets using the hydro­
thermal method. The photocatalytic activity was evaluated for hydrogen
production in the presence of methanol under light irradiation. 5% CuO/
TiO2 showed the highest activity (Fig. 28a), which attributed to the
efficient charge-separated revealed by the transient photocurrent mea­
surements (Fig. 28b), and improved charge absorption (Fig. 28c) caused
by the reduction in the bandgap energy (Fig. 28d). The work of Wu et al.
[182], for example, preferentially demonstrated that the impregnation/
calcination method was successfully applied to prepare Cu nanoparticles
on the surface of TiO2. Results showed that Cu can facilitate the charge
transfer, thereafter, enhancing the photocatalytic hydrogen production
of TiO2. Kumar et al. [183] illustrated that the improvement in the
photocatalytic hydrogen production activity of CuO/ TiO2 is due to the
quantum size of CuO and increased photo-excited electrons and hole
separation efficiency. This charge separation improvement was attrib­
uted to the formation of Cu2O, which facilitates the interfacial electron
transfer to generate hydrogen. Similarly, Nie et al. [184] fabricated Cu/
TiO2 as a highly efficient visible-light photocatalyst for photocatalytic
hydrogen generation. Enhanced hydrogen production activity was
mainly attributed to the Cu-SPR effect. The electrons generated from
TiO2 upon illumination can easily reduce the Cu2+/Cu+ species to Cu0,
Fig. 28. (a) Hydrogen evolution rate over a different amount of CuO quantum dots over TiO2, (b) transition photocurrent response, (c) Absorption curve, and (d)
Tauc plots for bandgap determination [180].
18
Fuel 303 (2021) 121207
which in turn promotes more electron-hole pair generation. Further­
more, copper nanoparticles act as a cocatalyst to trap the generated
electron from TiO2 and transfer them to the protons for more hydrogen
generation.
Enhanced photocatalytic hydrogen production of TiO2 by grafting of
Cu2S on its surface is documented by Guan et al. [185]. Herein, the
photocatalytic activity of Cu2S/ TiO2 was greatly enhanced compared to
bare TiO2, which ascribed to the visible light absorption property of
Cu2S, efficient charge separation and transfer provided by the formation
of the interfacial Schottky barrier, and the ability of Cu2S in lowing the
activation energy or overpotential for the proton reduction. It was
demonstrated by Yoong et al. [186] that copper doping onto TiO2 se­
miconductor photocatalyst has enhanced the photocatalytic hydrogen
production of TiO2. Different amount of the dopant loading varied from
2 to 15% was synthesized via combined calcination and wet impreg­
nation methods. Among the different amounts of Cu dopants, 10 wt%
Cu/TiO2 calcined at 300 ◦ C showed the highest hydrogen production
activity in the presence of methanol as an electron scavenger. Reduction
of the bandgap energy of TiO2 and improving the charge separation
performance due to the presence of Cu ions are believed to be respon­
sible for enhanced the photocatalytic performance. Xu et al. [187] also
studied the effect using different synthesis methods on the production of
hydrogen over Cu/TiO2 photocatalysts. Among the four different syn­
thesis methods used in the study, the sol–gel method exhibited the
highest activity even more than the Pt/Au loaded TiO2 that ascribed to
the high stability and efficiency, low-cost and high stability. Further­
more, this study showed that the distribution of Cu over TiO2 and the
chemical states of Cu are strongly affected by the applied synthesis
method. Active and cheap Cu/TiO2 photocatalysts were synthesized by
the photodeposition of Cu on the surface of TiO2 supports was docu­
mented by Montini et al. [188]. Importantly, the photocatalytic activity
of Cu/TiO2 photocatalysts is strongly dependent on the TiO2 supports.
Two types of supports were used in the study; titanium isopropoxide and
M. Ismael Fuel 303 (2021) 121207

titanyl sulfate. Interestingly, a sample containing 2.5 wt% Cu and pre­

pared from titanium isopropoxide support TiO2 exhibited the highest
activity. This could be ascribed to the longer lifetime of the electron/
hole pair of multiphasic TiO2 materials. Table 1 listed various doped
TiO2-based photocatalysts and their photocatalytic hydrogen activity
performance.

2.2.4. Semiconductors combination

The semiconductor combination between TiO2 and other semi­
conductors to construct a heterojunction structure is another significant
technique to harness visible solar radiations by reducing the bandgap
energy and promote charge separation for enhancing hydrogen evolu­
tion. [209], in principle, when the semiconductor photocatalyst with a
higher conduction band is combined with the semiconductor having a
lower valence band, electrons are moved from the higher CB semi­
conductor (semiconductor I) to the lower VB semiconductor photo­
catalyst (semiconductor 2), while photogenerated holes migrate in the
opposite direction. This way of charge separation is called type II het­
erojunction and is the most typical heterojunction system used for
enhancing the photocatalytic activity of TiO2 to produce hydrogen.
Therefore, effective charge separation is observed as shown in Fig. 29
[210]. Besides, type II heterojunction, the holes and electrons transfer in
the type I heterojunction in one direction; from semiconductor 1 to 2,
leading to accumulation of the charge carriers in one semiconductor (B),
which is negative for e-/h+ separation. Due to the mismatching between
the band positions of the two semiconductors, as a result, there is no
charge transfer and separation of electrons and holes between the two
semiconductors that usually happened in the type (III) heterojunction.
Graphitic carbon nitride (g-C3N4) as a robust metal-free photo­
catalyst has been widely used as a promising candidate for different
applications in photocatalysis [211–215]. Ismael et al. [216] recently
Fig. 29. Charge separation in composite semiconductors [208].
reviewed several applications of g-C3N4 in photocatalysis. Due to its
suitable band position (CB and VB position), it is considered to be a
promising candidate for the heterostructure composite formation with
TiO2. Recently, Lv et al. [217] in their work – a 3D camellia-like
NH4TiOF3/TiO2/g-C3N4 heterostructure was constructed by a conve­
nient method with higher photocatalytic hydrogen production activity.
They observed that there was a great deal of enhancement in the
hydrogen production, which is ascribed to the multiple refractions and
reflections of light within the catalyst, which greatly improved the ef­
ficiency of light absorption. Furthermore, the coupling of NH4TiOF3 and
TiO2 also effectually reduced the electron-hole recombination in the g-
C3N4. Ti3+ self-doping black TiO2/g-C3N4 hollow core–shell nano-
heterojunction was reported by Pan et al. [218]. The nano-
heterostructure was synthesized using the hydrothermal method and

Table 1
various doped TiO2-based photocatalysts and their photocatalytic hydrogen activity performance.
Years Photocatalyst Catalyst morphology Sacrificial reagent Reaction parameters H2 production activity Ref
-1 − 1
2016 W-TiO2/Au Spherical TiO2 Methanol 500 W Xe lamp/Pt 24 mmol g h [189]
nanoparticles
2018 Co, Ni, and Cu-doped NanoparticlesTiO2 Methanol UV light irradiation 85 μmol/h [190]
TiO2
2018 Ga-doped TiO2 NanoparticlesTiO2 Methanol 150 W Xe (310 nm < λ < 625 nm)/ Pt 5722 mmol g1 h1 [191]
2014 Bi-doped TiO2 NanofibersTiO2 Ethanol Hexagonal arrangement around the 800 μmol g− 1h− 1 [192]
reactor, 8 W visible light
2017 Cu+1/Cu0 –TiO2 Mesoporous TiO2 Methanol Solar light 1000 μmol/h [193]
2016 Cu-doped TiO2 Quasi spherical TiO2 Methanol Quartz cell/ 300 W Xe lamp 2.80 mol cm− 2h− 1
[194]
nanoparticles
2015 Au-Pt Alloyed TiO2 Spherical shape TiO2 Methanol 300 W Xenon arc lamp, (λ > 420 nm) 3500 μmol h− 1 [195]
2012 Bimetallic loaded Mesoporous TiO2 Methanol 300 W Xenon arc lamp, (λ > 420 nm) 1.7 cm3/h.gcat [196]
mesoporous TiO2-SiO2
2015 S-doped TiO2 Porous TiO2 Methanol AM 1.5 solar power system, 163.9 mmol h1 g1 [197]
nanopillars λ ≥ 400 nm
1 2
2014 N-doped TiO2 films NA Methanol Quartz cell, Xe lamp (300 W) 4500 mmol H2 h m /methanol [198]
2011 Cu-Ni/TiO2 Nanofibers TiO2 Ethanol UV-A and B, Pt, Pd/ pH = 7 700 μmol/h (UV-A) and [199]
2250 μmol/h (UV-B)
2012 B − N − TiO2 Crystalline Methanol Quartz reactor, 8 * 36 W light 14 μmol/50 mg [200]
nanoparticles fluorescent lamps
2017 Pd-Pt/Nb-doped TiO2 Nanoparticles TiO2 Methanol Hg(UV)-Xe (Vis) lamp (500 W), 0.7 mmol g-1h− 1
[201]
2012 Cu2O/Cu/TiO2 Nanotubes TiO2 Na2S/Na2SO3 350 W, Visible-light (λ > 420 nm) 45 μmol [202]
nanotube arrays
2015 Cu/TiO2 nanoparticles NanoparticlesTiO2 Titanium 500 W halogen lamp, visible light 11000 μmol/min [203]
tetraisopropoxide, Cu
(NO3)2⋅3H2O
2012 Be/Fe/Pt-loaded Nanostructure TiO2 Methanol 100 mW/cm2, electrolyte (KOH/ Photocurrent density (0.32 mA/ [204]
nanostructured-TiO2 film H2PtCl6) cm2), hydrogen rate (0.1 ml/h
films cm2)
2017 N-doped mesoporous MesoporousTiO2 Methanol 450 W Xe lamp, visible light 270 μmolg− 1 [205]
TiO2 (λ ≥ 400 nm)
2015 Fe-Ni/Ag/TiO2 Spherical TiO2 Ethanol A 500-W Xenon lamp, 400 nm cut-off 5000 umol/gcat [206]
nanocomposites glass filter
2016 Cu/N co-doped TiO2 Aggregate Methanol 500 W halogen lamp, 400 W medium 27.4 mmol g− 1h− 1 (UV) [207]
nanoparticles pressure halide lamp, 283 μmol g− 1h− 1 (UV)
2011 Fe- TiO2 Nanoparticles TiO2 Methanol 500 W Hg lamp 2400 μmol h− 1 [208]

19
M. Ismael
tested for hydrogen production. Enhanced photocatalytic activity of B-
TiO2/g-C3N4 nano-heterojunctions was attributed to the efficient charge
separation revealed by the transient photocurrent, PL, EIS experiments.
Nasir et al. [219] prepared a 1D branched TiO2 loaded Au/g-C3N4 QDs
hybrid and analyzed its photocatalytic hydrogen activity under visible
light. Authors found that the hybrid exhibits an obvious activity owing
to the efficient charge separation and improved light absorption offered
by the type II heterostructure system and the presence of plasmonic Au,
respectively. Likewise, Nasir et al. [220] synthesized the same hybrid
without loading of Au over g-C3N4 quantum dots. The activity was
enhanced compared to the pure TiO2 or g-C3N4 but less than that with
Au nanoparticles, confirming the role of Au in enhancing the photo­
catalytic performance. Geng et al. [221] noted that the construction of
Ag/TiO2/g-C3N4 heterojunction nanocomposite by self-assembly
enhanced photocatalytic hydrogen production. The higher activity of
the nanocomposite is due to the formation of the active site through the
coordination of Ag+ ions with the g-C3N4 and the distribution of the TiO2
nanoparticles forming the heterostructure. Moreover, Chai et al. [222]
synthesized (g-C3N4)-Pt-TiO2, showing highly effective visible-light
hydrogen production activity performance for bare g-C3N4 and TiO2.
A well-aligned band position for the formation of the heterostructure
together with the role of Pt in enhancing charge separation is respon­
sible for the enhancing activity of the composite. In another study, Yan
et al. [223] reported the synthesis of visible-light TiO2-g-C3N4 composite
material for hydrogen production activity in aqueous methanol solution
using a sacrificial reagent. The improved composite activity has been
allocated to improve the absorption of visible light. Recently, Ramos
et al. [224] prepared type II g-C3N4 coupled TiO2 heterojunction pho­
tocatalyst using the hydrothermal method. The highest hydrogen pro­
duction activity was achieved with the heterojunction structure
containing a high amount of TiO2 (1:4). The higher activity of the
composite compared to that of pure g-C3N4 or TiO2 is assigned to the
Fig. 30. (a) Hydrogen production activity as a function of time in an aqueous solution containing different amount of Pt deposited graphene compared to P25, (b) PL
spectra of pure and nanocomposites, (c) UV–vis diffuse reflectance spectra of pure and nanocomposites, and (d) Corresponding Tauc plot for bandgap determina­
tion [223].
20
Fuel 303 (2021) 121207
reduced bandgap energy, large pore size, enhanced charge separation,
and suitable band positions of both semiconductors forming the com­
posite. Similarly, Cheng et al. [225] prepared TiO2 graphene nano­
composite by the solvothermal reaction, followed by a remarkable
increase in photocatalytic efficiency in hydrogen production using
CH3OH as an electron donor and Pt as a cocatalyst (Fig. 30(a)) 10 wt%
GR-P25 was the optimum and presents the highest activity, which
attributed to the light absorption enhancement ability and charges
separation efficiency confirmed by the photoluminescence and the
UV–Vis and experiments, respectively (Fig. 30(b-d)).
Likewise, Zeng et al. [226] hydrothermally constructed graphite
oxide (GO)-TiO2 nanocomposite for H2 production at the light of
λ ≥ 420 nm irradiation and 2 wt% GO-TiO2 exhibited the highest ac­
tivity. Shifting the light absorption into the high wavelength region is
believed to be the responsible factor for enhancing hydrogen production
activity. Interestingly, Corredor et al. [227] synthesized rGO/TiO2
composites with different ratios of reduced graphene oxide and tested
them toward hydrogen evolution in the presence of methanol. Their
study compared the photocatalytic activity of pure TiO2 and 2% rGO.
Importantly, they showed that applying argon in removing hydrogen
from the reaction mixture has shown effective in recovering the
hydrogen generation rate over TiO2 for long operation times, while rGO
is reduced due to the increase in the defects in its structure. A novel
PANITiO2/rGO photocatalysts (PANI: polymerized aniline) was syn­
thesized by the ultrasonic method reported by Ma et al. [228]. PAN­
ITiO2/rGO photocatalyst exhibited the highest photocatalytic hydrogen
activity compared to that of TiO2/rGO and pure TiO2 photocatalysts
(Fig. 31a&b). Furthermore, Enhanced activity was attributed to the
enhanced light absorption and the reduction of the bandgap energy
(Fig. 31c&d). Besides the π conjugated structure of graphite and gra­
phene, other oxides and sulfides with suitable redox potential can
combine with TiO2. For instance, Miwa et al. [229] prepared various
M. Ismael
Fig. 31. (a&b) Hydrogen evolution rate over different photocatalysts (photocatalysts containing 0.45% PANI showed the highest activity), (c) Absorption spectra,
and (d) Tauc plot of PANITiO2/rGO, TiO2/rGO, and TiO2 [226].
primary oxide binding nanocomposites TiO2, such as ZnO, SnO2, CuO,
Al2O3, and CuO/Al2O3/TiO2, using a hybrid high-temperature mixing/
solid-state reaction process. Results indicated that ternary composite
displayed higher activity than binary composite, and 0.2 wt% CuO/
0.3 wt% Al2O3/TiO2 received the highest activity. Due to their ability to
harvest visible light, Bi-based semiconductors are widely studied in
photocatalytic water splitting. Among them, BiYO3 was widely owing to
the suitable bandgap energy (2.6 eV) that can utilize visible light [230].
Nevertheless, as a single semiconductor, BiYO3 has some limitations in
practical applications in photocatalysis, such as efficiency of charge
transport and light absorption capacity. For that reason, Qin et al [231]
recently synthesized TiO2/BiYO3 photocatalysts by a facile sol–gel
method. Charge separation efficiency provides by type I heterostructure
between the two semiconductors is responsible for the enhancement of
its photocatalytic hydrogen production activity. In another study, Zhao
et al. [232] reviewed TiO2/CdS nanocomposites with different micro­
structures for different applications in photocatalysis and photovoltaics.
Alenzi et al. [233] decorated Ag+ nanoparticles over TiO2 to form Ag/
TiO2 film for hydrogen production in the presence of methanol. This
study clearly showed that the hydrogen production activity is enhanced
in the presence of silver ions, which is related to the efficient charge
separation.
Similarly, Zhao et al. [234] compared two synthesis methods used
for the preparation of Ag/TiO2 nanocomposite. Interestingly, photo­
catalyst prepared by ultrasonic spray pyrolysis shows higher photo­
catalytic hydrogen production and CO2 photoreduction than that
prepared by the wet impregnation method. Authors claim that better
distribution of the silver ion and large surface area of the nanocomposite
synthesized by the second route is responsible for high activity
enhancement. Yu et al. [235] successfully fabricated CuO/CF/TiO2
nanocomposite using combined impregnation and calcination ap­
proaches. Among different weight ratios of carbon fiber used, 1 wt%
21
Fuel 303 (2021) 121207
shows the highest activity that may be ascribed to the decrease charge
recombination. She et al. [236] modified TiO2 nanosheets by Cu(OH)2
and their activities was evaluated for hydrogen production. 2% Cu(OH)2
was optimum and reaches the highest activity. This remarkable
enhancement in activity was attributed to the efficient charge separation
offered by the composite formation. In another study, Pei et al. [237]
prepared an N-doped TiO2/graphene nanocomposite for the determi­
nation of hydrogen activity. Results indicated that nanocomposites
exhibited higher activity due to the decrease in bandgap energy and
suitable band matching between the two semiconductors lead to smooth
charge transfer and separation. With MWCNT-TiO2 composites loaded
with different contents of CNT, Reddy, and co-workers [238] studied
their hydrogen production performance in glycerol aqueous solutions.
0.1 wt% CNT presented the highest activity due to the enhancement of
light absorption efficiency. The AgIn5S8/TiO2 composite photocatalysts
were studied by Li and co-workers [239] for the photocatalytic pro­
duction of hydrogen. Encouragingly, the resulting g- AgIn5S8/TiO2
heterojunctions prepared by the ultrasonic-deposition method showed
higher activity than that prepared via the hydrothermal method. This
superior activity may be ascribed to the better dispersion of AgIn5S8 over
TiO2. Moreover, Yermokhina and his group [240] systematically studied
the mesoporous Ni/TiO2 nanocomposite photocatalyst for improved H2
evolution. Results demonstrated that doped materials showed higher
photocatalytic activity than that of pure TiO2, which is attributed to the
high surface area. Molybdenum disulfide (MoS2) with a narrow bandgap
energy of ~ 1.29 eV is considered as a promising catalyst to extend the
sunlight absorption range and improve hydrogen production activity by
edge S - Mo - S active sites [241]. Liu et al. [242] proposed that eosin-
sensitized Au/Cu nanoalloy/TiO2/MoS2 ternary hybrid led to high
quantum efficiency for
photocatalytic water splitting to generate hydrogen. This remarkable
improvement is mainly attributed to the synergistic effect between the
M. Ismael Fuel 303 (2021) 121207

Au/Cu nanoalloy and TiO2/MoS2, which facilitate the charge separation
and improve the light absorption efficiency. Afanasiev and co-workers
[243] combined MoS2 “inorganic fullerenes” with high surface area
TiO2 to achieve enhanced hydrogen generation rate in water-methanol
slurries. Interestingly, Enhanced hydrogen production MoS2 inorganic
fullerenes/TiO2 composite was mainly ascribed to the transfer of long-
live photogenerated stored electrons (accumulated) electrons from the
TiO2 to MoS2 inorganic fullerenes, the contact between the MoS2 and
TiO2, and excellent dispersibility of MoS2/ inorganic fullerenes and
stability of its colloidal suspensions in water-methanol mixtures.
Anatase/Rutile biphasic TiO2 nanoparticles@MoS2 nanosheets hetero­
junctions were reported by Zhong et al. [244]. Photocatalytic activity of
the heterojunction was assessed for hydrogen production under solar
irradiation. Effective charge separation between the titania phases as
well as between them and the surface of TiO2 nanoparticles@MoS2
nanosheets heterojunctions was responsible for the photoactivity
enhancement of the system. Other semiconductors with an appropriate
band position could be considered as promising candidates to couple
with TiO2, such as Fe2O3 [245], Bi2O3 [246], and In2S3 [247]. The
composite formation between the semiconductors was reported to play a
key role in the inhibition of the charge recombination rate. Nonetheless,
this technique has some drawbacks, such as photocorrosion in the
aqueous phase of some composite-forming semiconductors affecting
their stability [248,249] and also finding suitable couples of semi­
conductors with band alignment to facilitate the separation of the
charge carrier. Table 2 listed different TiO2-based photocatalysts and its
composites with different morphology and photocatalytic hydrogen
activity performance.
2.2.5. Dyes sensitization
Besides metal and nonmetal ion doping, noble metal loading, and
composite formation, dye sensitization is another significant technique
to harvest visible solar radiations for enhancing hydrogen evolution.
Several dyes such as safranine and others are considered to be promising
candidates for visible light sensitivity. Fig. 32 shows the most common
dyes used to sensitize TiO2. They can be successfully utilized in solar
cells as well as photocatalytic systems to sensitize TiO2. According to
this method, electrons were injected from the excited dyes that adsorbed
on the surface of the TiO2 to the CB of TiO2, where they were used to
reduce water and produce hydrogen as illustrated in Fig. 33 [274].
For instance, Jin et al. [275] sensitized that eosin dye CuO incor­
porated a TiO2 catalyst for photocatalytic hydrogen production at light
irradiation of λ > 420 nm in the presence of different electron donors.
Enhance photocatalytic activity of the sensitized photocatalyst was
ascribed to efficient electron immigration between the dye molecule and
the composite. Ru-complexes are the most popular used dyes in photo­
sensitive TiO2 owing to the suitable energy bandgap and absorption,
excellent stability in aqueous solutions, and relatively high efficiency
[276]. For instance, Zhang et al. [277] achieved highly visible-light
photocatalytic hydrogen production over a TiO2 system sensitized by
binuclear RuII bipyridyl (bpy) complex [Ru2(bpy)4(BL)]
(ClO4)2 (BL = bridging ligand) without using cocatalyst, accompanied
by a remarkable enhancement of photocatalytic capability and stability
in hydrogen production. Abe et al. [278] evaluated sensitized visible-
light Pt/TiO2 photocatalysts over different dye for H2 production from
a water-acetonitrile containing iodide. Decreased bandgap energy and
charge transfer between Pt/TiO2 and dye are believed to be responsible
for the higher hydrogen production activity of the sensitized photo­
catalyst. Likewise, Park et al. [279] sensitized Pt/TiO2 with Ru(bpy)2+
3
without anchoring groups in the presence of different anions. PO3– 4 was
most efficient and facilitated stable H2 production. This could be
attributed to the role of PO3–
4 in changing the charge of platinized TiO2
under the acidic condition from positive to negative, which allowed the
Ru(bpy)2+3 to adsorb to the surface of Pt/TiO2, facilitating electron
transfer from the photosensitizer to the conduction of TiO2. Neverthe­
less, Ru-complexes are expensive materials, toxic restrict their wide­
spread practical application. Therefore, looking for novel metal-free
organic dyes that could extend the light absorption to the NIR region is
crucial for improving the H2 production activity of dye-sensitized TiO2.
Recently, Ding et al. [280] sensitized platinized TiO2 with two indeno

Table 2
listed different TiO2-based photocatalysts and its composites with different morphology and photocatalytic hydrogen activity performance.
Years Photocatalyst Catalyst Morphology Sacrificial Reaction parameters H2 production activity Ref
reagent

2015 NiO/TiO2 composite Nanofibers TiO2 Methanol 300 W Xe lamp 337 μmol h− 1g− 1
[250]
2016 CuOx/TiO2 thin film Nanorods film Methanol 300 W Xe lamp 53 mmol m− 2h− 1
[251]
2012 urchin-like Bi2S3/TiO2 Urchin-like sphere Ethanol UV-lamp 18 W cm− 2 14.2 ml of H2 [252]
2017 TiO2-ZnO nanocomposites Nanostructure Ethanol High pressure Hg pen-lamp, UV 1050 μmol h− 1 [253]
irradiation,
2013 mesoporous-assembled TiO2–ZrO2 Mesoporous TiO2 DEA 300 W Xe arc lamp, 400 nm cutoff [254]
nanocrystals filter,
2017 Ag2O, Bi2O3, ZnO/TiO2 Spherical shape TiO2 Glycerol 350 W Xe arc lamp, 200 μmol g-1h− 1 (Ag2O) [255]
2012 TiO2/graphene sheets nanocomposites Rod shape TiO2 Na2S/Na2S3 500 W Xe lamp, UV–vis light, 28 μmol h− 1 [256]
2013 CuO/TiO2 nanorod Multiwall tubular Methanol 150 W of 2 metal halide light bulbs 670 μmol h− 1g− 1cat [257]
2014 rGO/TiO2 nanowire microsphere Spherical TiO2 Methanol 500 W Xe lamp, Pt 85 μmol min− 1 [258]
composites
2015 porous CuO/TiO2 rods Rod shape TiO2 Methanol 300-W xenon lamp, 15 mmol g− 1h− 1 [259]
2014 Au–TiO2–graphene composites Nanoparticles TiO2 Methanol 420 nm-LEDs (3 W), 296 μmol h− 1 g− 1 [260]
2016 Ag–TiO2/graphene composite Nanostructure TiO2 Methanol visible light irradiation (λ ≥ 420 nm) 225 μmol h− 1 g− 1 [261]
2014 Ag-P25-Gr nanocomposites Two dimensional sheet Ethanol Xenon lamp, 2.25 mmol g− 1 [262]
structure
2017 TiO2-ZnO Nanoparticles TiO2 Ethanol Hg lamp λ = 254 nm, 2.2 mW/cm2 1048 μmol h− 1 [263]
2015 Pt@MWNT/TiO2 Nanotubes TiO2 Na2S/Na2S3 450 W (λ ≥ 420 nm) 435.9 μmol h− 1 [264]
2014 g-C3N4/TiO2 Intact block structure Methanol 500 W Xe lamp, 53 μmol h− 1 [265]
2014 Cu2O/TiO2 Nanorods TiO2 Glycerol Sunlight irradiation, 50,339 µmol h− 1 g− 1cat [266]
2013 C60-d-CNTs/TiO2 Nanostructure TiO2 TEOA 300 W Xe lamp 600 µmol h− 1 [267]
2016 TiO2/WO3 nanofibers Nanofibers TiO2 Methanol 300 W Xe arc lamp 1600 µmol g− 1h− 1 cat [268]
2014 AgPd@Pd/TiO2 Nanoporous TiO2 Formic acid 700 W Xe lamp 70 ml/min [269]
2016 Au-TiO2@GO core–shell Core-shell structure NA UV (125 W) and visible, light (250 W), 114 μmol/h [270]
pH = 2.5
1
2014 CoOx/TiO2 nanocomposites Nanocrystals TiO2 Methanol/ UV-light 410 μmol g− [271]
Ethanol
2017 TiO2/CdS Hierarchical composite Na2S/Na2S3 350 W Xe lamp, 51.4 μmol h− 1 [272]
2016 MoS2/TiO2 Nanorods TiO2 Ethanol 300 W Xe lamp, 4500 μmol h− 1 g− 1
[273]

22
M. Ismael
Fig. 32. Chemical structures of common dyes used to sensitize TiO2. (a) Eosin, (b) Safranin, (c,d) Ru-complexes, (e) indeno[1,2–b]thiophene, and (f) Porphyrin.
Fig. 33. Electron injection in the dye-sensitized TiO2 for photocatalytic H2
production [272].
[1,2–b]thiophene-based organic sensitizers to significantly enhance
photocatalytic hydrogen production by extending the spectral response
to the near-infrared-light region. Results indicated that S5@Pt/TiO2
blue dyes (S5: D-A-π-A: donor–acceptor-π-acceptor) exhibited higher
photocatalytic hydrogen activity than S6@Pt/TiO2 (S6: D-π-A). 2, 3-
diphenylquinoxaline of S5 has great influence in enhancing the photo­
catalytic activity of S5 due to disperse donor electron, improve stability,
and enhance the light absorption. Correspondingly, Lai et al. [281] used
multicarbazole-based organic dyes to sanitize Pt/TiO2 for the determi­
nation of hydrogen production activity under visible light irradiation.
Authors have synthesized three different multicarbazole-based organic
dyes named 2C, 3C, and 4C according to the amount of the dyes used.
They investigated that 3C@Pt/TiO2 revealed the highest activity for 3 h
irradiation. After 3 h irradiation, the activity was decreased due to the
removal of electron acceptor cyanoacrylate moiety from the
multicarbazole-based organic dyes molecule during the photocatalytic
process. Also, there are numerous ways used to attach dyes with semi­
conductor surfaces, such as electrostatic interaction, hydrogen, and co­
valent bonding, and many more. Among them, electrostatic interactions
are more effective in the improved photosensitization process [282]. For
instance, Choi et al. [283] explored the applicability of visible-light
organic dye-sensitized TiO2 particles in the production of hydrogen
and the degradation of organic pollutants. Anchoring groups and elec­
tron donors have a great effect on hydrogen production activity.
Porphyrin and their metallic derivatives with conjugate structure have
gained more attention due to their intense and efficient light absorption
ability in the panchromatic region, strong S and Q-band, electron
23
Fuel 303 (2021) 121207
transfer ability, high fluorescence, thermal and chemical stability, and
appropriate energy levels for the photosensitization of different semi­
conductors. Therefore, they have been widely applied in the field of dye-
sensitized semiconductors for red/near-IR-light persuaded H2 produc­
tion and DSSCs [284]. Moreover, Due to its unique macrocycle structure,
the photo-electronic properties can be easily modified by introducing
diverse metal ions. Thus, porphyrins are considered to be suitable can­
didates for designing functional nanomaterials. The study of Banerjee
et al. [285] indicated that the hydrogen production activity of
porphyrin-based porous polymer and their composites, which were
synthesized using the ball-milling method, was better than the parent
precursor under the exposure of visible light. Their results showed that
the highest activity was ascribed to the role of porphyrin in enlarging the
surface area and promoting the charge separation efficiency. Liu et al.
[286] tested a series of Sn-porphyrins with different functional groups
and Pt nanoparticles as a sensitizer for Pt/TiO2 and tested for the H2
evolution activities. Enhanced the photocatalytic activity of Sn-
porphyrins sensitized Pt/TiO2 was assigned to the synergetic effect be­
tween the sensitized TiO2 and the Q-band of Sn-porphyrins. Interest­
ingly, Gonuguntla and co-workers [287] sensitized TiO2 photocatalyst
with a panchromatic Zinc-porphyrin sensitizer and checked for
hydrogen production in the presence of TEOA or glycerol as sacrificial
reagents under visible light irradiation. They have observed that the
highest activity of Zinc-porphyrin sensitized TiO2 is due to the effective
charge transfer from porphyrin to the CB of TiO2. Recently, Huang et al.
[288] prepared meso-tetra(4-hydroxyphenyl) porphyrins sensitized TiO2
by the sol–gel method. The photocatalytic activity was greatly influ­
enced by changing the central metal ions of the porphyrin ring and the
Pt/meso-tetra(4-hydroxyphenyl) porphyrins -Pd-TiO2 exhibits the
highest activity. The authors claimed that high surface area and efficient
charge separation were responsible for enhanced the photocatalytic
performance. Moreover, zinc-5-(4-carboxyphenyl)-10, 15, 20-tri (3-
pyridyl) porphyrin) sensitized Pt/g-C3N4 reported by Wang et al. [289]
generates an apparent quantum yield of hydrogen up to 25.1% under
visible light irradiation, which ascribed to the efficient charge separa­
tion between the sensitizer and the g-C3N4. Kim et al [290] successfully
produced hydrogen under visible light irradiation in a tin (Sn)
porphyrin (P)-sensitized TiO2 system in the pH range of 3–11. The spe­
cial structure of porphyrin and its connection with tin facilitate the
electron injection process to TiO2. Lee et al. [291] studied the effect of
Pt/TiO2 grafted in visible light irradiation by dyes R-groups (hydrophilic
or hydrophobic). The results showed that moderately hydrophilic R-
anchoring groups exhibited greater sensitization activity than
M. Ismael
Fig. 34. Anchoring of different dyes containing different R groups on the surface of TiO2 and the corresponding activity for hydrogen production [289].
hydrophobic (Fig. 34).
However, instability because of light or thermal degradation of dye
molecules and the formation of intermediates during the reactions has
been reported as major drawbacks associated with dye sensitization
[292,293].
2.2.6. Modification of the morphological architecture of TiO2
Enhancing the photocatalytic activity of TiO2-based semiconductors
could be also achieved through the synthesis of TiO2 with specific
morphology. Fig. 35 summarizes the most common morphological ar­
chitecture of TiO2, which they have great influence on enhancing the
photocatalytic activity [294–299].
For example, mesoporous titania (TiO2) seems to be the most
promising candidate as a highly photocatalytically active photocatalyst
because it has a high surface-to-volume ratio and offers more active sites
at the surface of the photocatalyst to initiate the redox reaction, unique
electronic structures, excellent ability for light absorption, and sufficient
electron transport properties [300]. For instance, Huang et al. [301]
fabricated mesoporous TiO2 nanofibers by a facile vapothermal-assisted
topochemical transformation of preformed H-titanate nanobelts. It was
found that the hydrogen production activity was 2 times higher than
that of P25. The oriented alignment, suitable mesoporosity, high surface
area, and efficient charge separation are crucial in enhancing the pho­
tocatalytic performance. Rusinque et al. [302] synthesized Pd-doped
mesoporous TiO2 by the sol–gel method. Among differently doped Pd
Fig. 35. Morphological architecture of TiO2, (a) mesoporous, (b) nanorods, (c) nanowires, (d) nanotubes, (e) nanosheets, and hollow sphere structures [292–297].
24
Fuel 303 (2021) 121207
photocatalysts, 0.25 wt% Pd-TiO2 exhibits the best activity under visible
light in the presence of ethanol as a scavenger. Hence, apart from the
high surface area, porosity reduction of bandgap energy, the separation
efficiency of electron-hole pairs is another factor responsible for high
photoactivity. Guan et al. [303] obtained a novel oxygen vacancy and S-
doped hetero-nanostructured TiO2/Cu2S photocatalyst by NaBH4
reducing Cu doped TiO2 using a sol–gel method. Importantly, this novel
hetero-nanostructured photocatalyst exhibits improved H2 generation
rate from an aqueous solution containing 0.35 M Na2S and 0.35 M
Na2SO3 without noble metal. This markedly enhanced photocatalytic
activity is attributed to the efficient charge separation provided by the
formation of the composition system, and extend the light absorption
range. Furthermore, mesoporous materials possess a versatile defective
structure as well as a large exposed surface, which are particularly
important in photocatalysis [304]. It has been reported that mesoporous
materials with pore size in nanoscale can provide a surface defect for
photocatalytic surface reaction, ensuring good accessibility during
photocatalytic [305]. These defects should carefully control because
excess defects could reduce photocatalytic activity [306]. Thus, excess
defects site should be removed to develop an efficient defect site for
charge separation enhancement. In this regard, Li et al. [307] carefully
controlled the concentration of defects (lattice distortion or point effect)
by improving the crystallinity of mesoporous-structured anatase TiO2,
resulting in increasing the charge transfer resistance, which is unfa­
vorable for the photocatalytic performance. The photocatalytic
M. Ismael
hydrogen production was enhanced by the introduction of Ti3+ atomic
defect, which plays a key role in enhancing the charge separation as well
as the hydrogen generation. Additionally, Due to their high surface-to-
volume ratios, efficient charge transport and separation, and enhanced
light harvesting, nanorods as 1D nanostructure are widely used in
photocatalytic applications [308]. Recently, Bashiri et al. [309] deco­
rated Fe2O3 on the surface of one-dimensional TiO2 nanorods for the
determination of photoelectrochemical hydrogen activity. Enhanced
hydrogen evolution activity, as well as the photocurrent density of the
1D TiO2@Fe2O3 nanorods photocatalyst, is due to the low charge
transfer resistance, long lifetime of the electrons, and negative flat band
potential, which they proofed using EIS, and Mott-Schottky plots,
respectively. Moreover, the authors claimed that increasing the hydro­
thermal time up to 24 h can improve the crystal growth of titania and the
length of the nanorods. Similarly, Bashiri et al. [310] decorated TiO2
nanorods with reduced graphene oxide (rGO) using the hydrothermal
method for the determination of hydrogen production in the photo­
electrochemical cell (PEC). A maximum hydrogen activity of
1200 mmol/cm2 of TiO2nanorod@rGO compared to that of TiO2@rGO
is attributed to the synergistic effect between the two phases of titania
(anatase and rutile), the high surface area of TiO2 nanorods, and the
high electron mobility of rGO. Zeng et al. [311] constructed a novel
hybrid tandem photocatalytic fuel cell by attaching a silicon solar cell to
the back of a silicon-doped TiO2 nanorod array for the determination of
hydrogen production coupled with organic pollutants degradation.
Enhanced photoelectrochemical performance of the silicon-doped TiO2
nanorod array was attributed to improving charge transport efficiency,
which proofed by The EIS and IMPS experiments. Chen et al. [312] use a
photodeposition method to decorate Co on TiO2 nanorods to enhance
the photocatalytic hydrogen production activity. The 2.0 wt% Co/TiO2
nanorods photocatalyst exhibits the highest activity, which can be
attributed to the role of Co metal in reducing the H2 overpotential as
Fig. 36. Hydrogen production rate over different photocatalysts compared to the most active (Ti0.996Nb0.002Rh0.002O2) (a) in methanol, (b) in pure water, (c) UV–Vis
(DRS) absorption spectra, and (d) Photoluminescence spectra for determination of charge separation efficiency [311].
25
Fuel 303 (2021) 121207
well as in facilitating the charge separation efficiency. In another study,
Huang et al. [313] prepared Rh/Nb codoped anatase TiO2 nanorods by a
sol–gel-hydrothermal and solid-state phase transformation method
using Ti(OC4H9)4, RhCl3⋅3H2O, and NbCl5 as precursors for determi­
nation of hydrogen production. The Rh/Nb codoped anatase TiO2
nanorods (Ti0.996Nb0.002Rh0.002O2) showed an obvious increased in the
hydrogen production activity in methanol solution (7.85 mmol g-1h− 1)
(Fig. 36a), and pure water (0.99 mmol g-1h− 1) (Fig. 36b) under simu­
lated sunlight, far higher than that for pure TiO2 nanorods and Pt-loaded
P25, respectively. This higher activity was mainly attributed to the
improved visible light absorption and efficient charge separation as
shown in Fig. 36c&d, respectively. Importantly, Enhanced charge sep­
aration efficiency due to the presence of Nb that introduces an extra
electron into Rh-doped TiO2, which maintains the charge compensation,
suppresses oxygen vacancies, and avoids Rh4+ species. Furthermore, this
study showed that the presence of Nb shifts the CB edge of Rh-doped
TiO2 toward vacuum energy, make them thermodynamically satisfied
for the water reduction reaction.
Other micro-nano structures such as nanowires, nanotubes, nano­
sheets, can improve the photocatalytic activity of TiO2 by providing
sufficient specific surface area for increasing the photocatalytic active
sites [314]. Ou et al. [315] fabricated 2D ultrathin MoS2-modified black
Ti3+-TiO2 nanotubes using an electrospinning–hydrothermal treat­
ment–reduction method. The obtained nanotubes photocatalyst was
tested for hydrogen evolution reaction and exhibited 15 times higher
than that of bare TiO2 nanotubes, which recognized the role of 2D MoS2
in enhancing the electron diffusion and a unique structure of MoS2/
Ti3+–TiO2 nanotubes. In another work, Tian et al. [316] synthesized
mesoporous carbonate-incorporated phase-junction TiO2 nanotubes by
olive oil-assisted electrospinning. The outstanding photocatalytic
hydrogen production performance (6108 μmol h− 1 g -1), which is about
6 times higher than that of the commercially available P25, was
M. Ismael
endorsed to the enhanced light absorption and charge separation due to
the refined porous structure and the presence of double phase (anata­
se–rutile) of TiO2, respectively. Reddy et al. [317] prepared reduced
graphene oxide and TiO2 nanotubes composites photocatalysts by a
hydrothermal method. The optimized 5rGO-TiO2 showed higher
capacitance (160F/g specific capacitance), and also higher hydrogen
production (24,880 μmol/g/h) under natural sunlight. This remarkable
activity is due to the accelerated separation of electron-hole pairs and
inhibited their recombination. Gao et al. [318] synthesized Bi/
Bi2MoO6/TiO2 nanotubes photocatalysts using the solvothermal method
and tested not only for hydrogen production activity but also for
degradation of organic dyes and removal of Cr (VI) metal ion. The
highest hydrogen production rate reached 173.41 μmol⋅h− 1.cm− 2. The
synergistic effect between Bi2MoO6 and TiO2 nanotubes is responsible
for the charge separation enhancement. Moreover, the surface plasmon
resonance effect of Bi also has a great influence on enhanced photo­
catalytic performance. Pan et al. [319] prepared the Z-scheme CdS
quantum dots/Ni2P/Black Ti3+-TiO2 nanotubes through the growing of
2D Ni2P lamellas on the surface of TiO2 nanotubes. The photocatalytic
activity of the obtained photocatalyst was evaluated for hydrogen pro­
duction. A noticeable enhancement of around 3303.85 μmol/g h of H2
was mainly ascribed to the role of 2D Ni2P and Ti3+ in facilitating the
electron diffusion, Z-scheme mechanisms in enhancing the charge sep­
aration efficiency, and improving light absorption and utilization
through the formation of nanotubes structure and oxygen vacancy.
Furthermore, the fabrication of TiO2 hollow-sphere has been extensively
reported as an effective way to enhance its photocatalytic activity
because it can offer large specific surface areas and improve the light
scattering properties of TiO2 [320]. For instance, Jiang et al. [321]
boosted the photocatalytic activity of TiO2 hollow sphere for hydrogen
production under solar light irradiation by dual cocatalysts (Ag and
RuO2). Their findings revealed that hydrogen production was enhanced
due to the spatial charge separation offered by the presence of the two
cocatalysts. Recently, Seadira et al. [322] loaded different metal ions on
nanostructured TiO2 hollow spheres to enhance their hydrogen pro­
duction activity in the presence of glycerol. Among different metal ions
loaded, Cu showed the highest activity, which was assigned to the
enlarged surface area, reduced bandgap energy, high crystallinity, and
the spatial morphology of the hollow sphere TiO2 that enhanced the
charge separation efficiency. Hollow TiO2 anatase spheres with Au and
RuO2 dual co-catalysts were documented by Rahman et al. [323]. Au
nanoparticles were coated on the surface of TiO2 using Polystyrene by
the sol–gel method, whereas, impregnation and calcination methods
were used to load the Ru to form the desire photocatalyst. The highest
hydrogen evolution activity was obtained for the photocatalyst with two
dual cocatalysts (3165 mmol g− 1), which much higher than that of using
one cocatalyst. This enhanced activity was attributed to the role of both
cocatalysts and the special structure of the photocatalysts in increasing
the charge separation efficiency. She et al. [324] designed a hollow-
structured TiO2 sphere with dual cocatalysts (MOx and Pt), where M is
ultrasmall metal nanoparticles. MOx was firstly introduced into zeolite
and Pt was decorated on the outer shell. PdOx@TiO2@Pt exhibits the
highest hydrogen production activity (0.45 mmol h− 1) that ascribed to
the role of PdOx@TiO2 and Pt that act as a hole scavenger and electron
trapping sites, respectively. Besides, the activity of modified hollow
spheres in hydrogen production, there are also tested for degradation of
organic pollutants (RhB) [325] and removal of antibiotics [326].
Additionally, three-dimensional (3D) photocatalysts have been widely
studied in the field of photocatalysis due to their high surface area,
facilitating the movement of charge carriers, and enhancing the light-
harvesting [327,328]. Lately, three-dimensional ordered macroporous
materials with a certain ratio of TiO2 and g-C3N4 were reported by Liu
et al. [329]. The photocatalytic activity of the 3D-CN/Ti was evaluated
for hydrogen production under simulated sunlight. Among different CN/
Ti ratios, the 3D-25CN/Ti exhibits an excellent hydrogen production
rate and stability, which is mainly ascribed to the efficient charge
26
Fuel 303 (2021) 121207
separation provided by the formation of the heterostructure and the
special morphology of the three-dimensional ordered macroporous.
Furthermore, the Authors demanded that the optical property of the 3D-
25CN/Ti was also enhanced by extending the range of light response to
the visible region. Zhang et al. [330] synthesized 3D flower-like
TiO2@Ni(OH)2 core–shell heterostructure by solvothermal approach
for determination of solar hydrogen production. The improved photo­
catalytic performance of the unique p-n heterostructure was attributed
to the promotion of the charge separation and the presence of more
surface active sites. Hu et al. [331] deposited different noble metals
nanoparticles on defective 3D TiO2 hierarchical spheres. The sol­
vothermal method was applied to the synthesis of 3D TiO2 hierarchical
spheres with oxygen vacancies, and then a direct redox reaction was
used to deposit the noble metals on porous 3D TiO2 hierarchical spheres.
The photocatalytic activity of M/TiO2 (M: noble metal) was tested for
hydrogen evolution. Pt/3D defective TiO2 showed the highest activity
under full arc spectrum, whereas Au/3D defective TiO2 showed the
highest activity under visible light irradiation. Their investigations
indicate that the oxygen vacancy and the noble metals have a great in­
fluence in enhancing the light absorption, while the deposited noble
metals have a main role in promoting the charge separation. Yan et al.
[332] designed and fabricated hydrogenated 3-dimensional branched
TiO2 nanorod arrays via a three steps method. CdS were deposited on the
hydrogenated 3-dimensional branched TiO2 nanorod arrays. In this
photocatalytic system, a Pt wire was used to connect conductive sub­
strate FTO of the CdS/ hydrogenated 3-dimensional branched TiO2
nanorod arrays to form a high active CdS/Hydrogenated-3D-TiO2/Pt
photocatalyst. This novel photocatalyst has higher photocatalytic
hydrogen production activity than that without Pt-wire, confirming the
role of Pt-wire in enhancing the hydrogen production of the whole
photocatalytic system. Recently, carbon quantum dots (CQDs) have
gained great attention due to their low-cost, water-solubility, superior
stability, distinct optical and electronic properties, environmental
friendliness, and size-dependent photoluminescence [333]. Thus, car­
bon quantum dots (CQDs) have attained increasing attention for pho­
tocatalytic hydrogen production applications [334]. Genc et al. [335]
synthesized carbon quantum dots from Gingko Biloba using the micro­
wave method. The carbon quantum dots was used as a sensitizer of TiO2
and tested for hydrogen production under visible light irradiation in the
presence of TEOA as a sacrificial reagent and Pt nanoparticles as a
cocatalyst. Enhanced photocatalytic hydrogen production activity of
TiO2 is due to the role of CQDs in enhancing the charge separation ef­
ficiency. Similarly, Sargin et al. [336] obtained green carbon quantum
dots (CQDs) from edible mushroom Agaricus bisporus (as a carbon
source) by facile microwave irradiation. The CQDs were used to sensi­
tize the TiO2, and their activity was evaluated for hydrogen production
under visible light irradiation. CQDs/TiO2 showed hydrogen production
of 472 mmol g-1h− 1, and the activity was furtherly enhanced by the
addition of Pt (1458 mmol g-1h− 1). Promoted charge separation effi­
ciency in the CQDs/TiO2 photocatalytic system is the main reason for
enhanced hydrogen production activity. In another related study, Sui
et al. [337] prepared CQDs/TiO2-001 with remarkably enhanced
hydrogen production activity. Their results revealed that the higher
activity of CQDs/TiO2-001 even higher than that of TiO2-001 and CQDs/
P25, which is mainly ascribed to the efficient charge separation offered
by the formation of synergistic effect between the two semiconductors.
Additionally, Yu et al. [338] hydrothermally synthesized CQDs/P25 and
tested for hydrogen production under UV and visible light irradiation.
Based on the photocurrent and the photovoltage measurements, CQDs
play an important role in enhancing the charge separation efficiency and
responsible for the enhancement of hydrogen production activity of
TiO2. Pan et al. [339] synthesized carbon quantum dots (CQDs) modi­
fied porous g-C3N4/TiO2 two-dimension (2D) nano-heterojunctions via a
simple method. Porous g-C3N4 photocatalyst was prepared by a thermal
polycondensation, afterward; a hydrothermal method was used to
introduce the TiO2, and then CQDs were added to graphitic carbon
M. Ismael Fuel 303 (2021) 121207

nitride and titania. After irradiated by a 300 W Xe lamp, the obtained
heterojunction (CQDs/C3N4/TiO2) showed an obvious hydrogen pro­
duction activity, which implied the dual function CQDs with high cat­
alytic activity in decomposing H2O2, which improve the water-splitting
reaction and reducing the poisoning the photocatalyst. In addition, the
up-conversion fluorescence could improve light utilization. Other rea­
sons, such as the porous structure of g-C3N4 and heterojunction forma­
tion also have a great influence on improving the photocatalytic
performance by promoting the charge separation efficiency. The as-
obtained CQDs/hydrogenated TiO2 nanobelts heterostructures
revealed increased visible-light absorption and extended its photo­
absorption region to near-infrared were prepared by Tian et al. [340].
The improved photocatalytic activity of the CQDs/hydrogenated TiO2
nanobelts heterostructures can be attributed to improved optical ab­
sorption, charge carrier trapping, and enhancement of the photo­
generated electron-hole separation of oxygen vacancies and Ti3+ ions in
TiO2 nanobelts formed by hydrogenation. In another work, Liu et al.
[341] designed and fabricated direct Z-scheme Cd0.5Zn0.5S/CQDs/TiO2
nano-film composites via a reflux process in aqueous using 3-mercapto­
propionic acid as a stabilizer. The ternary system shows excellent
hydrogen production activity higher than that of pure TiO2 and CZS/
TiO2, which mainly implied the role of carbon quantum dots in
enhancing the optical properties and charge separation efficiency of the
ternary photocatalyst. Zhou and coworkers [342] used the photo­
deposition method to sensitize the Pt/TiO2 nanocomposites with the
carbon quantum dots. CQDs-sensitized TiO2/Pt nanocomposites exhibit
greater hydrogen production activities, which can be ascribed to the
efficient charge separation between the quantum dots and the TiO2 that
improve the hydrogen production activity. Further TiO2 photocatalysts
with different morphological structure and their enhanced hydrogen
production are summarized in Table. 3.
2.2.7. Defect engineering to enhance the photocatalytic activity of TiO2
Apart from the above-mentioned strategies, defect engineering is an
effective approach to promote the photocatalytic performance of TiO2.
In particular, recent studies have revealed that semiconducting prop­
erties such as light absorption, selectivity, and the photoactivity of TiO2,
etc., can be modulated by its defect disorder [352,353]. Among different
kind of defects, Point defects including oxygen vacancies and Ti3+ in­
terstitials are two probable defects in the reduced-rutile and -anatase
structures have attracted attention to promote the photocatalytic
properties of TiO2 [354–356]. These defects have a great influence on
improving the photocatalytic performance of TiO2 for hydrogen pro­
duction [357]. Reduced TiO2, which contains Ti3+, has been demon­
strated to extend the light absorption to visible light and increase the
charge mobility [358–360]. While, other photocatalytic properties, such
as the electronic structure, charge transport, and surface properties of
TiO2 are closely related to oxygen vacancies [361–363]. Furthermore,
oxygen vacancies are carefully investigated by theoretical calculations
and experimental characterizations, which revealed that they can act as
adsorption and active site, and believe to impact the charge recombi­
nation process in photocatalysis [364,365]. Since Mao et al. [366] re­
ported that the high-performance TiO2 with a surface disorder or defects
can be achieved by hydrogen reduction treatment, this hydrogenation
method has gained great attention for improving the photocatalytic
activity of anatase TiO2 nanostructures by creating defect disorders on
their surface [367,368]. For instance, Liu et al. [369] obtained black
titania from TiO2 nanotube (NT) arrays by applying high-pressure H2
treatment and showed an obvious activity for hydrogen production
without using any cocatalyst. Interestingly, normal treatment (atmo­
spheric H2/Ar annealing) does not cause this conversion. Ti3+ defect-
structure created in the anatase nanotubes and responsible for the
highest activity and revealed using the electron spin resonance (EPR). In
another study, Tian et al. [370] used NaBH4 to reduce pure TiO2
nanobelts to the reduced TiO2 nanobelts. The high hydrogen production
activity and degradation activity of the reduced TiO2 nanobelts were
mainly ascribed to the creation of Ti3+ and oxygen vacancy, which can
ascribe to their role in increasing the visible light absorption, promoting
charge carrier trapping, and hindering their recombination, thus
improved the photocatalytic activity. Furthermore, this study showed
that the ratio of Ti3+ was optimized (55.8%) and presented the best
activity. Wu et al. [371] created titanium vacancies (acceptor/donor)
that were incorporated in the ultra-small yellow TiO2 and tested for
hydrogen production under visible light irradiation (Fig. 37a) without
using any dopants or cocatalysts. The improved activity of the yellow
TiO2 compared to the normal TiO2 is due to the role of the accept­
or–donor defect in enhancing the charge separation efficiency
(Fig. 37b), and improving the light absorption (Fig. 37c&d).
Furthermore, Wei et al. [372] successfully prepared self-doped TiO2
by a simple hydrothermal method employing Ti and H2O2 as precursors.
Ti3+ species as well as the formation of oxygen vacancies are strongly
affecting the hydrogen production of the self-doped TiO2 photocatalyst.
Importantly, the concentration of H2O2 and the hydrothermal reaction
time have a great influence on the Ti3+ species and the oxygen va­
cancies. Their findings reveal that the optimum oxygen vacancy is
contributed to the efficient photocatalytic activity of the prepared
photocatalyst. In another study, Song et al. [373] fabricated a composite
titania thin film consisted of quasi-aligned single-crystalline rutile
nanorods embedded in sol–gel derived anatase aggregates. Controlled
reaction between Ti and hydrogen peroxide was responsible for the
deposited of the single-crystalline rutile nanorods on the Ti substrate.
The photoelectrochemical behavior of the composite film was studied in
details and represented that the presence of the anatase/rutile couple
can improve the charge separation, resulting in enhancing the a steady-
state photocurrent density more than double the simple sum of those
generated by the two components alone. Similarly, Wu et al. [374]

Table 3
TiO2-based photocatalyst with different morphological structure and their enhanced hydrogen production.
Years Photocatalyst Catalyst Morphology Sacrificial Reaction parameters H2 production activity Ref
reagent

2013 C/N codoped mesoporous TiO2 Mesoporous TiO2 Methanol 450 W Xe lamp/ visible light 500 mmol g− 1 [343]
2019 spherical TiO2 particles Spherical TiO2 Methanol 150 W Xe lamp/ solar light/Pt 350 μmol/min [344]
2014 porous anatase TiO2 microspheres Microsphere TiO2 Methanol 300 W Xe lamp/ UV light/Pt 27 μmol/h [345]
2011 hierarchically branched Nanorods TiO2 NA Xe lamp (AM 1.5G, 88 mW/cm2) Photocurrent density [346]
TiO2 nanorod (0.83 mA/cm2)
2015 H2Ti3O7 nanorods and Cu2O/TiO2 Nanorods TiO2 Glycerol Solar irradiation, 50,339 mmol h− 1 gcat− 1
[347]
nanorods
3
2017 Pt-doped meso TiO2 Mesoporous TiO2 Ethanol 15 W Black-Light-Blue lamp, 5.5 μmol/cm [348]
2017 C-doped TiO2@g-C3N4 core–shell Core-shell hollow Methanol 300 W Xe lamp, 420 nm cutoff filter 35.6 μmol/g.h [349]
hollow nanospheres nanospheres TiO2
2018 3D N-TiO2/g-C3N4@NixP Hierarchical nanostructure TEOA 300 W Xeon-lamp, cutoff filter 650 μmol/h [350]
hierarchical nanostructure TiO2 (λ = 350–780 nm),
1
2011 Mesoporous-assembled TiO2 Mesoporous TiO2 NA A 300 W high-pressure Hg lamp, UV 409.2 μmol h− [351]
nanocrystals irradiation

27
M. Ismael
Fig. 37. (a) Hydrogen production rate, (b) Photoluminescence spectra, (c) UV–Vis (DRS) absorption spectra, and (d) Tauc plot for bandgap determination of yellow
and normal TiO2 [369]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
prepared Large-area films with ordered titania nanorods on titanium
substrates through direct oxidation of Ti with hydrogen peroxide. The
obtained nanorods was thermally treated at 450 ◦ C and tested for pho­
todegradation of RhB. The thermally treated nanorod film exhibited a
stable and high crystallinity, resulting in enhanced photocatalytic ac­
tivity. It has been reported that nanotube titanic acid (NTA) was used as
a layered TiO2-based material due to its advantages such as large surface
areas, strong absorption ability, and unique structure [375]. For that,
Xing et al. [376] applied a simple calcination method to synthesize BCN-
TiO2 nanocomposites. A hexagonal boron carbon nitride (BCN) semi­
conductor and nanotubular titanic acid (NTA) were used as precursors
and the activity obtained nanocomposites were tested for hydrogen
production under visible light irradiation. Their characterization results
confirmed that heating the NTA to a high temperature can create a single
electron oxygen vacancy, which is very beneficial in enhancing the
photocatalytic activity through enhancement the charge separation and
improvement of the light absorption. Zhang et al. [377] hydrothermally
synthesized C–N self-doped TiO2 photocatalysts for determination the
hydrogen evolution activity. The creation of oxygen vacancies and Ti3+
during the synthesis process were determined using the electron para­
magnetic resonance (EPR) and X-ray absorption near-edge structure s­
pectroscopy (XANES) and believed to be responsible for enhanced the
photocatalytic activity of the C–N self-doped TiO2 photocatalysts
through improving the optical properties. Hou et al. [378] demonstrated
that the photocatalytic performance of TiO2 can be affected by both the
surface and bulk oxygen vacancies. In their study, nanotube titanic acid
was annealed at different temperatures possesses different types and
concentrations of oxygen vacancies. The authors claimed that different
types of oxygen vacancies will be obtained through different calcination
conditions (in air, single-electron-trapped oxygen vacancies, whereas, in
bulk and surface oxygen were produced in a vacuum). Both types of
oxygen vacancies show hydrogen production activity under different
light illumination. Nanotube titanic acid–air (400 ◦ C) exposed a higher
hydrogen evolution rate under UV light, whereas nanotube titanic acid-
28
Fuel 303 (2021) 121207
vacuum (400 ◦ C) revealed a higher hydrogen evolution rate under
visible light. Cao et al. [379] recently demonstrated that the oxygen
vacancies in TiO2 nanoparticles enhanced their photocatalytic hydrogen
production activity. Furthermore, they also obtained the optimum
quantity and distribution of the oxygen vacancies in TiO2 nanoparticles.
Enhanced hydrogen production activity was mainly assigned to the
improved electronic structure and light absorption capacity. Cai et al.
[380] improved the photo splitting of H2S into H2 evolution of the
anatase TiO2 with active {0 0 1} facet through the oxygen defect strat­
egy. The photocatalytic hydrogen production activity was improved due
to the role of oxygen vacancy in inducing an intermediate energy level
and reduces the bandgap energy, which is revealed by the UV–Vis (DRS)
measurements. Consequently, the charge separation efficiency was also
enhanced and observed from the PL spectra. Greatly important, the
adsorption ability of H2S was also improved by shifting the adsorption
energy to a more negative value. Zhang et al. [381] examined the role of
oxygen vacancy and Ti3+ defects in enhancing the photocatalytic
hydrogen production activity of Au@TiO2 photocatalyst in the presence
of ethanol. The Au@TiO2 photocatalyst was prepared in the presence of
different concentrations of NaBH4 as a reducing agent. Their investi­
gation exhibited that the concentration of oxygen vacancy, the Ti3+, as
well as the number of electrons on Au were increased with increasing the
concentration of the reducing agent, which lead to an increase in the
selectivity and photocatalytic activity of the photocatalyst. Kong et al.
[382] successfully synthesized g-C3N4/Ti3+-doped TiO2 composite by
polycondensation of urea followed by hydrogenation treatment to create
Ti3+ defects. The photocatalytic activity of the obtained g-C3N4/Ti3+-
doped TiO2 composite was tested for hydrogen production and showed
an obvious enhancement, which is attributed to the critical role of the
Ti3+ defects in the construction of the Z-scheme pathway for efficient
charge transfer and separation. In another study, Mohajernia et al. [383]
enhanced the photocatalytic activity of the reduced TiO2 nanostructures
through the introduction of point crystal defects. Different types of de­
fects were obtained under different applied conditions and characterized
M. Ismael Fuel 303 (2021) 121207

using the EPR. Results obtained from the EPR analysis showed that the big challenge because it strongly depends on the characteristics of
presence of two types of defects, mainly surface-exposed Ti3+ and lattice photocatalyst and substrate, and the continuous variation of the solution
embedded Ti3+ centers, and are responsible for optimizing the hydrogen pH during the photocatalytic reaction, resulting in continuous formation
production activity of the reduced TiO2. Yu et al. [384] synthesized and depletion of hydronium cations and hydroxide anions according to
defect-rich TiO2 mesocrystals with the mesoporous structure using a the following equations: [396].
hydrolysis method and tested for hydrogen production under visible
light irradiation. The presences of Ti3+ species, as well as the meso­ TiOH + H+ = TiOH+
2 (1)
porous structure, are responsible for the photocatalytic activity TiOH + OH− = TiO- + H2O (2)
enhancement. Ti3+ species can improve the visible light absorption and
prolong the lifetime of the charge carriers, while mesoporous structure Generally, hydrogen evolution reaction (HER) is a two-electron
can enlarge the specific surface area of the defect-rich TiO2 meso­ transfer reaction and can occur in both acidic and basic medium as
crystals. Xu et al. [385] prepared N doping in TiO2 by a mild thermal represented in equations 1&2, respectively. Normally, active catalysts in
method involve the flowing of gaseous Ar-NH3-Ar (AN) at 450 ◦ C. Ti3+/ the electrochemical process are required to overcome activation energy
oxygen vacancy pairs were formed under these thermal conditions and barriers (overpotential).
revealed by the EPR, XPS, and EDS analysis. Enhanced photocurrent
In acidic media: 2H+ + 2e- → H2 (1)
density around 5 times higher than that of pristine TiO2 was mainly
ascribed to the enhanced light absorption capacity proofed by the In neutral or alkaline media: 2H2O + 2e- → H2 + 2OH- (2)
UV–vis absorption spectra, and for increased the charge density and
reduced the flat bandgap energy proofed by the Mott-Schottky plots. Xu These reaction mechanisms can be achieved through either the
et al. [386] introduced defects based on lattice distortion in TiO2 mi­ Volmer–Heyrovsky or the Volmer–Tafel mechanism [397,398] as shown
crospheres for visible light photocurrent generation enhancement. in Fig. 38 [399].
Enhanced photocurrent generation of the TiO2 microspheres was mainly Volmer reaction is the first common step, in which electron reacts
attributed to the combined effect of lattice distortion and defects. De­ with proton gathered on the surface of the catalyst to give an interme­
fects lead to narrow bandgap energy by elevating the valence band; on diate adsorbed hydrogen (H*) atom. After that, the adsorbed hydrogen
the other hand, lattice distortion enhances the charge migration. Thus intermediate is consequently accompanied by either amalgamation of
the existence of both Ti3+ defects and lattice distortion is contributed to an adsorbed H* atom with an electron and a proton (Volmer-Heyrovsky
the highest photocurrent generation. Wen et al. [387] applied strain pathway) or a combination of two H* atoms (Volmer-Tafel pathway)
engineering to tune the lattice parameters of anatase TiO2. Their results and can be described according to the following equations:
showed that the elongation of lattice parameter a of anatase TiO2 leads In acidic solution, the HER is considered as a multi-step reaction (Eqn
to the shift-up of the conduction band bottom and can thus accelerate (1)–(3)):
the reduction reactions of O2, which is responsible for the photocatalytic H+ + e− + * → H* (Volmer) (1)
enhancement of the anatase TiO2 for degradation of toluene and
photoreduction of Cr3+. Lan et al. [388] developed defective meso­ (2)
−
H* + H+ + e → H2 (Heyrovsky)
porous TiO2 microspheres with excellent mesoporosity and stable de­
H* + H* →H2 (Tafel) (3)
fects through a reductant co-assembly approach. A maximum
H2 evolution rate of 19.8 mmol g− 1 h− 1 was obtained due to the critical In alkaline solution, the reaction formula for the HER is represented
role of mesoporous structure in enlarging the specific surface area and as:
the role of both mesoporous structure and atomic vacancy in effective
charge transportation and enhanced the light-harvesting. H2O + e− → OH− + H* (Volmer) (4)
− −
H* + H2O + e → OH + H2 (Heyrovsky) (5)
3. Different operating parameters affect the photocatalytic
hydrogen production process H* + H* →H2 (Tafel) (6)

In photocatalytic hydrogen production, the following are operating Moreover, the pH of the prepared solution has a great influence on
parameters that affect the process: surface area and particle size, pH, the final size of TiO2 nanoparticles. Additionally, their small size raises
sacrificial agent, Amount of cocatalyst loading, calcination temperature, the conduction band and lowers the valence band, resulting in changing
photocatalyst load, light source and intensity, and cocatalyst deactiva­ the band structure of TiO2. This band shift affects the catalytic properties
tion. These factors are discussed in detail in the following sections. and splits the bandgap of the semiconductors because of a quantum
confinement effect [400–404]. Bahnemann et al. [405] have already
reviewed that acid-base properties of the metal oxide surfaces can have
3.1. Influence of pH
considerable have a great influence on their photocatalytic activity.
Recently, Estahbanati et al. [406] performed a kinetic study on photo­
It can be considered that the development of hydrogen through the
catalytic hydrogen production from different alcohols in a pH range of
splitting of water depends on the concentration of protons reduced by
2–12. Results indicated that the maximum hydrogen production rate
the photogenerated electron into hydrogen molecules that are greatly
was obtained at a pH of 8 due to the interaction effect and TiOH group
affected by the solution pH. It is one of the most important parameters
dissociation (Fig. 39). It has been proofed that TiO2 particles tend to
that mainly affecting the rate of photocatalytic hydrogen production by
agglomerate under acidic conditions resulting in reducing the surface
changing photocatalyst agglomeration and controlling the substrate
area, which has an important role in photon absorption and improve­
adsorption on the photocatalyst surface [389]. Furthermore, pH is
ment of photocatalytic hydrogen production [407]
strongly dependent on the characteristics of photocatalyst and substrate
With Cd0.5Zn0.5S solid solutions prepared by hydrothermal method
and is always changing during the reaction [390]. Additionally, the pH
and co-precipitation method, Peng and coworkers [408] studied their
of the suspension may have a profound impact on the characteristics of
visible-light hydrogen evolution from aqueous solutions of glycerol.
the photocatalyst, such as functional groups [391], particle size
Zn0.5Cd0.5S-G exhibited higher photocatalytic activity due to the higher
dissemination [392], and surface charge [393]. Alternatively, pH affects
surface area. Importantly, the basicity that affects the redox potential of
the dissociation of the substrate (sacrificial reagents) [394] and their
glycerol influences the rate of hydrogen evolution. In another study, Wu
interactions with the surface of the catalyst [395]. Nevertheless, the
et al. [409] systematically studied the efficiency of H2 evolution for
study of the influence of the pH effect on the photocatalytic system is a

29
M. Ismael Fuel 303 (2021) 121207

Fig. 38. The schematic illustration of the hydrogen evolution mechanism in both acidic and basic media [397].

Fig. 40. The effect of the pH value on the H2 production rate [407].

Fig. 39. Influence of pH on the hydrogen production rate using three different Pt deposited TiO2. This study indicated that pH has a great influence on
alcohols as sacrificial reagents [405]. the rate of hydrogen production over Pt/TiO2 photocatalyst and clearly
showed that the highest activity was obtained under weakly basic con­
ditions. Moreover, Zou et al. [414] successfully loaded Cu ions on the
CuOx species over TiO2. Interestingly, the positive charge in the CuOx
surface of rutile TiO2 via the solvothermal method for the determination
center and weak basic pH (ca. 10) affect photo-induced charge transfer
of hydrogen activity performance. At pH = 6, the photocatalyst shows
and hydrogen production rate. Changing pH will affect the band edge of
the highest activity, further increasing pH, the activity decreases.
the semiconductor and the surface properties of the photocatalyst
Alkaim et al. [415] obtained TiO2 nanoparticles via a facile hydrother­
(Fig. 40).
mal method, which showed high performance in photocatalytic
CuAlO2/TiO2 heterojunction photoelectrodes are studied by Brahimi
hydrogen evolution. The study shows that TiO2 nanoparticles loaded
and coworkers [410] for H2 evolution under visible light using S2− and
with 0.4–0.5% Pt and pH = 5 in the presence of EDTA show the highest
S2O2−
3 . The highest activity was obtained at pH ~ 11. Furthermore, the
activity. Importantly, by increasing pH, the activity decreases that may
adjustment of pH has a great influence on the bandgap of the catalyst.
be attributed to the charge similarity of TiO2 and EDTA. Cross-linked the
Nada et al. [411] constructed a TiO2/RuO2 semiconductor containing
hierarchical sulfonated graphene oxide (SG)–TiO2 composites nano­
methyl viologen as an electron donor. The enhanced photocatalytic
composites with tunable band structure were synthesized by Gao et al.
performance for hydrogen production was obtained in acidic media
[416]. The photocatalytic activity of the prepared photocatalysts was
because of the higher availability of H+ ions. Similarly, the highest
evaluated for hydrogen production in a wide pH range. Photocatalyst
photocatalytic hydrogen production over Pt/rutile/TiO2 can be ob­
with 2% graphene oxide at pH = 11 shows the highest activity (Fig. 41a)
tained at pH 5.5 [412]. Zhou et al. [413] investigated the influence of
due to efficient charge separation, high surface area, and more light
different glucose on photocatalytic hydrogen production performance of
absorption (Fig. 41(b-d)).

30
M. Ismael Fuel 303 (2021) 121207

Fig. 41. (a) Hydrogen production activity of different composites containing different amounts of graphene oxide, P25 nanoparticles, and bare TiO2 spheres; (b)
Photoluminescence spectra for determination of charge separation efficiency (c) N2 adsorption/desorption isotherm for determination of specific surface area (inset:
pore size distribution); and (d) UV–vis spectra of bare TiO2 spheres and the most SG–TiO2-2 (inset: Tauc plot) [414].

Moreover, Yin et al. [417] developed a hydrothermal method for the the pH, the hydrogen rate was sharply decreased. The explanation of
synthesis of graphitic carbon nitride sensitized TiO2. After that, the these results that when the pH > 3, fewer photoactive materials were
photocatalytic hydrogen production activity was enhanced by loaded Cu formed (PW12O-3 40). Furthermore, at high pH, H3PW12O40 was
(OH)2 cocatalyst. Importantly, Cu(OH)2/g-C3N4/TiO2 exhibited the completely decomposed.
highest photoactivity at pH = 8. In another study, Badawy et al. [418]
studied the photocatalytic hydrogen production activity of mesoporous
3.2. Sacrificial reagents
TiO2 prepared via a simple sol–gel method at a wide range of pH.
Mesoporous TiO2 at pH = 3 showed the highest activity. Herein, pH
As mentioned earlier, the overall water splitting is a very challenging
value has a great influence on the band position and charge surface of
reaction to conduct as it is an energetic uphill reaction and followed by a
mesoporous TiO2 that affects their photocatalytic hydrogen production.
largely positive Gibbs free energy (H0 = 286 kJ mol− 1). Recently, many
In another study, Fu et al. [419] prepared noble-metal-loaded TiO2
review articles have also been published describing the various prop­
photocatalysts. Their photocatalytic activities were evaluated in the
erties of the photocatalytic water splitting process, including funda­
production of hydrogen in the presence of glucose. Maximum hydrogen
mental principles, nature of the photocatalyst, the role of sacrificial
production was observed at pH = 11, then the photocatalytic activity
reagents, cocatalyst, and photocatalytic mechanism [422–441]. The
decreases at higher pH. This study shows that the photocatalytic
sacrificial agents act as electron donors, consuming photogenerated
behavior is strongly dependent on the pH, and the weak basic condition
holes in the TiO2 valence band, whereas, the metal co-catalysts loading
is favorable for the highest activity. However, in general conclusion,
on the surface of the photocatalyst act as hydrogen evolution sites,
based on the previous research, the photocatalytic hydrogen evolution
which act as electron sink and accept the photogenerated electrons from
reaction is enhanced in the basic media for the reasons mentioned
the TiO2 conduction band. Thereafter, the addition of sacrificial agents
above. Recently, Song et al. [420] studied the hydrogen evolution rate
(typically electron donors such as different alcohols, ethylene glycol, or
over four different BaTiO3/TiO2 core/shell photocatalysts. Importantly,
glycerol) with oxidation potentials lower than water further enhances
at intermediate pH and 600 ◦ C, the BaTiO3/TiO2 core/shell photo­
electron-hole pair separation in TiO2. In such systems, hydrogen can be
catalysts showed the highest activity that ascribed to the effect of pH on
produced either through water splitting (H2O → 1/2O2 + H2) or alcohol
the surface potential, more negatively charged species adsorbed on the
photoreforming (e.g. CH3OH (methanol) + H2O → CO2 + 3H2
surface and draw more holes to the surface and the oxidation half-
CH3CH2OH (ethanol) + 3H2O → 2CO2 + 6H2, C3H8O3
reaction. Fu et al. [421] sensitized Pt/TiO2 photocatalysts over a se­
(glycerol) + 3H2O → 3CO2 + 7H2). The role of the sacrificial reagent is
ries of Keggin-structure heteropoly blue anions (PW12O-3 40, phospho­
shown in Fig. 42 [442]. Glycerol, ethanol, and methanol are the most
tungstic blue, and others) and tested for hydrogen evolution activity
common alcohols, which are widely used as sacrificial reagents in
under visible light activity at different pH (1–5), and observed that the
photocatalytic hydrogen production. Glycerol is produced in a large
maximum hydrogen production was obtained at pH = 1, with increased
amount (10%) as a byproduct of the biodiesel production process [443].

31
M. Ismael
Fig. 42. Schematic of the principles of (a) water reduction or (b) oxidation in the presence of electron donors and acceptors used as sacrificial reagents, respec­
tively [440].
Ethanol is the most common simple alcohol which can be produced by
the fermentation of saccharides [444]. Another simple alcohol is
methanol, which can be produced by direct pyrolysis of raw lignocel­
luloses [445]. Also, methanol was found more promising in a gas phase
system because here the boiling point and the ability of vaporization are
the key factors controlling the performance of alcohol as a sacrificial
reagent in the gas phase. In principle, when the photocatalytic reaction
is carried out in aqueous solutions containing electron donors, photo­
generated valence band holes irreversibly oxidize the electron donor and
can enhance e-/h+ separation. This improves the H2 evolution reaction
(Fig. 42a). On the other hand, in the presence of an oxidizing agent or
electron acceptors such as silver or iron ions, the photogenerated elec­
trons in the conduction band are taken by them and an O2 evolution
reaction is improved (Fig. 42b).
Galinska et al. [446] in their work - Pt-TiO2 catalyst with higher
activity in photocatalytic processes, reported on the effect of different
sacrificial reagents on photocatalytic hydrogen production under ul­
traviolet (UV) irradiation. Among different sacrificial reagents used,
methanol (CH3OH) shows that the highest hydrogen production activity.
Lin et al. [447] reported on the influence of different sacrificial reagents
on the photocatalytic hydrogen production over N-doped TiO2 sup­
ported on Pt powders. Photocatalysts were synthesized by the two-
microemulsion technique. Among the sacrificial reagents used in this
study, the methanol solution exhibited the highest hydrogen production
activity. Guzman et al. [448] also found that in the presence of methanol
aqueous solution as a scarifying reagent and D2O over a Cu/S-TiO2
catalyst under UV illumination, the hydrogen evolution was enhanced.
The increased activity in hydrogen evolution was largely due to the
presence of methanol that acts as an electron donor. The role of sacri­
ficial reagents as an electron donor or acceptor is reviewed by Schneider
et al. [449]. Wang et al. [450] fabricated CuS/TiO2 nanocomposite by
hydrothermal method. The photocatalytic activity of the nanocomposite
Fig. 43. (a) Photocatalytic activity CuS/TiO2 composites containing different wt % of CuS compared to single photocatalyst under 500 W Xe lamp irradiation, and
(b) Schematic diagram of the charge transfer mechanism of the nanocomposite [448].
32
Fuel 303 (2021) 121207
photocatalyst was assessed to produce hydrogen in a methanol aqueous
solution. 1% CuS/TiO2 showed the highest activity (Fig. 43a) due to the
efficient charge separation provided by composite structure and meth­
anol (Fig. 43b).
Umer et al. [451] noticed that carbon nanotubes modified TiO2 he­
terojunction dispersed in montmorillonite nanoclay prepared by com­
bined sol–gel and impregnation approach. The visible-light
photocatalytic activity of the synthesized photocatalyst was studied for
H2 evolution with different sacrificial reagents. Among different sacri­
ficial reagents used in this study, glycerol has the highest activity
(Fig. 44a) and the optimum amount was 5% (Fig. 44b).
Tahir et al. [452] successfully constructed La modified TiO2
embedded over carbon nanotubes nanocomposite for photocatalytic
hydrogen evolution in the presence of aqueous glycerol as a sacrificial
reagent. Enlarged the surface area, and enhanced charge separation
provided by suitable band structure in the composite are responsible for
the hydrogen production activity enhancement. Moreover, It is well
known that the use of hole scavengers remarkably enhances TiO2-pho­
tocatalyzed H2 evolution in which the VB holes are consumed instead of
water, making the system electron-rich and promoting hydrogen evo­
lution reaction. For instance, Yasuda et al. [453] reviewed sacrificial H2
production in the presence of different sacrificial reagents, such as
polyols, carboxylic acids, and saccharides. Similarly, Lopez et al. [454]
synthesized Pt deposited TiO2 photocatalyst using a sol–gel method for
the production of hydrogen. Methanol has produced better results
because it more efficiently traps holes. Fajrina et al. [455] fabricated
montmorillonite dispersed g-C3N4/TiO2 nanocomposite via sol–gel/hy­
drothermal method for photocatalytic hydrogen production in the
presence of aqueous glycerol. Hindered charge carriers recombination
offered by the composite structure and the role of sacrificial reagent,
bringing an excellent performance. Moreover, Liu et al. [456] studied
the overall water-splitting of Pt/TiO2 using different sacrificial reagents.
M. Ismael
Fig. 44. (a) Comparison of different sacrificial reagents for photocatalytic H2 evolution over the catalyst under visible light irradiation, and (b) Effect of different
concentration of glycerol for H2 production over the catalyst under solar-light irradiation [449].
Among various sacrificial reagents studied, CH3OH and Fe(NO3)3 were
the most efficient electron donor and acceptor, respectively, for the
photocatalytic generation of hydrogen and oxygen over Pt/TiO2 cata­
lyst. In another study, Madhumitha et al. [457] successfully constructed
the core–shell TiO2/Fe2O3 photocatalysts via precipitation method using
different sacrificial reagents. Results showed that TiO2/Fe2O3 photo­
catalysts present the highest photocatalytic hydrogen evolution when
EDTA is used as a sacrificial reagent. Kumari et al. [458] successfully
prepared the TiO2/carbon nanotube nanohybrid using the impregnation
method for determining the hydrogen production activity in the pres­
ence of glycerol as a sacrificial reagent. Results clearly have shown that
glycerol enhanced the hydrogen production activity compared to the
methanol solution. In another study, Wang et al. [459] compared
different sacrificial reagents on the photocatalytic hydrogen production
of TiO2. Among different sacrificial reagents used, TiO2/methanol shows
the best hydrogen evolution activity. Chung et al. [460] enhanced the
photocatalytic hydrogen activity of Ni-loaded TiO2 using ethanol and
methanol. Results indicated that sacrificial reagents greatly enhanced
the photocatalytic activity because they could capture the photo­
generated holes and enhanced the charge separation. Slamet et al. [461]
studied Pt-loaded TiO2 nanotube arrays for hydrogen production ac­
tivity in the presence of glycerol as a sacrificial reagent. The photo­
catalytic activity of the prepared photocatalyst was improved in the
presence of glycerol due to its obvious role in charge separation effi­
ciency. Furthermore, Yan et al. [462] used sodium sulfide/sulfite as a
hole scavenger for hydrogen production enhancement in the presence of
CoOx-loaded TiO2/CdS photocatalyst. The role of sacrificial reagents
and cocatalysts was believed to be responsible for the higher activity.
Recently, modified modification of Pt/TiO2 with Nafion (Nf) to obtain
Nf/Pt/P25 photocatalyst for determination of the hydrogen production
was documented by Wu et al. [463]. Their study showed that the
replacement of EDTA as a common sacrificial widely used in the liter­
ature with TEOA lead to enhance the hydrogen production activity in
the presence of RhB that act as a sensitizer. TEOA exhibits much higher
activity mainly due to its effective coupling with RhB and high dielectric
constant, which are both favorable for the rapid regeneration of RhB
molecule, confirming the high activity of RhB-Nf/Pt/P25-TEOA system
compared to other photocatalysts (Nf/Pt/P25, Pt/P25, and P25). In
another interesting study, Tahir et al. [464] embedded Cu nanoparticles
over 1D/1D In2O3/TiO2 NRs/NWs heterojunction to enhance hydrogen
production activity in the presence of different sacrificial reagents.
Interestingly, among all, glycerol emerged as the best candidate in terms
of holes scavenger, owing to its lowest oxidation potential. This is
because less energy is required to oxidize glycerol for hydrogen pro­
duction, followed by ethylene glycol, methanol, and ethanol. Also,
glycerol has extra hydroxyl groups compared to other alcohols (meth­
anol and ethanol have monools, ethylene glycol is diols, and glycerol has
33
Fuel 303 (2021) 121207
three hydroxyl groups). In the same research group, Tahir et al. [465]
Fabricated montmorillonite dispersed Ag/pCN-TiO2 heterojunction for
stimulating photocatalytic H2 evolution using two/three phases of
photo-reactor systems. In a slurry system, using glycerol as a sacrificial
reagent gives higher activity. The α-H atom and OH group present in
alcohol structures define the amount of H2 production in a liquid phase
photocatalytic system [466]. Similarly, Dosado et al. [467] studied the
effect of different sacrificial reagents on hydrogen production over a
series of titania nanorods prepared by calcination of hydrogen titanate
nanotubes at different calcination temperatures and supported with gold
nanoparticles. A 0.5 wt% Au/titania nanorods calcined at 600 ◦ C pho­
tocatalysts demonstrated the highest H2 production activity in the
presence of glycerol as a sacrificial reagent. The highest activity for
glycerol is attributed to the numbers of the hydroxyl group, which in­
fluences alcohol polarity, alcohol adsorption strength and binding mode
on TiO2, and also the oxidation potential of the alcohol. Moreover,
several studies were also reported on the effect of different sacrificial
reagents on the activity of TiO2 support for H2 production. Wang and co-
workers [468] studied the correlation between the different aliphatic
alcohols as sacrificial reagents and the hydrogen production rate over
Pt/TiO2 nanotubes. Among different alcohol tested in the study, meth­
anol exhibited the highest activity. Bowker et al. [469] studied the
hydrogen production rates of Pd/P25 photocatalyst in the presence of
different alcohols under UV light irradiation. Their results revealed that
Pd/P25 photocatalyst in the presence of glycerol showed the highest
activity. In another study related to the same group, Bowker et al. [470]
investigated that the highest hydrogen production activity was obtained
for Au/P25 photocatalyst in an aqueous solution containing methanol.
Bahruji et al. [471] studied the effect of 20 different alcohols on the
hydrogen production activity of the Pd/P25 system using 20 different
sacrificial reagents and observed that triols (alcohol with three OH
groups) presented the highest activity. Their results investigated that the
electron donor alcohol must have a-H adjacent to the OH group(s),
which affects the polarity, adsorption strength, and binding mode on
TiO2. Furthermore, Li et al. [472] reported that the hydrogen production
activity of Cu2O/P25 photocatalysts under UV irradiation is strongly
related to the polarity of the sacrificial reagent. Their study connects the
relation between the polarity of the alcohol and the hydrogen produc­
tion activity and observed that Cu2O/P25 photocatalysts showed the
highest activity in the presence of methanol. Su et al. [473] demon­
strated that the high hydrogen production activity of the Pd(shell)–Au
(core) nanoparticles deposited on TiO2 was obtained in an aqueous so­
lution containing methanol. Further studies were also reported on
applying different alcohols with different concentration for photo­
reforming production of hydrogen [474,475]
The sacrificial reagent was mainly used for most of the research done
on the overall water splitting. Nevertheless, if H2 is produced by a
M. Ismael Fuel 303 (2021) 121207

photocatalytic process using solar energy and sacrificial agents supplied photocatalytic performance for hydrogen evolution. The optimum
by biomass; it will be a most promising sustainable energy source. amount of 11.87 wt% of both cocatalysts (CNT and Ni(OH)2)
(Fig. 46a&b) present the highest activity due to the efficient charge
separation by the two cocatalysts.
3.3. Amount of cocatalyst loading
Wang et al. [483] systematically studied the efficiency of the H2
evolution of TiO2 loaded with two cocatalysts (CuS and NiS) constructed
In heterogeneous photocatalytic systems, cocatalysts were mainly
by a simple hydrothermal approach. The optimal ratio was 5 wt% for
used to enhance the photocatalytic hydrogen activity performance of the
both cocatalysts show the highest activity (800 mmol h− 1). They found
photocatalyst by improving the charge separation efficiency. Noble
that the reduction in the bandgap energy, more visible light absorption,
metals are commonly used as cocatalyst because their Fermi energy level
and efficient charge separation by cocatalysts are responsible for
is usually lower than that of TiO2 [476], making them a suitable
enhancing photocatalytic performance. Yang et al. [484] enhanced the
candidate to form a Schottky barrier at the metal/TiO2 interface. It’s
photocatalytic hydrogen evolution of TiO2 using MoS2 and g-C3N4 as
widely accepted that the amount of cocatalyst has a great influence on
cocatalysts and the optimal was 1.0 wt% for two cocatalysts. The effi­
the photocatalytic hydrogen production performance by providing more
cient charge separation provided by two cocatalysts is responsible for
active sites for hydrogen production at the surface of the photocatalyst.
higher activity. Zhang et al. [485] used a solvothermal synthesis tech­
However, depositing more cocatalyst above the optimum value, the
nique to prepare TiO2 photocatalysts with NiS cocatalyst. 7 wt% NiS was
hydrogen evolution rate decreases due to the occupation of the surface-
optimum and displayed the maximum level of activity. Sreethawong
active site lead to the reduction of the surface area. Furthermore, the
et al. [486] compared the photocatalytic hydrogen production of Cu-,
higher dose of the cocatalyst prevents the light to reach and activate the
Pd-, and Au-loaded mesoporous TiO2. Photocatalysts were prepared by
TiO2 for charge carrier production, and therefore decreasing the H2
the sol–gel method. 2 wt% Au photocatalyst exhibited the highest ac­
production. Besides, the excess amount of cocatalyst loading can act as a
tivity. Moreover, Chen et al. [487] successfully loaded different weight
recombination center [477,478]. Therefore, the amount or concentra­
ratios of CuO cocatalyst over TiO2 for hydrogen production determi­
tion of the cocatalyst should be optimized to obtain the maximum
nation in the aqueous solution containing ethanol. 1.25 wt% CuO
hydrogen production activity under light illumination. For instance, Lv
exhibited the highest activity. New non-noble-metal co-catalyst Mo2C
et al [479] compared the photocatalytic hydrogen evolution of the
used in combination with CdS for hydrogen production enhancement
graphene loaded by Cu and Pt acts as cocatalysts. Cu-graphene per­
was reported by Ma and co-workers [488]. 2.0% Mo2C/CdS was opti­
formed higher activity than that of a pure graphene cocatalyst but still
mum and shows higher activity than Pt/TiO2 and even much higher than
lower than the robust Pt cocatalyst (Fig. 45a). The optimum amount of
pure CdS. Zong et al. [489] successfully loaded MoS2 over CdS photo­
Cu and Pt was 1.5% (Fig. 45b).
catalyst for hydrogen production enhancement. MoS2 was used as a
In another study concerning other cocatalysts, the work of Wu et al
cocatalyst and the optimal was 0.2 wt% shows the highest activity even
[480] for example successfully fabricated Bi2O3-TiO2 composite photo­
more than noble metals. Herein, the role of MoS2 in the enhancement of
catalysts by the simple impregnation-calcination method. The results
charge separation plays a key role in improving hydrogen production
indicated that the optimum amount of the Bi2O3 cocatalyst loading was
activity. Wang et al. [490] modified TiO2 by Ti(IV) and Ni(OH)2 that
0.89% mol shows the highest hydrogen production activity in aqueous
acts as the hole and electron scavengers, respectively. The photo­
glycerol solution due to the facilitated separation of photogenerated
catalytic activity of the modified TiO2 photocatalyst was tested for
electron-hole pairs. It is well-documented that MoS2, a famous cocata­
hydrogen production. 1 wt% of Ni(OH)2 and 0.1 wt% Ti (IV) show the
lyst, was widely used in constructing heterojunctions with TiO2 in
highest activity. Efficient charge separation providing by the presence of
photocatalytic utilizations. For instance, Xiang et al. [481] synthesized
the two cocatalysts is responsible for the higher activity of TiO2.
TiO2/MoS2/graphene composite by two-steps hydrothermal method for
Mahadik et al. [491] hydrothermally prepared Ni(OH)2/CdS/ZnIn2S4/
hydrogen evolution activity. The higher activity of the composite pho­
TiO2 heterostructure film on the FTO substrate. A Photoelectrochemical
tocatalyst was attributed to the efficient charge separation providing by
property of the prepared film was investigated for hydrogen production.
the composite formation and the presence of a cocatalyst. Herein, the
Ni(OH)2 as a cocatalyst plays an important role in the enhancement of
cocatalyst traps electrons and provides more surface active sites for
their activities. Chen et al. [492] enhanced the photocatalytic perfor­
hydrogen reduction. Furthermore, Ni(OH)2 could be used as a cocatalyst
mance of TiO2 photocatalysts by loading them with CoSx. The highest
for the enhancement of hydrogen production over TiO2, For instance,
hydrogen production activity was obtained when the amount of catalyst
Wang et al. [482] fabricated TiO2-Ni(OH)2/carbon nanotubes (CNT)/
is 10 wt% (Fig. 47a&b). CoSx as a cocatalyst enhanced charge separation
CdS hybrid photocatalyst, presenting a dramatically improved

Fig. 45. (a) Effects of different cocatalyst loaded graphene 2.0 photocatalysts on H2 generation evolution in CH3OH under UV–vis light irradiation, and (b) Different
Cu contents in GP 2.0 photocatalysts, (1) 0, (2) 0.5% Cu, (3) 1.0% Cu, (4) 1.5% Cu, (5) 2.0% Cu, (6) 3.0% Cu, (7) 5.0% Cu, (8) 8.0% Cu under the same condi­
tions [477].

34
M. Ismael Fuel 303 (2021) 121207

Fig. 46. (a) H2 evolution on the hybrid photocatalysts loaded with different amounts of Ni(OH)2, and (b) different amounts of CNT (carbon nanotubes) [480].

Fig. 47. (a&b) H2-evolution activities of CoSx/TiO2 containing different wt % of CoSx and (B) H2-evolution rate of (a) bare TiO2, and different wt % of CoSx over
TiO2 (b) 0.1%, (c) 1%, (d) 5%, (e) 10%, (f) 25%, and (g) 50%, (c) Typical transient photocurrent responses of (a) bare TiO2, and different wt % of CoSx over TiO2 (b)
1%, (c) 10%, and (d) 50%, and (d) UV–vis absorption spectra and corresponding photographs (inset) of (a) bare TiO2, and different wt % of CoSx over TiO2 (b) 1%,
(c) 10%, and (d) 50% [490].

(Fig. 47c), and light absorption (Fig. 47d), resulting in enhancing the
hydrogen production.
Moreover, Shen et al. [493] studied the effect of catalyst loading on
the hydrogen production activity of TiO2. CuO and Co3O4 were used as
dual-cocatalysts in this study and show that these cocatalysts enhanced
the photocatalytic performance of TiO2. Both cocatalysts are beneficial
in improving interfacial charge transport and separation, resulting in
high photocatalytic performance. Tin diselenide (SnSe2) is an n-type
semiconductor with a narrow bandgap of about 1.37 eV with a CdI2 type
layered structure [494] can also be used as a catalyst to enhance the
hydrogen production activity. For instance, Nasir et al. [495] recently
coupled low-cost and available tin diselenide with TiO2 fiber and g-C3N4
quantum dots to improve its efficiency for photocatalytic water splitting.
Their results showed that the loading of SnSe2 has a great influence on
enhancing photocatalytic hydrogen production through improving the
separation of charge. Li et al. [496] distributed a highly conductive
Ti3C2 MXene and MoS2 rich in molybdenum vacancies on the TiO2
nanosheets through a two-step hydrothermal method. Then, a unique
structure of MoxS@TiO2@Ti3C2 composite with molybdenum vacancies
containing double cocatalysts is achieved. MAX phases, the precursors of
MXenes, have the general formula of Mn+1AXn, where M is an early
transition metal, A is a group IIIA or IVA element, X is carbon and/or
nitrogen, and n = 1, 2, or 3 [497]. Besides MoS2 is an abundant and low-
cost cocatalyst and can be easily used as an alternative to the high-cost
noble metal cocatalyst [498]. The obvious hydrogen production activity
of the new composite containing double cocatalysts was ascribed to the
role of molybdenum vacancies in the suppression of the charge recom­
bination as well as in the role of the double cocatalysts in enhancing the

35
M. Ismael Fuel 303 (2021) 121207

charge separation efficiency. reagents. Alkaim et al. [507] hydrothermally synthesized TiO2 nano­
Other cocatalysts can be used to enhance the photocatalytic particles with high surface area and their photocatalytic activity was
hydrogen production of TiO2, including cobalt sulfide quantum dots evaluated for hydrogen production in the presence of EDTA as a sacri­
[499], Co(OH)2 [500], and Ni(HCO3)2 [501]. However, the optimum ficial reagent. Different photocatalyst concentrations were loaded in this
amount of the cocatalysts, and their cost remaining big challenges. study (0.2–2.5 g/L-1), and they observed that the highest hydrogen
production activity was observed for the photocatalyst concentration of
1.0 g/L-1, Further increase the catalyst content in the suspension leads to
3.4. Photocatalyst load
decrease the hydrogen production activity, which is mainly ascribed to
the shielding effect. In another study related to the same group, Alkaim
Previous studies have shown that the amount of photocatalyst has a
et al. [508] applied a hydrolysis method to synthesize TiO2 nano­
significant influence on H2 production [502]. Generally, Maximum
particles with a high surface area. Photocatalytic hydrogen production
hydrogen production was obtained at the optimum photocatalyst con­
was evaluated from the biomass-derived compound (citric acid) as well
centration, above this optimum value, hydrogen production was usually
as in the presence of TEA. The optimum amount of photocatalyst loading
decreased due to the photons cannot be continually injected, which
was a critical factor in enhancing the photocatalytic activity, and it was
leads to the recombination of electrons and holes [503] Besides, an
1 g/L-1 in the presence of citric acid and 2 g/L-1 in the presence of TEA.
excessive amount of catalyst in aqueous solution shields the incident
An increase in the amount of photocatalyst leads to a decrease the ac­
light, and further prevents the generation of electrons from the catalyst.
tivity, which may ascribe to the agglomeration and shielding effect.
Furthermore, heavy loading of catalysts leads to the agglomeration of
Naffati et al. [509] synthesized hybrid photocatalysts containing
the photocatalyst particle, thereafter, the surface of the catalyst is un­
different amounts of carbon nanotubes (CNTs) and TiO2 by a one-pot
available to absorb photons and generate electrons/holes pairs. For
oxidation/hydrothermal route. The photocatalytic activity of CNT/
instance, Nada et al. [504] studied the effect of different catalyst con­
TiO2 hybrid was tested for hydrogen production in an aqueous solution
centrations on the photocatalytic activity of RuO2/TiO2 photocatalyst.
containing methanol and glycerol as sacrificial reagents and Pt nano­
Different concentrations of the RuO2/TiO2 photocatalysts were tested
particles as a cocatalyst under UV-LED irradiation. Their results showed
and revealed that 2gL-1 has the maximum hydrogen production activity.
that 1%CNT-Pt/TiO2 displayed the highest activity (Fig. 48a&c) and the
Daskalaki et al. [505] obtained the maximum hydrogen production
activity is highly dependent on the carbon nanotubes content in the
under simulated sunlight in the presence of glycerol as a sacrificial re­
hybrid (Fig. 48b&d).
agent over 2.66 g L-1 0.5%Pt/TiO2 photocatalyst. Besides, their results
Madhumitha et al. [510] synthesized the core–shell nano TiO2/
showed that the amount of Pt content and glycerol concentration have a
Fe2O3 photocatalyst via coprecipitation method in the presence of
detrimental effect on photocatalytic performance. Salgado et al. [506]
different sacrificial reagents and tested doe hydrogen production. 0.2 g
also reported an enhanced hydrogen production rates for optimum Au/
TiO2/Fe2O3 catalyst dosage in the EDTA as sacrificial agent exhibited
TiO2 catalyst loading up to 0.2 g/L-1. The photocatalytic activity was
the highest activity. The authors claimed that efficient charge separation
tested under simulated sunlight in the presence of different sacrificial

Fig. 48. Rate of hydrogen evolution (a, and c), and total hydrogen production (b, and d) from an aqueous solution containing methanol (a, and b) and glycerol (c,
and d) using different Pt/TiO2 and CNT-Pt/TiO2 photocatalysts [507].

36
M. Ismael
was the key factor in enhancing photocatalytic performance.
3.5. Light source and intensity
The light source and intensity is an important parameter because it
can control the amount of electron/hole pairs generated on illuminated
photocatalyst [511]. Madhumitha et al. [510] studied the effect of the
light irradiation on the hydrogen evolution rate of the core–shell nano
TiO2/Fe2O3 photocatalyst using three different visible lamps of 47, 74,
and 96 W/m2 light irradiances. They found that irradiated TiO2/Fe2O3
photocatalyst with 96 W/m2 exhibited the highest hydrogen evolution
that may be attributed to the generation of more electron and holes
pairs, which are used to reduce the water of hydrogen ion. Stelma­
chowski et al. [512] noted the influence of light power on the efficiency
of hydrogen production of the Pd-TiO2 photocatalyst. They irradiated
the Pd-TiO2 photocatalyst with two different power of Xe-arc lamps
(225, and 300 W), and they observed that the hydrogen evolution rate
was sharply decreased with 225 W irradiation, whereas, with a 300 W
power source leaving the system as a gas with more stability. Xing et al.
[513] found that light intensity plays a critical role in the photocatalytic
reaction rate of Au/TiO2 photocatalyst. The catalyst was prepared by the
photodeposition method, and its photocatalytic activity was checked for
hydrogen activity at different light intensities of 0–7 kW/m2 and has a
super-linear law dependence on the light intensity (Rate α Intensity,
with n > 1). However, at a light intensity of 7–9 kW/m2, the dependency
becomes sub-linear (n < 1), which means that increase in the light in­
tensity above 7 kW/m2 showed a slight increase in the hydrogen pro­
duction (Fig. 49a-d). The explanation of the results is at the light
intensity of 7 kW/m2, the surface plasmon resonance of gold was the
critical factor in the super-linear relationship, whilst, for the light in­
tensity of the range 7–9 kW/m2, the faster recombination rate of elec­
trons and holes limits was the main reason.
Fig. 49. Hydrogen evolution rates in 1–9 kW/m2 light intensities of different Au/TiO2 catalyst loading (a) 0.1 g/L, (b) 0.5 g/L and (c) 1 g/L;,(d) Influence of light
intensity on hydrogen production rate [511].
37
Fuel 303 (2021) 121207
Yoshida et al. [514] produced hydrogen from the reaction of
methane and water over Pt/TiO2 at nearly room temperature. The
apparent quantum yield of the hydrogen production rate was obtained
from the high light intensity (60 mW cm− 2) compared to that of lower
intensity (2 mW cm− 2). Authors claimed that the formation of surface
organic species and intermediate were influenced by the high light in­
tensity. Kumar et al. [515] dispersed Ag2O nanoparticles on TiO2
nanotubes to form nano-heterojunction. They studied the influence of
light intensity on the photocatalytic hydrogen production over Ag2O/
TiO2 nano-heterojunction., and they observed that the highest hydrogen
production activity (55.8 mmol h-1g-1cat) was obtained in the summer­
time with a light intensity of 1358.8 W/cm2, on the other hand, the
hydrogen production rate was 24.8 mmol h-1g-1cat that achieved in the
wintertime with a light intensity of 790 W/cm2). Wang et al. [516]
fabricated a novel Cu2O/Au/TiO2 photocatalyst composite film using
combined of three synthesis methods and tested for hydrogen produc­
tion under UV light, visible light, and solar light. The Cu2O/Au/TiO2
photocatalyst composite exhibited the highest hydrogen production
activity under solar light illumination. Authors believed that under solar
irradiation, the charge separation was efficient due to the presence of
the surface plasmon resonance of Au and the formation of the composite
structure. Nomikos et al. [517] studied the effect of incident light in­
tensity on the photocatalytic hydrogen production rate over Pt/TiO2
photocatalyst in the presence of methanol as a sacrificial reagent. The
effect of incident light intensity was studied in the range from 0.5 to 3.0
mWcm− 2 and observed that the light intensity of 2.3 mWcm− 2 exhibited
the highest activity. Further increase in the light intensity up to 3.0
mWcm− 2 does not companied with an increase in hydrogen production
activity. Importantly, the authors thought that under weak light illu­
mination, band bending is relatively high for efficient charge separation,
and the rate is the first-order kinetics. While, with increasing light in­
tensity, the band bending decreased and the surface reactions strongly
M. Ismael Fuel 303 (2021) 121207

compete with processes involving electron-hole recombination. the rate presence of the intermediate such as formaldehyde and formic acid on
becomes half order. the surface of Pt/TiO2 during the photoreforming of methanol, and these
intermediate are responsible for the deactivation of Pt/TiO2 toward
hydrogen production (Fig. 50a-d).
3.6. Catalyst deactivation
Chang et al. [525] fabricated a nanocomposite comprising gold (Au)
nanodisks and TiO2 nanophases sandwiched between zeolite nanosheets
Up-to-date, most of the published studies are concentrated on pho­
and tested for hydrogen production through photoreforming of meth­
tocatalytic hydrogen production using methanol as a sacrificial reagent
anol. They observed regular deactivation during methanol photo­
in a process called methanol-reforming [518,519]. During this process,
reforming because of the formation of an intermediate. This
some physical and chemical changes on the catalyst occur because of
deactivation process was attributed to the chemisorbed CO accumulated
their exposure to light irradiation. Due to the relatively small surface
on Au in the absence of oxygen. Due to its higher affinity to be adsorbed
area of most photocatalysts, charge carriers require more time to sepa­
on metallic Au, when the oxygen is absent, the CO is accumulated and
rate, thereafter can recombine easily on the surface of the catalyst, thus
does not convert to the CO2, which leads to blocking the surface of
these charges could reduce or oxidize the catalyst causing deactivation
metallic Au, resulting in the deactivation of the photocatalyst. Lopez
[520]. For example, cadmium sulfide is one of the most common in
et al. [526] tested the Pt-modified TiO2 for hydrogen production in
photocatalysis technology due to its low bandgap energy, which can be
presence of different alcohols. Authors thought that several intermediate
activated under visible light. Nevertheless, these materials can be easily
such as formaldehyde, formic acid, and carbon dioxide could be formed
subjected to photocorrosion during the photocatalytic reaction under
through methanol-reforming, causing deactivation of the photocatalyst.
the illumination of light, restrict its wide applications [521,522]. For
Haselmann et al. [527] investigated a sudden deactivation of Pt/P25
instance, Villa et al. [523] demonstrated that the photocatalytic activity
during the initial stages of photocatalytic H2 evolution from aqueous
of N-doped TiO2 for hydrogen production under visible light irradiation.
solution in the presence of methanol. They suggested that the CO gen­
They noted that there is a clear deactivation of the catalytic activity
eration through the decomposition of methyl formate is responsible for
between the first and the second experiment, which due to the nitrogen
blocking the active sites on the noble metal co-catalyst and thus result in
leakage to the solution in the form of NH+4 that revealed by the total
significantly slower reaction kinetics, resulting in deactivation of the
organic carbon experiment (TOC). Recently, Huang et al. [524] found
photocatalyst. Chung et al. [528] used a one-pot synthesis method to
that the Pt-loaded TiO2 photocatalyst suffers from a deactivation prob­
prepare Pt functionalized TiO2 and evaluated it for H2 production. Au­
lem. They observed that the formation of intermediates such as form­
thors appealed that slow CO-poisoning and metal encapsulation might
aldehyde and formic during the methanol-reforming over Pt/TiO2 plays
also initiate the deactivation of the materials. Most importantly, the
a major role in the deactivation of Pt/TiO2 photocatalyst. The gas
presence of sodium ions used in the synthesis procedure can strongly
pressure of generated H2 through the photocatalysis process, structural
affect the hydrogen production activity, and the photocatalytic mate­
change, and phase transition have revealed by the TEM, XRD, Raman
rials should be carefully washed before running the experiment. Besides,
spectra, and UV–vis spectroscopy are not changed and are not respon­
the above-mentioned parameters, the duration of the photocatalytic
sible for the deactivation process. On the other hand, XPS proofed the

Fig. 50. H2 production from methanol photo-reforming over (a) Freshly prepared, (b) Methanol photo-reforming over the non-deactivated Pt/P25 sample, deac­
tivated Pt/P25 sample and reactivated Pt/P25 sample The water washing treatment of Pt/ P25, H2 production of Pt/P25 (c) and P25 (d) in aqueous methanol with
different intermediates, 1 ml HCHO or 1 ml HCOOH [522].

38
M. Ismael
reaction can affect the total photocatalytic performance [115,395].
4. Conclusion and future perspective
With this review, recent progress in TiO2-based photocatalysts, and
the development of modification techniques for photocatalytic H2 pro­
duction have been systematically discussed. More important, this
comprehensive review briefly explained the influence of the operation
parameters on the photocatalytic hydrogen production over TiO2-based
photocatalysts. In future research and development on photocatalytic
hydrogen production via water splitting can be focused on the next
aspects:
• Low cost and effective preparation method: synthesis methods are very
important that directly affect the whole photocatalytic hydrogen
production process. Researchers in the future should focus their work
on the development of the new synthesis methods using cheap,
environment-friendly, and non-toxic precursors for the synthesis of
the nanoparticles materials. Nevertheless, the sol–gel method
remaining the promising method in the preparation of TiO2 nano­
particles because it’s performed under mild conditions. Furthermore,
the obtained nanoparticles have good crystallinity, high surface area,
and small particle size.
• Enhancement of visible light absorption: visible light absorption is the
first step in the photocatalysis process, more light absorption means
more charge carrier generation on the photocatalytic surface,
resulting in the enhancement of the whole photocatalytic hydrogen
process. Thus, the improvement of this process is a critical step in
hydrogen production activity. Several approaches need to be devel­
oped in the future, including the doping of metal and nonmetal el­
ements. The big challenge in this step is to reach the optimum
concentration of the doped materials either in the lattice or in the
interstitial part of the TiO2. However, more dopant concentration
can act as recombination centers that lead to a decrease in the
photocatalytic hydrogen production of TiO2.
• Improvement of charge separation efficiency: charge separation is also
an important step in the photocatalytic hydrogen production of TiO2
nanoparticles. After the charge excitation step, the electron-hole
pairs should be efficiently separated and transferred to the surface
of the photocatalyst to initiate the redox reaction. If this step is not
occurring as fast as possible, the charge carriers will be recombined
either in the bulk or on the surface of the TiO2 photocatalyst.
Cocatalyst loading and composite formation were developed to be
promising methods to inhibit the charge carrier’s recombination. But
these two methods have some limitations and need to be developed.
Most of the published studies used noble metals as a cocatalyst, these
metals are very expensive. Thus, searching for other cheap transition
metals should be researched. In addition, composite formation be­
tween two semiconductors with suitable band position is also not an
easy task process, since not all semiconductors can couple with TiO2.
• Sacrificial reagents (electron donor or acceptor) and the design of novel
photocatalytic system for overall water splitting
Using sacrificial reagent to trap the photogenerated valence band
hole is commonly used in photocatalytic hydrogen production over
TiO2-based materials. Alcohol, like methanol or ethanol, is commonly
used in this process. However, it will be very beneficial for our envi­
ronment if we could replace these sacrificial reagents with other waste
products chemicals from the industry like glycerol as a by-product of the
biodiesel industry. Researchers should focus on finding more sacrificial
reagents as waste products from the industry. If that will be done we will
kill two birds in one stone. It will be mostly important to produce
hydrogen from water without using sacrificial reagents. Therefore, the
big challenge for the photochemists is to design a photocatalyst for
overall water splitting. Appropriate cocatalysts such as Pt for H2 evo­
lution and Co(OH)2 for oxygen evolution could be used to split pure
39
Fuel 303 (2021) 121207
water and to suppress thermodynamically favored back reaction.
Further research should be done to replace the high cost Pt with other
low-cost transition metals. In this photocatalytic system, the photo­
generated holes are used in a productive half reaction, rather than
quenched with a sacrificial donor.
• Controlling the morphology of TiO2 photocatalysts: it’s widely accepted
that the synthesis of the porous materials has a great influence on the
photocatalytic hydrogen production of TiO2. Porosity increases the
specific surface area of the photocatalyst by providing a more
surface-active site for water reduction and facilitates the charge
transfer. Thus, developing synthesis methods for preparing high
surface area materials is still a difficult task because some of the
methods require chemicals for synthesis that are toxic to our envi­
ronment and the template used for some synthesis is also expensive.
• Stability of the photocatalyst
Cost-effective photocatalytic H2 producing systems should focus on
the use of visible-light active and stable photocatalyst in order to allow
their practical deployment. The stability of the photocatalytic activity is
one of the most important aspects in a photocatalytic process because
the stable photocatalysts have longer lifetime, easy to reuse or recover,
leading to simplify the whole process and decrease the overall cost.
Thereafter, clear challenges related to system stability must be overcome
and the prepared photocatalyst should be chemically and thermally
stable against photocorrosion and under light irradiation during the
photocatalytic reaction.
• Hydrogen transport and storage: Due to its high inflammability, special
safety rules should be taken in dealing with hydrogen. However,
hydrogen can be easily stored as pressurized gas and liquid com­
pounds and easily distributable through the pipeline.
It can be concluded that photocatalytic solar hydrogen generation
using TiO2-based photocatalyst is an effective and economical way for
sustainable energy production.
In summary, we can say:
(i) Metal and non-metal doping can enhance photocatalytic perfor­
mance due to narrow the bandgap energy.
(ii) Cocatalyst loading, composite formation, and dye sensitization
improve photocatalytic activity by facilitating charge transfer
and separation efficiency.
(iii) Defect engineering is also a promising method to enhance the
photocatalytic properties of TiO2-based photocatalyst by modu­
lating photocatalyst properties.
(iv) The pH has a thoughtful impact on the characteristics of the
photocatalyst, such as particle size dissemination, surface charge,
the dissociation of the substrate.
(v) Polarity and the number of hydroxyl groups present in the
sacrificial reagent also have a critical role in enhancing photo­
catalytic activity.
(vi) An optimum amount of catalyst loading has a high activity, while
with high concentration; the activity is decreased due to the
shielding effect, the same is true for the cocatalyst loading, with
heavy loading, the activity is decreased owing to the formation of
the recombination center.
(vii) Light intensity is an important parameter because it can control
the amount of electron/hole pairs generated on illuminated
photocatalyst.
(viii) Hydrogen production through methanol-reforming can cause
catalyst deactivation through the formation of intermediate
through the photocatalytic reaction.
M. Ismael Fuel 303 (2021) 121207

Declaration of Competing Interest [52] A. Meyer (a group of M. Wark), B.Sc. Thesis. Ruhr-University Bochum, Germany,
(2013).
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Additionally, 6 more papers will be submitted soon; his
[488] Prof.Dr. B. Ma, H. Xu, K. Lin, J. Li, Dr. H. Zhan, Prof.Dr. W. Liu, Prof.Dr. Can Li,
ChemSucChem. 9 (2016) 820-824. research interests include the synthesis of new photocatalytic
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