Fuel 307 (2022) 121745

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Emerging cocatalysts in TiO2-based photocatalysts for light-driven catalytic

hydrogen evolution: Progress and perspectives
Changlei Xia a, Thi Hong Chuong Nguyen b, c, Xuan Cuong Nguyen b, c, Soo Young Kim d,
Dang Le Tri Nguyen e, f, Pankaj Raizada g, Pardeep Singh g, Van-Huy Nguyen h, *, Chinh Chien
Nguyen b, c, *, Van Chinh Hoang i, Quyet Van Le d, *
a
Co-Innovation Center of Efficient Processing and Utilization of Forestry Resources, College of Materials Science and Engineering, Nanjing Forestry University, Nanjing,
Jiangsu 210037, China
b
Institute of Research and Development, Duy Tan University, Da Nang 550000, Vietnam
c
Faculty of Environmental Chemical Engineering, Duy Tan University, Da Nang 550000, Vietnam
d
Department of Materials Science and Engineering, Institute of Green Manufacturing Technology, Korea University, Seoul 02841, Republic of Korea
e
Division of Computational Physics, Institute for Computational Science, Ton Duc Thang University, Ho Chi Minh City, Vietnam
f
Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam
g
School of Advanced Chemical Sciences, Shoolini University, Solan (HP) 173229, India
h
Faculty of Biotechnology, Binh Duong University, Thu Dau Mot, Vietnam
i
School of Chemical & Biomolecular Engineering, The University of Sydney, NSW 2006, Australia

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

Keywords: TiO2-based photocatalysts have been maintained as the most prominent candidate for solar-driven hydrogen (H2)
cocatalysts evolution over the past decades. However, poor separation of generated electron-hole pairs has been considered
TiO2-based photocatalysts the bottle-neck issue, restricting the TiO2 activity. Coupling a TiO2 photocatalyst to cocatalyst(s) turns out to be
hydrogen production
the ideal strategy to suppress the charge recombination and offer robust active centres, boosting the H2 evolution
performance. This review aims at providing the frontier investigations of cocatalysts-integrated TiO2 for photo-
induced H2 evolution. Four types of cutting-edge development of cocatalysts, including metal (noble metal, non-
noble metal, bimetallic), metal sulfides and metal phosphides, 2D-MXenes, and dual materials-based cocatalysts,
have been successfully highlighted and discussed. The systematically provided cocatalysts, which remarkably
promote the charge separation and facilitate the surface reactions, bring out a roadmap to inspire the preparation
of superior TiO2-based materials for H2 evolution shortly. We expect this review could provide enriched infor­
mation to tailor the TiO2 supported active sites of cocatalysts for highly photo-induced H2 evolution.

1. Introduction
To date, the depletion of fossil fuels is among the biggest challenges
that humans have ever faced. An excellent strategy to lessen our
dependence on fossil fuels is to transition to renewable energy sources.
Accordingly, massive research and developments have been widely
focused on converting abundant solar energy into chemical energy in
recent years.
Nature has utilized solar energy to convert water and carbon dioxide
into oxygen and high-energy carbohydrates [1]. Learning from natural
photosynthesis, artificial photosynthesis is proposed, as depicted in
Fig. 1 [1,2]. Giacomo Ciamician mentioned the first idea at the begin­
ning of the 1900 s [3]. Honda and Fujishima verified the first experiment
of solar-driven water splitting at the beginning of the 1970 s [4].
Compared with fossil fuels, sustainable solar fuels, mainly hydrogen
(H2), are ideal energy carriers. In general, there are three distinct
methods to produce solar H2, including (a) electrolysis of water (H2O)
using a solar cell; and artificial photosynthesis via (b) photo­
electrochemical water splitting; and (c) photocatalytic water splitting
[2]. Multiple efforts are underway to explore artificial photosynthesis
(Table 1).
This review favors using solar energy instead of electricity to drive

* Corresponding authors.
E-mail addresses: nguyenletridang@tdtu.edu.vn (D.L.T. Nguyen), nvhuy@bdu.edu.vn (V.-H. Nguyen), nguyenchinhchien@duytan.edu.vn (C. Chien Nguyen),
quyetbk88@korea.ac.kr (Q. Van Le).

https://doi.org/10.1016/j.fuel.2021.121745
Received 1 April 2021; Received in revised form 28 June 2021; Accepted 15 August 2021
Available online 28 August 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
C. Xia et al.
the water-splitting as part of that strategy. This approach is a promising
strategy for sustainably H2 evolution at competitive costs [5]. Among
semiconductor photocatalysts, enormous progress has been made in
developing an advanced and broad group of titanium dioxide (TiO2) due
to its low price, high photocatalytic activity, considerable photo­
stability, and non-toxicity [6]. However, the primary technical barriers
of this system are low quantum performance and inefficient exploitation
of visible light, which restrain the potential use in H2 evolution [7].
To further solve these challenges and improve photocatalytic activ­
ities, it requires a fundamental understanding of heterogeneous TiO2
semiconductors at the molecular level. The basic principles of conven­
tional TiO2 photocatalyst have been comprehensively reported in the
previous study [8]. Fig. 2 illustrates three steps classified at the unit cell,
bulk, and surface phases during the photocatalytic reactions [9]. In
brief, the electron (e− ) will be excited from the valence band in the
conduction band when the light absorption with energy equal to or
greater than the bandgap. It is noteworthy that the photogenerated e−
and hole (h+) could follow several pathways upon excitation. For
example, the photogenerated e− -h+ pairs might undergo surface or
volume recombination, transfer to the acceptor (A) or donor (D) mole­
cules, respectively, and react with them on the surface. So far, many
approaches have been explored to improve the excitation, enhance the
charge transfer, inhibit the bulk and surface recombination, and pro­
mote the reduction and oxidation reactions [9]. Among these potential
approaches for enhancing the H2 evolution, combining TiO2 with co­
catalysts to form a hybrid structure has been considered. In a realistic
cocatalysts-TiO2-based system, cocatalysts have four primary positive
roles in guiding the charging kinetics in photocatalysis. Firstly, they
could act as a light-harvesting center that extends the light absorption of
the semiconductors [10]. Secondly, cocatalysts perform as an interface
with the semiconductor to effectively catch charge carriers and force­
fully encourage the separation of electron-hole pairs [11–13]. Thirdly,
they work as an efficient active site for supplying the trapped charges to
redox reactions [11,12]. Finally, cocatalysts take effect as alternative
reaction sites for suppressing the photocorrosion of semiconductors
[14]. In brief, these advances would enhance the light-driven catalytic
activity and selectivity and increase the stability of photocatalysts.
Up to the present, cocatalysts systems have been widely imple­
mented for various promising applications [15], including CO2 reduc­
tion [16], water splitting [17–20], H2 evolution [21–23], degradation of
organic contaminants [24]. In general, there are two critical roles of
cocatalysts that could be highlighted, including in charge trapping, and
surface and interface reactions, leading to effectively enhance the per­
formance of photocatalysts. Typically, Li et al. reviewed cocatalysts for
photocatalytic reduction of CO2 towards sustainable and green solar
fuels [9]. Various types of cocatalyst, including the biomimetic, metal,
metal-free, and multifunctional ones, toward selective photo(electro)
reduction and electroreduction of CO2 are successfully highlighted and
discussed. Bai et al. reported the strategies for surface design of co­
catalysts (e.g., the composition, facets and phases) toward
Fig. 1. From the natural photosynthesis by green plants towards the mimicking photosynthesis by photocatalytic water splitting. Adapted with permission from Kudo
and Miseki [2]. Copyright (2009) Royal Society of Chemistry. (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
2
Fuel 307 (2022) 121745
photocatalytic water splitting and CO2 reduction [25]. Recently, Nguyen
et al. provide comprehensive strategies for the utilization of Ti3C2Tx as a
catalyst for improving solar-driven catalytic H2 evolution, including
surface functional groups engineering, structural modification, and
cocatalyst coupling [21]. The latest signs of progress in the design and
construction of composite photocatalyst using Ni-based [26–28], Cu-
based [22], 2D transition metal dichalcogenides [29] for enhanced H2
evolution have also been reported. As an advanced and broad group of
TiO2-based photocatalysts, the interest in cocatalysts in TiO2 photo­
catalysis for light-driven catalytic H2 evolution, including water split­
ting and water reduction half-reaction, arises remarkable attention.
In this review, we timely highlight the recent progress in cocatalysts
design of TiO2-based photocatalysts, such as noble metals and non-noble
metals, developed for H2 evolution. Additionally, the design principles,
concepts, and functional mechanisms at the molecular level of each
developed cocatalyst for H2 evolution are also proposed. Furthermore,
the current challenges and prospects of tailoring cocatalysts in TiO2-
based photocatalysts will be discussed and summarized. We hope that
this comprehensive and thoughtful article could provide a guideline for
better tailoring the cocatalysts in TiO2 photocatalysis and understanding
the mechanism of H2 evolution.
2. Fundamentals of light-driven catalytic H2 evolution
To date, significant progress has been made in the ecologically
friendly, technologically reliable, and relatively low-cost light-driven
catalytic H2 evolution. This strategy has opened a new era in the field of
solar energy conversion to H2 evolution. This framework focuses on two
approaches for H2 evolution via real water spilling and water reduction
half-reaction (or photo-reforming) over heterogeneous TiO2-based ma­
terials, as shown in Fig. 3 [30]. Firstly, the actual water splitting could
be achieved using TiO2-based semiconductors with sufficient potential
to split H2O directly into H2 and O2 (left-hand reaction, Fig. 3). Herein,
the protons (H+) are reduced by e− to generate H2 molecules (ECB < E0
(H2/H+)), accompanied by the H2 evolution, while H2O is oxidized by
h+ to create O2 (EVB > E0 (O2/H2O)). In principle, the stoichiometric
generation of H2 and O2 is 2:1 in a molecular ratio. Since the water-
splitting reaction is restricted by (a) the bandgap energy (theoretical
bandgap energy > 1.23 eV, or > 2.0 eV to meeting the thermodynamic
proposed. This idea barrier) [31], and (b) the conduction and valence
bands potential (required sufficient negative and positive for the water
reduction and oxidation half-reactions, respectively) [2]. Based on the
above requirements, the deposition of cocatalysts in TiO2 photocatalysis
has been recently worked as promoters to effectively accelerate the
surface reaction kinetics and serve as charge trap centres to forcefully
separate e− -h+ pairs under light irradiation, leading to enhance the H2
evolution. Evidently, the catalytic performance depends on the co­
catalysts. Hence, it is undoubtedly a great challenge to achieve overall
water splitting.
Another approach that combines half-reaction of water reduction
C. Xia et al. Fuel 307 (2022) 121745

and oxidation of chemical substrates is recently reported, namely water
reduction sacrificial half-reaction or catalytic reforming (rectangular
reaction, Fig. 3). In principle, the adding chemical substrates as sacri­
ficial reagents (electron donors or hole scavengers, denoted as R) would
be reacted with h+ to create CO2, H2O, intermediates, etc. Following, the
remaining e− simultaneously reduces H+ to H2 molecules.
3. The roles and architectural structures of cocatalysts in TiO2-
based materials
So far, many studies have been explored to tailor the cocatalysts in
semiconductor/cocatalyst composites [9,25]. A large number of archi­
tectural structures of cocatalysts have been proposed. In particular, Bai
et al. reported five general cocatalyst structures, including (a) reduction
cocatalysts, (b) oxidation cocatalyst, (c) reduction–oxidation cocatalyst,
(d) plasmonic metal/sensitizer-semiconductor-cocatalyst, and (e) plas­
monic metal/sensitizer-cocatalyst [25]. Recently, Li et al. proposed six
configurations of cocatalysts for selective photocatalytic CO2 reduction
[9]. They are including (a) semiconductor supported single reduction or
oxidation cocatalyst systems; (b) semiconductor-dual (reduction and
oxidation) cocatalyst systems; (c) plasmonic metal–semiconductor-
cocatalyst systems; (d) dye/quantum dots-semiconductor (irradiated or
unirradiated)-cocatalyst systems; (e) dye/quantum dots-cocatalyst sys­
tems; and (f) semiconductor-carbon/metallic bridge-cocatalysts or
semiconductor-cocatalysts with coated layers. This review proposes five
basic configurations of cocatalysts in TiO2-based materials tailored for
photocatalytic H2 evolution, as shown in Fig. 4.
For the first approach, TiO2 supported single reduction cocatalyst
have attracted large attention, as shown in Fig. 4a. As a result, many
photocatalysts have been developed, including Pt/TiO2 [32–35],
CuO1− x/TiO2 [32], Cu/TiO2 nanorods [36], CuO/TiO2 nanosheets [37],
CoSx/TiO2 [38], RuO2-TiO2 [39], NiS/TiO2 [40], Sn/TiO2 [41], NiO/
TiO2 nanofibers [42], Cu(OH)2/TiO2 [43], MoS2@TiO2 [44], plate-like
Co(OH)2/TiO2 nanosheets [45], Ni/TiO2 [46], Cu/TiO2 [46], Co/TiO2
[46,47], NiSe/TiO2 [48], and Ti3C2Tx/TiO2 [49]. To further enhance the
photocatalytic activity, a more complicated architectural structures,

Table 1
The photocatalytic performance of various cocatalysts-integrated TiO2.
Materials Cocatalyst decoration method Test condition Performance Improvement (*) Ref.
(mmol⋅h− 1⋅g− 1)
Pt/TiO2-001 Deposition–precipitation Catalyst, 15 mg; sacrificial agent, CH3OH; light source, 300 21.9 3 (TiO2-101) [108]
W Xe lamp
Pt1/def-TiO2 Adsorption followed by H2 Catalyst, 20 mg; sacrificial agent, CH3OH; light source, 300 52.72 78.5 (f-TiO2) [109]
treatment W Xe lamp
ME-TiO2@Ru Adsorption- Calcination Catalyst, 50 mg; sacrificial agent, CH3OH; light source, 300 7.2 34 (pure ME- [111]
W Xe lamp TiO2)
Ni-a/TiO2 Molten salt synthesis Catalyst, 50 mg; sacrificial agent, CH3OH; light source, 300 1.89 4 (Ni-np/TiO2) [174]
W Xe lamp
CuSACs/TiO2 Adsorption-SiO2 Wrap- Sacrificial agent, CH3OH; light source, 300 W Xe lamp 16.6 34 (pure TiO2) [122]
Calcination-Etching
Co-TiO2 Impregnation Catalyst, 100 mg; solvent, NaOH 1M; sacrificial agent, 1.682 12 (bare TiO2 [175]
CH3OH; light source, 300 W Xe lamp NSs)
Pt-Au/T Ligand-assissted reduction Catalyst, 10 mg; sacrificial agent, CH3OH; light source, 300 8.01 60 (Au/TiO2) [134]
W Xe lamp; temperature, 20 ◦ C
TiO2-Pd@Pt Hydrothermal-Solvothermal Catalyst, 15 mg; solvent,DI water; light source, 300 W Xe 0.60 8.2 (TiO2-Pt) [183]
lamp; time, 4 h
Ag@Ni/TiO2 Photodeposition Catalyst, 50 mg; sacrificial agent, lactic acid; light source, 2.93 5.4 (Ag/TiO2) [82]
365 nm LEDs (23.0 mW cm− 2)
MoS2/TiO2 Chemical vapor deposition Catalyst, 10 mg; sacrificial agent, CH3OH; light source, 300 4.3 36 (pure TiO2) [144]
W Xe lamp
MoS2/graphene/ Hydrothermal Catalyst, 80 mg; sacrificial agent, C2H5OH; light source, 2.07 39 (TiO2) [176]
TiO2 350 W Xe lamp
TiO2–NiCoS-PC High temperature sulfuration Catalyst, 20 mg; sacrificial agent , CH3OH; light source, 300 1.29 2.4 (commercial [148]
W Xe lamp P25)
CMS/THS Self-assembly Catalyst, 100 mg; sacrificial agent, TEOA; light source, 300 44.43 39 (THS) [149]
W Xe lamp
N-TiO2/g- Photochemicaldeposition Catalyst, 50 mg; sacrificial agent, TEOA; light source, 300 W 5.44 7.5 (N-TiO2/g- [156]
C3N4@NixP Xe lamp C3N4)
CdS@TiO2/Ni2P Impregnation followed by Catalyst, 10 mg; sacrificial agent, Na2S and Na2SO3; light 13.91 2.99 (CdS@TiO2) [157]
Na2H2PO2treatment source, 300 W Xe lamp with AM 1.5G filter
NiCoP(1 wt%)/TiO2 Absorption followed by calcination Catalyst, 20 mg; sacrificial reagent, CH3OH; light source, 1.54 13.6 (TiO2) [158]
300 W Xe lamp
CoOx/TiO2/Pt Template-assisted atomic layer Catalyst, 35 mg; sacrificial reagent, CH3OH; light source, 7.88 4.88 (pristine [57]
deposition 300 W Xe lamp; temperature, 25 ◦ C TiO2)
RuO2/TiO2/Pt-B Chemical reduction Catalyst, 50 mg; sacrificial reagent, CH3OH; light source, 6.13 1.56 (RuO2/ [170]
300 W Xe lamp TiO2/Pt)
CuO/TiO2 Hydrothermal Catalyst, 20 mg; sacrificial reagent, CH3OH; light source, 2.0 20 (pure TiO2) [37]
300 W Xe lamp; room temperature
Cu-TiO2 nanowire Hydrothermal Catalyst, 50 mg; sacrificial reagent, CH3OH; light source, 4 5.1 trace (TiO2) [177]
× 3 W UV LEDS (365 nm, 80.0 mW cm− 2)
Ti3C2Tx/TiO2 Impregnation Catalyst, 30 mg; sacrificial reagent, CH3OH; light source, 2.65 9 (TiO2) [49]
200 W Hg lamp (285–325 nm); temperature, 25 ◦ C
Ti3C2@TiO2@MoS2 Hydrothermal Catalyst, 10 mg; sacrificial reagent, TEOA; light source, 300 6.43 87.1 (TiO2) [178]
W Xe lamp with AM 1.5filter; temperature, 25 ◦ C
Ni(OH)2/TiO2 Precipitation Catalyst, 50 mg; sacrificial reagent, CH3OH; light source, 4 3.06 223 (TiO2) [179]
× 3 W UV LEDS (365 nm, 80.0 mW cm− 2)
Pt/black TiO2 Impregnation Catalyst, 100 mg; sacrificial agent, CH3OH; light source, 5.2 1.7 (pristine [180]
300 W Xe lamp; time, 5 h TiO2)
Pt/Black TiO2–xHx Photodeposition Catalyst, 100 mg; sacrificial agent, CH3OH; light source, AM 8.2 13.44 (pristine [181]
1.5 (100.0 mW cm− 2) TiO2)

*: Compared sample; ME: multi-edge.

3
C. Xia et al.
Fig. 2. Schematic representation of fundamentals photocatalytic reactions in
heterogeneous TiO2 semiconductor. Adapted with permission from Li et al. [9].
Copyright (2019) American Chemical Society.
Fig. 3. Schematic representation of fundamentals light-driven catalytic reac­
tion pathways by excitation of the heterogeneous TiO2-based materials: water
splitting (left-hand reaction), substrates oxidation (right-hand reaction), and
water reduction sacrificial half-reaction or photo-reforming (rectangular reac­
tion). Adapted with permission from Huang et al. [30], License No.
5096380530042. Copyright (2020) Elsevier B.V.
such as TiO2 supported binary, ternary reduction cocatalysts, has been
considered. Various effective photocatalysts have been reported, such as
MoxS@TiO2@Ti3C2 [50], bilayers Pt-Ni/TiO2 nanotubes [51], Pt/PtO
phase-juncted nanodots on TiO2 (0 0 1) plane [52], Pd-IrOx/TiO2 [53],
and CuS-NiS/TiO2 [54].
Since the above approach only considers promoting the transferring
of e− between TiO2 and reduction cocatalyst, which might limit due to
the low efficiency of the hole generation and accumulation by TiO2. In
the second approach, TiO2 supported dual reduction–oxidation co­
catalysts are successfully proposed and fabricated with enhanced
4
Fuel 307 (2022) 121745
significance the photocatalytic H2 evolution, as shown in Fig. 4b. In
typical, many candidates, including TiO2-Co3O4-Pt [55], Cu2O/TiO2/
Bi2O3 [56], CoOx/TiO2/Pt [57], RuO2@TiO2@Pt hollow spheres [58],
Ni(OH)2-Ti(IV)/TiO2 [59], CuO/Al2O3/TiO2 [60],O-Co3O4/TiO2 [61],
Co-Ni/TiO2 [62], MOx@TiO2@Pt [63], CoOx/TiO2/CdS [64], and 1 T-
MoS2/P25/NiOx [65], have been reported to demonstrate the advances
on improving the efficiency of H2 evolution.
In another approach, enormous efforts have been made recently to­
ward exploring TiO2 supported plasmonic metal cocatalyst, as shown in
Fig. 4c. This rapid progress in enhancing H2 evolution by using noble
metal nanoparticles, such as Au, Ag, etc., as cocatalysts for providing
two prominent characteristics: a Schottky junction and localized surface
plasmonic resonance (LSPR) [66]. Accordingly, various plasmonic co­
catalysts have been explored as alternatives, such as Au/TiO2 [67], Au/
TiO2-Pt [68], Au@TiO2@RuO2 [69], TiO2-Fe2O3/Ag [70].
In the fourth approach, TiO2 supported dye cocatalyst are reported,
as shown in Fig. 4c. Yan et al. prepared Eosin Y dye-sensitized Ni(OH)2/
TiO2 for efficient light-driven H2 evolution [71]. The H2 evolution rate
in the presence of Ni(OH)2 is 90 times higher than that in the absence of
Ni(OH)2 under the same reaction conditions. The enhanced activity is
attributed to the efficient separation of e− -h+ pairs.
Last but not least, TiO2 supported carbon bridge cocatalyst, such as
V-TiO2/ reduced graphene oxide (rGO) [72], graphite oxide (GO)/TiO2,
GO/Pt/TiO2 [73], TiO2/Pt/rGO [74], rGO/TiO2 nanofiber [75], rGO/
TiO2/Pt [76], MoSx-rGO/TiO2 [77], MoS2/P25/graphene aerogel [78],
have been reported.
Notably, the semiconductors in these five configurations could be
replaced by the p-n and Z-scheme, S-scheme heterojunctions, or
homojunction. Meng et al. reported a direct Z-scheme TiO2/CdS binary
hierarchical photocatalyst for photocatalytic H2 evolution [79]. Unlike
conventional heterojunction-type (Fig. 5a), both TiO2 and CdS in direct
Z-scheme could generate e− -h+ pairs under light irradiation (Fig. 5b).
Hence, direct Z-scheme could maintain strong e− reducibility of the CdS
conduction band (CB) and strong h+ oxidizability of TiO2 valence band
(VB), resulting in fundamentally improving charge separation and
migration from TiO2 nanosheets to CdS nanoparticles.
The recent literature by Bai et al. are further discussed the integra­
tion of reduction cocatalysts, as schematically illustrated in Fig. 6 [25].
In typical, Fig. 6a depicts the first model, which is presented based on
the single reduction cocatalyst (TiO2 supported cocatalyst I). A few
recent publications are available, such as Pt/TiO2 [32], CuO1− x/TiO2
[32], CoSx/TiO2 [38]. To further promote photocatalytic activity, a
straightforward concept, namely TiO2, supported binary reduction co­
catalysts, has been considered. In the second model (Fig. 6b), TiO2
supported both cocatalysts I/II, in which cocatalysts are contacted and
loaded on TiO2. Both cocatalysts I/II, which are exposed to reduction
reactions, have similar functions. At the initial stage, MoxS@Ti­
O2@Ti3C2 [50], bilayers Pt/Ni/TiO2 nanotubes [51], Pd-IrOx/TiO2
[53], are reported with potential active for H2 evolution. Certainly,
there is no need to require both cocatalysts in direct contact with TiO2.
As schematically shown in Fig. 6c, cocatalyst II is selectively loaded on
cocatalyst I to form a supporting structure. Like the TiO2 supported
cocatalysts I/II, both cocatalysts I-II in TiO2 supported cocatalysts I-II
are also exposed to reduction reactions and play similar functions. To
learn this concept, Ren et al. reported Pt/PtO hybrid nanodots on hier­
archically porous TiO2 to greatly enhance the light-driven catalytic H2
evolution [52]. In another approach, core/shell-structured nano­
particles (with a noble metal or metal oxide cocatalyst I (Ni, Ag, Au,
CuO, etc.) core and cocatalyst II (NiO, Ni, CdS, etc.) shell) are proposed
as a new type of cocatalyst for light-driven catalytic H2 evolution
(Fig. 6d). In this concept, the cocatalyst II shell works as a protection
layer to suppress the re-formation of H2O from H2 and O2 on cocatalyst I
(core), resulting in promoting the forward reaction (2 H2O → 2 H2 + O2)
[80]. The validity of the above idea is successfully demonstrated via
many TiO2 supported cocatalysts I@II core–shell candidates, including
Ni@NiO/TiO2 [81], Ag@Ni/TiO2 [82], Au@CdS/TiO2 nanofibers [83],
C. Xia et al. Fuel 307 (2022) 121745

Fig. 4. Schematic illustration for five configurations of cocatalysts in TiO2-based materials: (a) TiO2 supported single reduction cocatalyst; (b) TiO2 supported dual
reduction–oxidation cocatalysts; (c) TiO2 supported plasmonic metal cocatalyst; (d) TiO2 supported dye cocatalyst; and (e) TiO2 supported carbon bridge cocatalysts.
Adapted with permission from Li et al. [9]. Copyright (2019) American Chemical Society.

Fig. 5. Schematic illustration for two mechanisms for explaining the charge separation: (a) conventional heterojunction-type and (b) direct Z-scheme. Printed with
permission from Meng et al. [79], License No. 5096381005254. Copyright (2017) Elsevier B.V.

CuO@NiO/TiO2 [84]. To further enhance the separation and transfer of
photogenerated charge carriers, TiO2 supported conductor-cocatalyst, in
which a conductor is used as a charging bridge between TiO2-cocatalyst,
is proposed, as schematically illustrated in Fig. 6e. For this concept,
Spanu et al. selectively placed Pt-WO3 by sequential W and Pt sputtering
at the top of TiO2 nanotubes [85]. They reported that the swift electron
transfer towards Pt for H2 evolution through WO3 plays an excellent role
and positively affects photocatalytic activity yield.
From the discussion above, we mainly discuss the single and binary
reduction cocatalysts. It notes that more complicated architectural
structures have been reported for cocatalysts (e.g., ternary cocatalysts)
in the literature. For example, Li et al. designed IrO2/SiC-NiOx/TiO2
four-component composite materials, which could enhance significant
catalytic performance [86]. More recently, Caudillo-Flores et al. re­
ported binary PtPd cocatalysts supported on Nb-doped TiO2 support
[87].
To summarize, significant progress to tailor the TiO2 supported
active sites of cocatalysts has been devoted. A large number of

5
C. Xia et al.
Fig. 6. Schematic diagram illustrating the surfaces and interfaces functions of
TiO2 and their reduction cocatalysts under light-irradiation: (a) TiO2 supported
cocatalyst I; (b) TiO2 supported cocatalysts I/II; (c) TiO2 supported cocatalysts
I-II; (d) TiO2 supported cocatalysts I@II core–shell; and (e) TiO2 supported
conductor-cocatalyst. Adapted with permission from Bai et al. [25]. Copyright
(2016) Royal Society of Chemistry.
architectural structures of TiO2 supported cocatalysts have been pro­
posed. The location of the modifiers (cocatalysts, conductors) on TiO2 is
crucial and very sensitive to efficient separation and transfer of photo­
generated charge carriers, resulting in further enhance the performance
of H2 evolution.
4. Cutting-edge development of cocatalysts-integrated TiO2 for
H2 evolution
The last decades have been witnessed numerous attempts devoted to
exploring the appropriate cocatalysts to boost the H2 evolution of TiO2
photocatalysts. Hitherto, the frontier investigations could be focused on
four types of cutting-edge development of cocatalysts: (a) metal (noble
metal, non-noble metal, bimetallic); (b) metal sulfides and metal phos­
phides; (c) 2D-MXenes; and (d) dual materials-based cocatalysts. The
following subsections will provide the state-of-the-art development of
each type of material in detail.
4.1. Metal-based cocatalysts
4.1.1. Noble metals cocatalysts
Noble cocatalysts have proven their superior capability prompting
the photocatalytic H2 evolution of TiO2 over the past decades. It has
been found that noble metal cocatalysts-decorated TiO2-based photo­
catalysts witness the enhancement in the electron migration from the
host material to metal cocatalyst, leading to enhance electron-hole
separation [9,88–91]. The nature of the noble metals-based active site
is appropriate for reducing reaction in terms of low free energy of H2
adsorption, which is close to the optimal value of zero (|ΔGH*|~0)
[92–94]. Various noble metal cocatalysts/TiO2 composite is efficient for
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Fuel 307 (2022) 121745
the generation of H2 from the water like Pt, Au, Ag, Rh [63,95–98]. In
this context, the size of metal nanoparticles remarkably impacts the
charge separation and catalytic performance efficiencies [99–101]. For
instance, Wang et al. employed ab initio molecular dynamics and hybrid
DFT to substantiate the effect of Pt’s particle size toward the photo­
catalytic H2 generation. It was found that the small size of Pt particles
prompts electron transportation from TiO2 to Pt cocatalyst, whereas a
larger size of Pt particles is beneficial for catalytic H2 evolution. As a
result, the Pt particles of approximately 1 nm could generate the highest
photocatalytic H2 evolution [33]. Dessal et al. experimentally investi­
gated the effect of Pt particle size toward the H2 evolution reaction over
TiO2 photocatalyst [99]. It turns out that the Pt clusters possessing the
particle size of ~ 1 nm and an appropriate weight percentage (e.g.,
0.2%) exhibited an optimal photocatalytic activity with the H2 evolution
rate of 170 mmol⋅g− 1⋅h− 1.
It is noteworthy that rare and expensive properties of noble-metal
cocatalysts have been considered critical obstacles limiting their usage
in the photocatalytic H2 evolution. The recent explosive growth in the
research of single-atom catalysts (SACs)-decorated TiO2 photocatalysts
has opened a novel avenue to prepare extraordinary material to boost
the photocatalytic H2 evolution. The employment of noble metal single-
atom cocatalysts offers numerous features as: (i) unsaturated coordina­
tion configurations of metal atoms assist in boosting the reaction kinetic.
In this context, the incorporation of metalSACS into the host TiO2 pho­
tocatalyst causes significant modifications of the electronic structure of
the support via coordination with atoms of the support. Such interaction
promotes the charge transfer, inhibits the electron-hole recombination
and prompts the activation of reactants; (ii) the metalSACs/photocatalyst
configuration could reduce the amount of employed noble metals while
achieving 100% atom utilization for the photocatalytic reactions
[102–107]. Such outstanding properties of noble metal-decorated TiO2
disclosed a potential platform to synthesis superior TiO2-based photo­
catalysts for H2 generation. Indeed, numerous efforts have been devoted
to developing high-performance noble metalSACs cocatalyst/TiO2 over
the past years. Pt-based single atom cocatalysts have received significant
attention. For instance, Wei et al. reported the preparation of PtSAC
incorporated facet TiO2-[0 0 1], which considerably facilitates the H2
evolution reaction compared to Pt/TiO2-101 [108]. Two essential fac­
tors could be pointed out as: (i) promote the charge separation of high
energy-photogenerated electrons within the [0 0 1] facet and (ii) offer
robust active sites for the H2 generation catalysts. For those reasons, the
PtSACs cocatalyst significantly enhances the photocatalytic performance
of water conversion into H2. Very recently, Chen et al. introduced an
outstanding investigation on the preparation of PtSACs on defective TiO2
[109]. This photosystem was prepared via a two-step synthesis in which
Pt precursor (i.e., H2PtCl6) was adsorbed onto sodium titanate-parent
material before being treated under the H2 agent (i.e., H2/Ar atmo­
sphere) shown in Fig. 7a. It is noteworthy that such preparation resulted
in incorporating PtSACs and the formation of disorder TiO2 layer and
(Fig. 7b-c). It turns out that the PtSACs encourages the formation of the
defective TiO2 with the existence of surface oxygen vacancies and
introduce Pt-O-Ti3+ sites, which steer the migration of photogenerated
charge carriers from Ti3+ to Pt atoms, leading to enhance the charge
separation and promoting the H2 generation reaction. As a result, the
photocatalytic performance of the presented material (denoted as Pt/
def-TiO2) considerably outperformed the samples f-TiO2 and Pt NPs/f-
TiO2 by the factors of 78.5 and 11.8, respectively, as shown in Fig. 7d-e
[109]. In another investigation, Hejazi et al. conducted incorporating
single Pt atoms on TiO2 anatase, which exhibited a superior improve­
ment in photocatalytic H2 evolution [110]. It was found that defective
surface centers (i.e., Ti3+) produced through an H2-conducted reduction
play a critical role in forming and stabilizing PtSACs. Such unique
incorporation significantly promotes photocatalytic performance. Such
pieces of evidence signify the essential role of defective surface centers
in forming PtSACs to boost the photocatalytic performance of TiO2
catalyst.
C. Xia et al.
Fig. 7. a) The diagram illustrates the process of preparation, b) HRTEM image, c) AC HAADFSTEM enlarged image, d) FT-EXAFS spectra, e) The photocatalytic H2
evolution rate of Pt1/def-TiO2 catalyst. Reprinted with permission from Chen et al. [109]. Copyright (2019) Angewandte Chemie International Edition.
In addition to single Pt atoms, RuSACs-based cocatalysts have ach­
ieved attention as a potential candidate for the TiO2 photocatalyst. Thus,
Zang et al. performed an excellent investigation to synthesize and pro­
bed the generation of Ru atoms on multi-edged TiO2 nanospheres
(denoted as ME-TiO2@Ru) for photocatalytic H2 generation [111]. The
ME-TiO2@Ru materials were obtained through a two-step synthesis, as
shown in Fig. 8a. In this case, Ru atoms incorporated into ME-TiO2 under
the Ru-O bonding, as shown in Fig. 8b. Interestingly, in this circum­
stance, photo-induced electrons transfer to isolated Ru atoms to undergo
photocatalytic H2 evolution. Indeed, the in situ x-ray absorption spec­
troscopy proved the migration of photogenerated electrons to Ru atoms
under irradiation, as shown in Fig. 8c. The intensity of the white-line
peak localized at 22.144 eV reduced upon irradiation, indicating that
Ru atoms are reduced upon illumination. In other words, the photo-
induced electrons transfer from ME-TiO2 to Ru atoms. Such a trans­
portation manner significantly promotes the lifetime of photo-induced
charge carriers, leading to boost photocatalytic H2 evolution (Fig. 8d).
Indeed, the photocatalytic H2 evolution was 323.2 µmol⋅h− 1, 34 times
higher than that of pure ME-TiO2 (Fig. 8e).
Furthermore, the DFT studies unveil that ME-TiO2@Ru offers an
appropriate platform in which the photogenerated electrons could
feasibly migrate from the ME-TiO2 to Ru atoms. Similarly, Li et al.
carried out the synthesis of RuSACs/TiO2 nanosheets [112]. The
7
Fuel 307 (2022) 121745
incorporation of Ru atoms enhances the light absorption and induces
oxygen vacancies to promote the charge separation and provide efficient
active centers to facilitate the photoreduction reactions. Consequently,
the amount of H2 produced over RuSACs/TiO2 nanosheets is considerably
higher than that of TiO2 nanosheets.
To this end, it can be said that noble metal single atoms remarkably
increase the solar-driven H2 evolution over TiO2 photocatalysts. The
existence of defective surface centers is essential for forming and sta­
bilizing single metal atoms through coordination. Such intimate inter­
action could be considered the root of the enhancement of light
absorption and charge separation while offering robust active sites for
the photocatalytic reaction.
4.1.2. Non-noble metal cocatalysts
The use of non-noble metal cocatalysts has attracted increasing
attention in recent decades. The low cost and abundance have been
considered the primary forces driving the exploration of novel non-
noble metal cocatalysts for photocatalytic H2 evolution [113]. Hith­
erto, numerous non-noble metal cocatalysts have been introduced as
efficient active sites as integrated on the TiO2 photocatalysts [114,115].
Transition metals (e.g., Ni, Cu, and Co)-based cocatalysts have been
considered the potential materials to promote the photocatalytic activity
TiO2.
C. Xia et al.
Fig. 8. a) Stages of synthesis ME-TiO2 @ Ru. Step 1: Ru is attached to the surface of ME-PT. Step 2: ME-PT @ Ru convert to ME-TiO2 @ Ru through pyrolysis, b) TEM
images, c) HAADF-STEM and elemental mapping images, d) XAFS spectra of ME-TiO2@Ru, e) Photocatalytic activity of the samples. Reprinted with permission from
Zhang et al. [111]. Copyright (2020) Science.
Ni-based cocatalysts have emerged as the bright candidate as the
cocatalysts for photocatalytic H2 evolution owing to their capability to
promote photocatalytic H2 evolution [27,116–119]. The DFT calcula­
tion over the Ni/TiO2 system unveils that Nin clusters decorated on TiO2
surface considerably lower the Gibbs energy of H2 adsorption compared
to clean TiO2 surface. In other words, Nin clusters are able to enhance
charge separation and promote the H2 evolution reaction [120]. Un­
doubtedly, controlling the size and interaction manner of Ni species on
the TiO2 support crucially drive to the H2 achievement. In this circum­
stance, the development of NiSACs/TiO2 photocatalysts has appeared as
an essential issue attracting considerable attention. In a recent study,
Xiao et al. prepared the NiSACs/TiO2 photosystem under the assistance of
the molten salts (e.g., the mixture of KCl and LiCl), as shown in Fig. 9a
[121]. It is noteworthy that the employment of molten salts possessing
an intense polarization induces a heavy modification on the TiO2 surface
8
Fuel 307 (2022) 121745
that is beneficial for the deposition of Ni atoms through Ni-O bonds, as
shown in Fig. 9b-d. Moreover, this synthetic approach also promotes the
generation of surface oxygen vacancies. The synergetic effect of those
features results in the efficient photocatalytic performance of NiSACs/
TiO2 photocatalysts (denoted as Ni-a/TiO2), which is comparable to Pt/
TiO2 as displayed in Fig. 9e. The DFT calculations suggest that obtained
Ni-a/TiO2 photocatalyst provides an appropriate free Gibbs energy for
the H2 evolution reaction explaining the high H2 achievement of Ni-a/
TiO2. This synthetic method has disclosed a very bright future to prepare
robust TiO2-based photocatalysts, containing both strong visible light
absorption and efficient charge separation.
The use of Cu and Co-derived cocatalysts has been considered as an
alternative candidate to enhance the photocatalytic activity of TiO2.
Similar to Ni-based cocatalysts, tailoring the size and states of Cu and Co
species has been a high priority. Indeed, the recently emerged efforts
C. Xia et al.
Fig. 9. a) Stages to the synthesis of Ni cocatalyst atomic on TiO2 nanoparticles via Molten Salt Mediated, b) AC-STEM dark-field image, c) X-ray energy-dispersive
spectroscopy, and d) EXAFS spectra of Ni/TiO2, e) H2 evolution performance of different samples. Reprinted with permission from Xiao et al. [121]. Copyright (2020)
Angewandte Chemie.
have been devoted to preparing atomic Cu and Co atoms on the TiO2
surface. For instance, Lee et al. offered an extraordinary strategy to
prepare Cu single-atom/TiO2 (CuSACs/TiO2), as shown in Fig. 10a-c
[122]. The EXAFS spectra (Fig. 10c) reveal the existence of Cu–O and
Cu-Ti bonding, explaining the decoration of Cu atoms on the TiO2 sur­
face. Such the presented manner resulted in improved photocatalytic
activity toward H2 evolution, as displayed in Fig. 10d. Indeed, the
amount of produced H2 was found to be significantly higher than those
of other metal cocatalysts (e.g., Co, Fe, Ni, and Rh). It was found that the
valence state of Cu atoms changed by photogenerated electrons causes
the lattice distortion of neighboring TiO2, benefiting the photocatalytic
performance (Fig. 10e). Very recently, Wu et al. provided the feasible
pathway for the atomic incorporation of Co onto the TiO2 nanosheets
[123]. The existence of Co atoms thus considerably promotes the charge
separation and function as actives sites driving the photocatalytic H2
evolution.
4.1.3. Bimetallic cocatalysts
The usage of bimetallic-based cocatalysts for the photocatalytic H2
evolution has garnered considerable attention because of: i) bimetallic-
derived materials possessing an appropriate work function could
enhance the charge separation compared to the mono-metal
9
Fuel 307 (2022) 121745
counterparts; ii) the Gibbs energy of H2 adsorption could be lowered
over bimetallic cocatalysts promoting the photocatalytic reduction, iii)
the use of bimetallic could enhance the sunlight utilization rooted in the
surface plasmonic resonance (SPR) effect, which also generate an
intense electric field and iv) the combination of metals could limit the
employment of precious metals leading to reduce the evolution cost
[124–126]. The last decades have been witnessed numerous efforts
devoted to exploring bimetallic systems-integrated TiO2. Thus, bime­
tallic cocatalysts (e.g., Pt-Cu, Ni-Cu, Pd-Au, Ni-Pd, Au-Pt, Au-Pd, Pt-Pd,
etc.) have been demonstrated to be the effective active sites for H2
evolution [127–133]. It has been found that the particle size, metal
composition, and deposit configuration are critical issues impacting the
efficiency of active bimetallic centers. Cutting-edge research of bime­
tallic cocatalysts has been exhibited that the Pt-contained bimetallic
systems offered the potential platform for photocatalytic H2 evolution.
Indeed, Cheng et al. reported the decoration of Pt-Au alloy clusters on
the TiO2, exhibiting an outstanding photocatalytic H2 evolution [134].
In this situation, the existence of Pt-Au alloy clusters provides an
appropriate scaffold for the adsorption of H2. The produced H2 at the
optimum condition was significantly higher than those of Pt and Au
mono-cocatalysts. In another investigation, Shahvaranfard et al. pre­
pared PtCu nanoalloy as an efficient cocatalysts for the TiO2 in which the
C. Xia et al.
Fig. 10. a) Diagram illustrating the single-atom synthesis of Cu/TiO2 photocatalysts by wrap–bake–peel process, b) EDS analysis in STEM mode, and c) The Ti K edge
spectrum in EXAFS analysis of Cu/TiO2, d) Comparison of photocatalytic activity for cocatalyst metal atoms, e) The photoactivation process of Cu/TiO2. Reprinted
with permission from Lee et al. [122]. Copyright (2019) Nature Springer.
presence of Cu on Pt promotes the charge separation and offers active
centers for H2 recombination [127]. In a very recent theoretical inves­
tigation, Wang et al. reported that Pt-Rh and Pt-Cu bimetallic cocatalysts
could function as robust cocatalysts to facilitate photocatalytic H2 evo­
lution [135]. According to the study, Rh and Cu atoms localized at the
nanoalloy-TiO2 interfacial contact provide an excellent electron-transfer
medium, which is beneficial for migrating photogenerated electrons
from the TiO2 to the alloy cocatalysts, as shown in Fig. 11a-d. Further­
more, the configurations of Pt-Rh and Pt-Cu lower the Gibb energy of H2
adsorption (i.e., ΔGH ~ 0) and H-H coupling barrier, which are very
beneficial for the photocatalytic reaction. Such pieces of evidence imply
a strong capability of Pt-based bimetallic toward the H2 evolution re­
action. The future could be witnessed the exploration of robust mate­
rials, especially Pt-Cu and Pt-Rh cocatalysts, significantly enhance the
photocatalytic achievement of TiO2.
In addition to Pt-based bimetallic, Ni-derived bimetallic systems
have been attracted attention [136]. In such an investigation, Spanu
introduced the formation of Ni-Cu cocatalysts onto the TiO2. Comparing
the chemical oxidation states of Cu and Ni species before and under UV
irradiation, the authors prove that the bimetallic species of Cu and Ni are
formed during the illumination from their oxides or hydroxides through
a dissolution and redeposition process, as shown in Fig. 11e-h. Conse­
quently, the as-generated NiCu bimetallic cocatalysts are considered the
10
Fuel 307 (2022) 121745
primary factor is driving the photocatalytic H2 evolution reaction. This
study offers an insightful description of the behavior of metal species,
which can assist in tailoring efficient bimetallic-derived non-noble
metals.
In 2015, Bai et al. reported an excellent core–shell cocatalyst
achieving from Pd@Pt quasi-core–shell [183]. It turns out that this type
of cocatalyst configuration improves the charge separation-enhanced
interfacial charge polarization, H2O adsorption-induced increase of
electron density, and lattice strain. It can be said that core–shell bime­
tallic cocatalysts provide a potential platform to tailor robust cocatalyst.
Very recently, Gao et al. tailored core@shell nanoparticles composed of
Ag-core and Ni-shell, resulting in an efficient cocatalyst as integrated on
the TiO2 photocatalyst [82]. Such cocatalyst configuration considerably
enhances the charge separation and surface chemical reaction compared
to the Ag-monometal cocatalyst. Thus, the photocatalytic H2 evolution
over Ag@Ni/TiO2 was found to be 5.4 times higher than that of Ag-TiO2.
4.2. Metal sulfides and metal phosphides-based cocatalysts
4.2.1. Metal sulfides
In 2008, Zong et al. introduced the first employment of two-
dimensional (2D) molybdenum disulfide as a cocatalyst for photo­
catalytic H2 evolution, disclosing a branch novel pathway for the
C. Xia et al.
development of metal sulfide-based cocatalysts [137]. Thus, the past
decades have been witnessed the discovery of numerous metal sulfide
materials, exhibiting the capability to promote the H2 evolution reac­
tion. 2D MoS2 cocatalysts have been considered as the most attractive
candidate to promote charge separation and H2 evolution reaction
rooted in the unique features as: (i) the MoS2 edge offers the active
centers possessing a low Gibb free energy of H2 adsorption, which is near
the zero value and high conductivity and (ii) the 2D MoS2 catalyst can
provide abundant of active sites for the catalytic reaction due to its high
11
Fuel 307 (2022) 121745
Fig. 11. Structures and IET energies for Pt7Rh6/
TiO2(1 0 1) (a), Pt7Cu6/TiO2(1 0 1) (b), Pt7Ir6/
TiO2(1 0 1) (c), Cu7Pt6/TiO2(1 0 1) (d), Reprinted
with permission from Wang and Gong [135].
Copyright (2021) Nature Communications, XAS
spectra of 5Ni5Cu-TiO2 under UV light illumination
for Cu K-edge (e) and Ni K-edge (f), Operando XAS
measurements of 5Ni5Cu-TiO2 for determining Cu
(g) and Ni (h) phase composition. Reprinted with
permission from Spanu et al. [136]. Copyright
(2020) ACS Catalysis.
exposed ration of atoms [138–143]. For these reasons, the integration of
MoS2 on the TiO2 photocatalysts has emerged as a promising tactic to
facilitate H2 evolution. For example, He et al. tailor the decoration of 2D
MoS2 on the TiO2 via edge-interfacial contact in which MoS2 nanosheets
were bound to the TiO2 at the edge position, as shown in Fig. 12a [144].
This interfacial manner resulted in a heterostructure with strong
electron-hole separation while providing the appropriate active sites for
the chemical reaction (Fig. 12b-c). As a result, the amount of photo­
catalytic H2 evolution was 36 times higher than that of pure TiO2
C. Xia et al.
Fig. 12. a) TEM image of TiO2/MoS2(E)3%, b) Photoluminescence intensity of samples, c) Rate of H2 evolution of TiO2, TiO2/MoS2(E)3% and TiO2/MoS2(B)3%, d)
Mechanism of electron transport under the UV light irradiation on TiO2/MoS2 (E). Reprinted with permission from He et al. [144]. Copyright (2016) Advanced
Energy Materials.
(Fig. 12d). Similarly, Wang et al. prepared ultrathin MoS2/yolk-shell
TiO2 heterostructure, exhibiting an excellent photocatalytic activity
[145]. Indeed, the outstanding performance is rooted in the intimate
TiO2-MoS2 interfacial contact through the Ti-S chemical linkage and the
exposure of rich-edge MoS2 ultrathin. Such interaction benefits the
charge transport and photocatalytic reduction, leading to prompt H2
evolution. Very recently, Ou et al. decorated the MoS2 on the black TiO2
nanotube, also witnessing an enhancement in the H2 evolution perfor­
mance [146].
In addition to MoS2, other transition metal sulfides (e.g., NiS, NiWSx,
CuxS) have emerged as alternative candidates to be employed as co­
catalysts for photo-induced H2 generation [22,40,54,147]. Recent
outstanding studies have pointed out that bimetallic sulfide could
emerge as an interesting candidate functioning the role of a cocatalyst
for TiO2. Indeed, Gao et al. reported that NiCoS-decorated TiO2 could
result in an excellent photocatalytic activity, 64.5 times higher than that
of pristine TiO2 [148]. Also, Niu et al. conducted the preparation of a
Co1.62Mo6S8-TiO2 heterojunction [149]. It has been found that the
Co1.62Mo6S8 cocatalyst decorated on the TiO2 support induces a superior
photocatalytic activity for H2 generation compared to the mono-metal
sulfide counterpart. Such outstanding achievement is rooted in the sig­
nificant enhancement of charge separation caused by the existence of
Co1.62Mo6S8 cocatalyst. In other words, this bimetallic metal sulfide
could offer a platform to promote the extraction of the photogenerated
electrons and proper active sites to produce H2. This investigation can
disclose a novel approach to design various bimetal sulfide cocatalyst to
promote the photocatalytic H2 evolution of the TiO2-based materials.
4.2.2. Metal phosphides
Metal phosphides have been demonstrated to be efficient materials
to carry out the reduction of water since the pioneer preparation of FeP
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Fuel 307 (2022) 121745
and Ni2P catalysts [150,151]. Numerous investigations have been
pointed out that metal phosphides possess unique properties that can be
utilized as robust photocatalytic H2 evolution: i) provide robust active
centers; ii) enhance the charge separation; iii) reduce overpotential, and
iv) enhance the photostability [152–155]. Unsurprisingly, the integra­
tion of metal phosphides-cocatalysts onto the TiO2 photocatalyst has
attracted the intention. Ni2P cocatalyst has been considered as the most
potential candidate to couple to TiO2-derived photocatalysts. Wu et al.
employed NixP as a cocatalyst to enhance the photocatalytic activity of
g-C3N4/N-TiO2 heterostructure [156]. The existence of NixP on the TiO2
significantly promotes the extraction of photo-induced electrons in TiO2,
leading to enhance charge separation. Therefore, the photocatalytic
activity for H2 evolution was 7.5 times higher than that of g-C3N4/N-
TiO2. Similarly, Wu et al. reported Ni2P/TiO2/CdS composite synthesis
in which Ni2P remarkably steers the separation of photo-induced charge
carriers and courage the photocatalytic reaction [157]. In another
investigation, Song et al. decorated Ni2P, NiCoP, and FeP onto the TiO2
photocatalysts [158]. It was found that the NiCoP/TiO2 heterostructure
delivered the highest photoactivity for H2 evolution. Such improved
catalytic performance is rooted in the enhancement of charge separation
and the reduced ability of the attached metal phosphide cocatalysts. It
can be said that the integration of metal phosphides-based cocatalysts
onto the TiO2 is still limited, which is originated from the restriction of
preparation method, requiring high pressure and temperature associ­
ated with extremely PH3 toxic gas. Such obstacles require more attempts
to tackle to produce an efficient metal phosphide/TiO2 photosystem for
the photocatalytic evolution of H2.
4.3. Two-dimensional (2D) MXenes
Two-dimensional early transition metal carbides (i.e., MXenes) have
C. Xia et al.
received significant attention as a potential class of material for energy
conversion applications [159–161]. In the field of photocatalyst,
MXenes, which have the general formula of Mn+1XnTx where M, X, and T
represent early transition metals (e.g., Sc, Ti, V, and Nb), carbon or ni­
trogen and functional groups (e.g., –OH, -O and –F), respectively, have
emerged as a great candidate as a superior cocatalyst for the water
reduction reaction [162]. Thus, MXenes-derived materials possess
unique properties turning out to be an excellent platform for catalytic H2
generation. Indeed, MXenes-based materials can offer a surface with an
appropriate Gibbs energy of H2 adsorption, high electrical conductivity,
hydrophilic surface, and large surface area [163–167]. Consequently,
coupling MXenes to TiO2 photocatalyst have attracted an increasing
concern over the past years.
It has been seen that the Ti3C2Tx MXene has been considered as the
most potential material coupled to the TiO2 photocatalysts to produce
H2. Numerous attempts have been devoted to exploring robust Ti3C2/
Fig. 13. a) Photocatalytic mechanism of Ti3C2Tx/TiO2 composite for photocatalytic H2 evolution, b) TEM and c) HRTEM images of 5-TC/TO, d) Comparison of
transient photocurrent between TiO2, 5-MTC / TO and 5-TC / TO, e) H2 evolution rate of 5-TC/TO and 5-MTC/TO. Reprinted with permission from Su et al. [49].
Copyright (2019) ACS Applied Energy Materials.
13
Fuel 307 (2022) 121745
TiO2 composites [98,168,169]. Recent movements have been shown
that tailoring the Ti3C2-TiO2 interfacial contact significantly prompts
the separation of photogenerated electrons. For example, Su et al. syn­
thesized Ti3C2Tx/TiO2 composite in which the Ti3C2Tx is existed in the
form of the monolayer, leading to the intensity of the interfacial contact
between Ti3C2Tx and TiO2 nanoparticles, as shown in Fig. 13a-c [49].
Such intimate contact considerably steers the electron migration to the
MXene Ti3C2Tx, causing a strong improvement in charge separation
(Fig. 13d). As a result, the obtained Ti3C2Tx/TiO2 composite (denoted as
5-TC/TO) prompts the photocatalytic activity toward H2 evolution in
comparison to multilayer Ti3C2Tx/TiO2 composite (denoted as 5-MTC/
TO) by a factor of 2.5, as displayed in Fig. 13e. This demonstration
implies that the utilization of MXenes-based cocatalysts could offer a
great alternative candidate to boost the photocatalytic performance of
TiO2. Engineering the interfacial manner and the structure of MXene,
TiO2 function the crucial parameters, which can enhance both light
C. Xia et al. Fuel 307 (2022) 121745

absorption and charge migration from TiO2 to MXenes. Oxygen oxidation cocatalysts, respectively, on the TiO2 nanotubes [57]. Such
vacancies-rich TiO2/MXenes and facet TiO2/MXenes are worth photo­ Pt/TiO2/CoOx proved an efficient photocatalytic H2 evolution. Simi­
catalytic systems, which could provide outstanding photocatalytic H2 larly, Li et al. recently introduced black Pt/TiO2/RuO2 photosystem,
generation platforms. exhibiting a strong capability to promote the charge separation, which is
originated by the co-existence of Pt and RuO2 cocatalysts, respectively
[170]. Very recently, Lin et al. prepared MoS2/TiO2/NiOx hetero­
4.4. Dual cocatalysts
structure proving a significant enhancement in the photocatalytic ac­
tivity [65]. Indeed, the amount of produced H2 was found to be
The utilization of dual cocatalysts has drawn significant attention in
comparable to the Pt-TiO2 photosystem.
recent attempts to boost the photocatalytic performance of TiO2. Syn­
In addition to spatial cocatalysts, the preparation of composite-based
ergetic effects of components could remarkably facilitate the charge
cocatalysts has garnered increasing attention recently. For example, Pt/
separation and catalytic reaction properties [15]. In this context, a TiO2
Cu1-x composite cocatalyst integrated on the TiO2 photocatalyst proved
photosystem containing spatial cocatalysts (i.e., reduction and oxidation
the considerable enhancement toward the photocatalytic H2 evolution
cocatalysts) and composite-based cocatalysts have been explored and
[171]. In this case, CuO1-x nanoparticles located between TiO2 and Pt
are discussed in detail.
could promote the charge separation, performance of Pt and restrict the
The decoration of two separated cocatalysts onto the TiO2 surface
back reaction. In the same manner, Ni3N-Auc-TiO2 photocatalyst was
aims to extract photogenerated electrons and holes simultaneously.
also prepared and outperformed the Pt/TiO2 catalyst, which is rooted in
Therefore, reduction and oxidation cocatalysts are required to have
the promoted charge separation and reaction kinetic-caused Ni3N-Auc
existed on the TiO2 photocatalysts. The charge separation, therefore,
cocatalysts [172]. In a very recent study, Liu et al. reported an
could significantly enhance compared to the mono-cocatalyst counter­
extraordinary investigation on Ru-Ti3C2/TiO2 heterostructure prepara­
part. Numerous effort has been devoted to incorporate two separated
tion, which showed an excellent photocatalytic activity [173]. This
cocatalysts on the TiO2 over the past decades. Zhang et al. spatially
composite photosystem was particularly obtained through a
deposited Pt and CoOx nanoparticles, functioning as the reduction and

Fig. 14. a) Diagram illustrating the

synthesis of TiO2 − Ti3C2/Ru, b) Micro­
scopy images of TiO2 − Ti3C2/Ru-20, c)
Compare Fermi level of TiO2 − Ti3C2/
Ru-20 with different illumination time,
d) The Fermi levels depend on the
lighting time and the open-circuit volt­
ages of TiO2 − Ti3C2, TiO2 − Ti3C2/Ru-
20, e) Photocatalytic activity for H2
evolution of different samples, f) The
vary of electron − hole pairs trans­
portation pathways on TiO2 − Ti3C2/Ru.
Reprinted with permission from Liu
et al. [173]. Copyright (2020) ACS nano.

14
C. Xia et al.
hydrothermal synthesis to deposit TiO2 nanosheets onto the existed
Ti3C2/Ru cocatalyst, as shown in Fig. 14a-b. In this case, Ti3C2 MXene
functions as a platform supporting TiO2 and Ru. Such configuration
resulted in an outstanding medium for charge migration and charge
separation. Indeed, the selective deposition of Ru clusters on the Ti3C2
MXene considerably lowers the Fermi level of composite cocatalyst,
providing an efficient charge transfer pathway, as shown in Fig. 14c-d.
Consequently, the obtained H2 evolution was found to be promoted
(Fig. 14e-f). Thus, this investigation offers a potent approach to signif­
icantly boost the photocatalytic achievement of TiO2 in which other
metal clusters and single metal atoms can be deployed on the MXene
support.
5. Concluding remarks and perspectives
Employing TiO2-based photocatalysts, so far, has remained a main­
stream approach to produce H2 via photocatalysis over the past decades.
Especially, the cutting-edge development of TiO2 unveils a novel
pathway to address the traditional limitation of TiO2, which is light
absorption. In this context, the development of cocatalysts functions an
essential role to promote the charge separation and reaction kinetic.
Generally, five configurations of cocatalysts in TiO2-based materials are
successfully proposed, including single reduction cocatalyst, dual
reduction–oxidation cocatalysts, plasmonic metal cocatalyst, dye
cocatalyst, and carbon bridge cocatalysts. Towards photocatalytic solar-
to-H2 evolution, the location of the modifiers (cocatalysts, conductors)
on TiO2 is crucial and very sensitive to efficient separation and transfer
of photogenerated charge carriers, resulting in further enhance the
photocatalytic performance. We might categorize TiO2 supported
cocatalyst into five models, based on the integration of reduction co­
catalysts, including cocatalyst I, cocatalysts I/II, cocatalysts I-II, co­
catalysts I@II core–shell, and conductor-cocatalyst. A superior
cocatalyst could be a game-changer, opening a bright route for large-
scale photocatalytic solar-to-H2 evolution.
To date, a large number of architectural structures of TiO2 supported
cocatalysts have been proposed. Notably, significant progress to tailor
the TiO2 supported active sites of cocatalysts has been devoted, which
could effectively promote H2 evolution:
• Metal-based cocatalysts: It can be seen that numerous efforts have
been devoted to preparing metal cocatalysts for the TiO2 material.
Metal single atoms catalysts have exhibited as emerging candidates
as their strong capability to promote the charge separation and
accelerate the reduction reaction. In this context, both precious (e.g.,
Pt, Ru) and non-precious (Ni, Cu) metal single catalysts-decorated
TiO2 have been introduced and exhibited outstanding photo­
catalytic performance. The critical challenge can be rooted in the
preparation method and TiO2 structure, requiring to offer an
appropriate medium to stabilize metal atoms on the TiO2 surface.
• Metal sulfides and metal phosphides: Employments of metal sul­
fides metal phosphides have been proposed as the alternative can­
didates to replace noble metal cocatalysts. These materials are also
proven the enhancement in the charge separation and catalytic re­
action. MoS2 nanosheets and Ni2P cocatalysts are the most promi­
nent materials, exhibiting a remarkable enhancement in the
photocatalytic activity coupling to the TiO2. However, the current
efficiencies are still far from the expectation. Therefore, double ef­
forts are required to prepare high-quality metal sulfides and metal
phosphides-derived cocatalysts. Also, the nature of interfacial con­
tact should be considered to promote charge separation.
• 2D MXenes: It has been realized that 2D MXenes have emerged as a
hot spot topic because of their unique properties for the H2 evolution
reaction. Ti3C2 MXene has been coupled to TiO2 and provided the
catalytic activity improvement while using other MXenes is still
limited. Unquestionably, the amount of produced H2 evolved over
15
Fuel 307 (2022) 121745
MXene/TiO2 composites is still low, which could be suffered from the
nature of MXenes surface and improper interfacial contact.
• Dual cocatalysts: The utilization of dual cocatalysts has been pro­
posed to enhance the charge separation within TiO2. The review
focus on the development of spatial and composite-based cocatalysts.
The former is associated with the incorporation of reduction and
oxidation cocatalysts to extract photogenerated electro-hole pairs
simultaneously. The latter, composite cocatalysts, have appeared to
be promising to promote the charge separation. Thus, this approach
can provide an excellent medium for charge separation and catalytic
reaction thanks to the synergetic effect of the utilized components.
The future will be witnessed the blooming of this type of co-catalyst,
which could provide a new milestone in the H2 photocatalytic per­
formance of TiO2.
Although many efforts have been made, the research and develop­
ment of coupling a TiO2 photocatalyst to cocatalyst(s) is still in infancy
and required further studies in the coming years. Indeed, the current
photocatalytic H2 achievements of cocatalysts-integrated TiO2 is far
below the target solar-to-H2 conversion, which is 10% [182]. In this
study, the outstanding properties of TiO2, it’s low cost and the emer­
gence of robust cocatalysts have successfully disclosed a worth a try
approach to establish a new milestone in the photocatalytic hydrogen
production. Additionally, many challenges in achieving a substantial
enhancement in the activity and stability of light-driven catalytic H2
evolution shoul be addressed to open new opportunities for photo­
catalytic H2 evolution for coupling a TiO2 photocatalyst to cocatalysts,
some issues could be considered as follow:
• Revealing and understanding the physicochemical characteristics,
features and functions of cocatalysts at the fundamental level: To
date, there is no systematic study on the influence of physicochem­
ical cocatalyst characteristics (e.g., chemical composition, phase
structure, dimension, morphology, structure, size distribution,
valence state, and surface area), features and functions of cocatalysts
to the photocatalytic H2 evolution. Therefore, it is of great impor­
tance to further explore this research direction. Notably, the idea to
reveal the in-situ change in the physicochemical properties via the
operando techniques and theoretical computations could provide
attractive guidance for the further design of novel high-performance
H2 evolution cocatalysts.
• Manipulating physicochemical characteristics of coupling a TiO2
photocatalyst to cocatalysts: Since the synthesis and dispersion
methods of cocatalysts might directly influence physicochemical
cocatalyst characteristics, novel techniques for coupling a TiO2
photocatalyst to cocatalysts should be explored.
• Explorating new coupling a TiO2 photocatalyst to cocatalysts with
focusing on high activity, excellent stability, and low cost for pho­
tocatalytic H2 evolution: As we have mentioned above, there are four
approaches to tailor cocatalysts have been listed, including metal-
based cocatalysts, metal sulfides, and metal phosphides, 2D
MXenes, and dual cocatalysts. The search for effective coupling of a
TiO2 photocatalyst to cocatalysts is the next research frontier. Single-
atom cocatalysts, biococatalysts (enzymes or bacteria as cocatalysts)
could be a tremendous promising though challenging.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgements
Dr. Quyet Van Le was supported by Brain Pool Program through the
National Research Foundation of Korea (NRF) funded by the Ministry of
C. Xia et al.
Science and ICT (grant number 2020H1D3A1A04081409). Thi Hong
Chuong Nguyen was funded by Vingroup Joint Stock Company and
supported by the Domestic Master/ PhD Scholarship Programme of
Vingroup Innovation Foundation (VINIF), Vingroup Big Data Institute
(VINBIGDATA), code VINIF.2020.TS.55. Prof. Xia thanks to the funding
support from Natural Science Foundation of Jiangsu Province
(BK20200775), and Advanced Analysis and Test Center of Nanjing
Forestry University.
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