解説

先進セラミックス研究センター年報（2021）. Vol. 10, 16‑24

Study on Facile Preparation of Composite Photocatalyst Based on
Titanium Dioxide and Their Photocatalytic Hydrogen Evolution Performance
Xinxin Jiang, Masayoshi Fuji
Advanced Ceramics Research Center, Nagoya Institute of Technology
3-101-1 Honmachi, Tajimi, Gifu 507-0033, JAPAN
Abstract

As an important area in the field of advanced materials, TiO2-based photocatalysts have always been researched hot pots. At
present, most of the applications of TiO2-based photocatalysts are still in the experimental stage. This research uses commercial
TiO2 as the main material and aims to simplify the synthesis method and reduce the experimental cost. This work uses the cocatalyst as the starting point to investigate a metal co-catalyst, sulfide co-catalyst, and phosphide co-catalyst. Cu, MoSx and MoP
are respectively used to construct a catalytic system to improve the photocatalytic hydrogen production ability of the material.
Good loading methods are applied, such as in-situ photo-deposition, ultrasonic adsorption, etc., to optimize the synthesis steps,
promote the transfer of electrons and holes between the different materials and improve the photocatalytic performance of thecomposite materials. The photocatalytic reaction mechanism was revealed by studying the morphology of the catalyst, thecombination mode, the separation efficiency of the photogenerated carriers, and the photocatalytic hydrogen production activity
under ultraviolet light. The results of this study provide technical support and a theoretical basis for the design and preparation of
low-cost, simple and efficient photocatalytic systems.
Keywords: Titanium dioxide, molybdenum phosphide, molybdenum sulfide, cuprous oxide, photocatalysts, hydrogen.

1. Introduction

Photocatalytic technology is expected to play animportant role in future energy expansion by solving theincreasingly serious energy depletion and environmental
deterioration. As an important field of advanced
materials, TiO2-based photocatalysts have always beenstudied as hot spots. Titanium dioxide itself has aphotocatalytic activity in the ultraviolet region.
However, it is still in the experimental stage. The easy
recombination of high numbers of photogenerated
electrons and holes reduces the number of active species
that can cause redox reactions and impedes the TiO2
photocatalytic performance. The co-catalyst composite
photocatalysts are an effective way to solve thisproblem. Not only are some co-catalysts cheaper andeasier to synthesize, but they also provide internal
electron transfer channels in the composite to facilitatecharge transfer in the photocatalyst and improve its
ability to generate hydrogen. Ni, Cu and their oxides,
some transition metal sulfides (such as MoS2, WS2, NiS
and CuS, etc.) and transition metal phosphides (such as
NiP, MoP, CoP, CuP, etc.) are used as non-precious metalhydrogen evolution promoters. and received widespreadattention.

Cu 2 O has a bandgap of 2.2eV and is a p-typesemiconductor. Recent literature has shown that Cu2O
supported by TiO 2 can act as a cocatalyst forphotocatalytic hydrogen production with performancecomparable to Ag and Au[1, 2]. In addition, part of the Cu+
particles is reduced to Cu (0) particles during thephotocatalytic process, which can effectively improvethe carrier transfer efficiency during the photocatalytic
process[3].
Molybdenum phosphide (MoP) has attracted extensive
attention due to its platinum-like electronic structure,
low synthesis cost, high catalytic activity, and acid andalkali resistance. According to density functional theory(DFT) calculations, the P atoms in transition metal
phosphides (TMPs) play an important part in thehydrogen production process. Owing to its highelectronegativity ( χ= 2.1), the P atom has a strong
ability to extract electrons, so it can attract an electronfrom the metal atom when combined with a metalelement[4, 5]. Therefore, MoP is a potential cocatalyst to
modify TiO2 to enhance its photocatalytic activity.
Molybdenum sulfide has a special two-dimensional
layered structure and is the most promising electronic
promoter to replace the noble metal Pt. Numerous― 16 ―

Study on Facile Preparation of Composite Photocatalyst Based on Titanium Dioxide and Their Photocatalytic Hydrogen Evolution Performances t u d i e s h a v e s h o w n t h a t Ti O 2 m o d i f i e d w i t hmolybdenum disulfide (MoS 2 ) nanoparticles cansignificantly improve the performance of photocatalytichydrogen production[6, 7]. In addition, increasing thenumber of unsaturated S atomic active sites located at
the material edge is an important strategy to enhance thephotocatalytic hydrogen production performance ofsemiconductor materials [8]. In general, the irregulararrangement of atoms in amorphous materials tends toform more atomic defect sites or unsaturated active sites
than in crystalline materials. Therefore, the modificationof semiconductor materials by synthesizing amorphousmolybdenum sulfide (a-MoS x) is a feasible way to
improve photocatalytic performance.
Based on the above background, this study uses
commercial titanium dioxide as the main material. Using
cheap materials such as Cu, MoS x , and MoP as
cocatalysts, the synthesis method is simplified and thephotocatalytic hydrogen production capacity of thematerials is improved.
2. The design and preparation of TiO2/Cu2O/Cucomposite photocatalyst and its photocatalytic
water splitting performance

The B-TiO 2 /Cu 2 O/Cu composite material was
synthesized in two steps involving in-situ photodepositionand hydrogenation treatment. Briefly, commercial P25(TiO2) was dispensed in a test tube containing a solutionof absolute ethanol and methanol. A specific amount of
CuCl2 was added and dissolved by stirring. Argon gas
was used as a purge gas for half an hour, then irradiatedwith ultraviolet light for one hour to reduce the Cu
particles on the surface of the TiO2 to obtain the TiO2/
Cu2O/Cu powder. The TiO2/Cu2O/Cu powder was thenmixed with NaBH 4 powder and heated at a specifictemperature, and the hydrogenation reaction occurred.
The hydrogenated TiO 2/Cu 2O/Cu powder was thenobtained. A schematic diagram of the whole process wasshown in Scheme 1. The TiO 2/Cu 2O catalysts withC, 350 °C, anddifferent annealing temperatures of 300 °400 °C, are called TC6-300, TC6-350, and TC6-400,
respectively. The TiO 2/Cu 2O catalysts with different
content Cu, called TC2, TC4, TC6, TC8 and TC10,
respectively (The nominal mass fraction of Cu relative
to TiO 2 was 6 wt%, and the resulting sample waslabelled TC6.). hydrogenated Cu2O and TiO2 powder,called H-Cu2O/Cu and B-TiO2.
Fig. 1 shows the X-ray diffraction measurements ofeach sample. The XRD results indicated that Cu2O and
Cu are in situ loaded on the surface of the TiO2.
Figure 2 shows TEM images of the B-TiO2/Cu2O/Cu(TC6-350) sample which can more clearly be used toobserve the distribution of copper particles on the TiO2
surface. The TEM surface morphology shows thepresence of Cu2O/Cu particles on the TiO2 surface assmall islands or surface deposits.
The photocatalytic activity of the prepared samples
was evaluated by a hydrogen evolution test. As shown in
Figure 3, the photocatalytic activity of pure TiO2 and
B-TiO2 for water splitting under ultraviolet irradiation isvery poor. Comparing the TC6 sample with the BTC6
sample, it can be seen that due to the reduction of thespecific surface area of the TiO2 after the hydrogenation
treatment, the copper precursor adsorbed on the surfaceof the titanium dioxide decreases during thephotodeposition process (Table 1). As a result, the actual
copper content of the BTC6 sample is much lower thanthat of the TC6 sample, which ultimately leads to adecrease in the hydrogen evolution performance. When
Cu2O/Cu particles are deposited on the surface of TiO2,
the photocatalytic hydrogen release capacity of TiO2/
Cu2O/Cu is enhanced. When the copper loading reaches
6%, the TC6 sample reaches the maximum hydrogen
evolution efficiency. After the hydrogenation treatment,
the photocatalytic hydrogen release ability of the
B-TiO 2 /Cu 2 O/Cu sample is further enhanced. The
maximum release of TC6-350 under ultraviolet light isabout 8.5mmol h -1g -1, which is 40 times that of the

Scheme 1 Schematic illustration for the synthesis route of the B-TiO2/Cu2O nanoparticles (TC6-350).
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Xinxin Jiang, Masayoshi Fuji

Fig. 1 XRD patterns of the as-prepared samples: (a) TiO2,

B-TiO2, TC6 and TC6-350, (b) Cu2O/Cu and Hydrogenated
Cu2O/Cu, (c) TiO2/Cu2O/Cu with different copper loadings, (d)TC6 samples formed at different hydrogenation temperatures.

Fig. 2 TEM and HR-TEM images of the B-TiO2/Cu2O/Cu(TC6-350) samplehydrogen evolution rate of pure TiO2. With the increasein the hydrogenation temperature, the photocatalytic
activity of the B-TiO2/Cu2O/Cu samples first increased,
then decreased[9]. The decrease in performance with theincreasing annealing temperature can be attributed to
two aspects. (1) The specific surface area is reduced.
The results show that the lower specific surface area ofthe sample has a greater impact on its catalytic
performance[10]. (2) The concentration of bulk defects
increases. Titanium dioxide has two kinds of defects,
namely bulk defects and surface defects[11]. The surface
defects can trap carriers and transfer them to surfaceadsorbed materials to promote the separation ofphotogenerated electrons and holes. The bulk defects
will trap carriers and recombine them. As the annealing
temperature increases, the concentration of the bulk
defects increases, thereby reducing the catalytic
performance of the sample. This is consistent with the
PL result. This phenomenon has also been reported in aprevious publication[12].
Scheme 2 illustrates the mechanism of the photocatalyst.
When Cu 2O is loaded on the surface of B-TiO 2, the
B-TiO 2/Cu 2O hybrid exhibits an n-n semiconductor
system. Due to the relative position of the energy band
potential, the photogenerated electrons are transferredfrom the conduction band of Cu 2O (-0.41eV) to the
conduction band of B-TiO2 (-0.32eV). In addition, theFermi energy level of Cu is lower than that of the n-type
Cu2O and B-TiO2. The electrons on the CB of TiO2 canfurther migrate to Cu until the system reaches
equilibrium, and the photogenerated electrons reduce H+
to H2 on the surface of the copper particles. At the sametime, the photo-generated hole on the valence band of
the B-TiO2 is inserted into the valence band of Cu2O,
and the methanol adsorbed on the surface is oxidized,
thereby inhibiting the recombination of the charge
carriers. Due to the synergistic effect of the B-TiO 2/
Cu2O heterojunction and metallic copper particles, thecopper-loaded black TiO 2 helps to expand the lightabsorption range, improve the separation efficiency ofthe carriers, and improve the photocatalytic hydrogen
evolution ability. Therefore, B-TiO 2/Cu 2O/Cu is an
attractive photocatalyst under ultraviolet radiation.

Fig. 3 Photocatalytic activity tests for H2 evolution by the as-prepared samples under UV light― 18 ―

Study on Facile Preparation of Composite Photocatalyst Based on Titanium Dioxide and Their Photocatalytic Hydrogen Evolution Performance

Table 1 Physical characteristics of the B-TiO2/Cu2O/Cu catalysts.

Catalyst

Specific surface area (m2 g-1)

TiO2
B-TiO2
Cu2O/Cu
BTC6
TC6
TC6-300
TC6-350
TC6-400

50.7
43.2
5.64
36.8
46.0
46.3
44.9
37.0

Scheme 2 Scheme of the photocatalytic mechanism of the

B-TiO2/Cu2O/Cu photocatalysts for the evolution of H2 anddegradation of the RhB.

3. The design and preparation of TiO2/MoP
composite photocatalyst and its photocatalytic
performance for water splitting

In Chapter 2, the coordination effect of the copper cocatalyst and hydrogenation of TiO 2 successfully
improved the hydrogen evolution performance of thecatalyst. However, the preparation of the catalyst
involves multiple synthesis steps, the experimental
control is relatively complicated, and the preparation isrelatively complicated. Since metallic copper particles
are extremely easy to oxidize in the air and water, it isdifficult to control the ratio of Cu1+ and Cu (0) particles.
This is not conducive to further optimising the catalytic
performance.
As far as we know, there are few reports about themodification of TiO 2 by MoP and its application tophotocatalytic water splitting. During the photocatalytic
preparation process, high-temperature calcination oftencauses changes in the catalyst, such as a decrease in thespecific surface area and lack of active sites, resulting ina decreased photocatalytic performance. In this chapter,
sodium hydrogen hypophosphite was used topore volume
cm3 g-1
0.401
0.241
0.04
0.241
0.323
0.317
0.282
0.251

phosphorylate MoO 3 powder to prepare the MoP
powder, which was combined with commerciallyavailable TiO 2 using a simple ultrasonic dispersion
method. The subsequent annealing steps are reduced,
manufacturing costs are reduced, and the photocatalytichydrogen generation performance is improved. A
schematic diagram of the entire process is shown in
Scheme 3.
The phase structure of the TiO2/MoP photocatalyst canbe characterized by an XRD pattern, as shown in Figure
4. Figure 4 shows the characteristic peaks of TiO2 and
MoP, indicating that the TiO 2/MoP composite was
successfully synthesized.
Figure 5 shows a TEM image of the TiO 2/MoP-5p
sample. The MoP particles are rougher than the TiO2
particles and form uniform agglomerates with them, thus
providing a good interface contact, exposing more
surfaces/boundaries and increasing the active sites.
In Figure 6, we analyzed the hydrogen production
efficiency of the TiO2, MoP and TiO2/MoP samples. The

Scheme 3 Schematic illustration showing the synthesis route of

the TiO2/MoP nanoparticles.

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Xinxin Jiang, Masayoshi Fuji

Fig. 4 (a,b) X-ray diffraction profile results of as-prepared samples

Fig. 5 TEM images of TiO2/MoP-5p: (a), (b), (c), (d)and corresponding magnification of HRTEM image(e), (f).

pure TiO2 photocatalyst has almost no photocatalytic
activity. This is mainly due to the lack of high-efficiency
elect ron promoters a nd t he high elect ron-hole
recombination rate[13]. The pure MoP photocatalysts also
have no photocatalytic activity, which is due to themetallic proper ties of MoP [14]. W hen t he TiO 2
photocatalyst was combined with MoP, the photocatalytic
activity of all the TiO2/MoP samples was significantly
improved. With the increase in the MoP loading, thehydrogen evolution performance of TiO2/MoP gradually
improved. The hydrogen evolution rate of TiO2/MoP-5p is
the highest, reaching 4.3mmolg-1h-1. Compared to the TiO2
photocatalyst, the photocatalytic hydrogen production
performance of the TiO2/MoP photocatalyst is improved
18-fold. To determine the stability of the TiO2/MoP
sample, four repeated experiments were carried out(Figure 6(b)). Obviously, the TiO2/MoP-5p sample wasable to maintain a stable and effective hydrogenproduction rate during the repeated experiments. After thefive repeated experiments, the hydrogen evolution rate
remained at 64%. After four cycles of experiments, thehydrogen evolution performance of the sample rapidly
dropped. This is due to the prolonged hydrogen evolution
reaction and photo corrosion of the MoP co-catalyst.

Fig. 6 (a) Photocatalytic activity tests for H2 evolution by the as-prepared samples under UVlight. (b) Photocatalytic stability of the TiO2/MoP-5p photocatalyst.
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Study on Facile Preparation of Composite Photocatalyst Based on Titanium Dioxide and Their Photocatalytic Hydrogen Evolution Performance

A possible mechanism is proposed to illustrate theimprovement in the hydrogen production performanceof the TiO2/MoP catalyst, as shown in Scheme 4. When
MoP is loaded on the surface of TiO2, the TiO2/MoP
hybrid exhibits a typical metal-semiconductor system.
Under ultraviolet radiation, titanium dioxide can bequickly activated to generate photo-generated electrons
and holes. Because the work function of the MoP (5.61
eV) is higher than that of TiO2 (4.21 eV), electrons in
the conduction band of the TiO 2 can be quickly
transferred to the surface of the MoP particles instead of
returning to the defect energy level or reducing therecombination of the VB and holes. Due to the betterhydrogen affinity of MoP, H+ is quickly captured andreduced to H2. At the same time, due to the high holetrapping ability of methanol, the holes can quickly
oxidize the methanol on the TiO2 surface. Due to the low
impedance between the TiO2 and MoP and the highquality metal-semiconductor system, the developed
TiO 2 /MoP hybrid can effectively separate photogenerated electrons and holes and move them to thesurface of the MoP and TiO2 particles, respectively. Thisis the reason for the highly-enhanced photocatalytichydrogen production activity.

Scheme 4 Schematic diagrams illustrating the possible

photocatalytic mechanism of the TiO2/MoP photocatalyst.

4. The design and preparation of TiO2/MoSx
composite photocatalyst and its photocatalytic
performance for water splitting

In the previous chapter, using MoP as a co-catalyst, acatalytic system with simple synthesis steps and a betterhydrogen evolution performance was introduced.
However, due to the limitation of the MoP preparation
process, there are fewer active sites on the MoP body,which restricts the further improvement of its catalytic
performance. How to use a simple method to prepare a
cocatalyst with abundant active sites to construct acatalytic system with high catalytic performance has
become the research focus of this chapter. In this study,
we synthesized an amorphous molybdenum sulfide
electron co-catalyst-modified TiO 2 (TiO 2 /a-MoS x )photocatalytic material by the in-situ adsorptionphotodeposition conversion method to improve thephotocatalytic hydrogen production performance.
B r i e f l y, P 2 5 w a s m i x e d w i t h t h e a m m o n i u mtetrathiomolybdate, then by light irradiation, theammonium tetrathiomolybdate was reduced tomolybdenum sulfide and adsorbed on the surface of theTiO 2. A schematic diagram of the whole process isshown in Scheme 5. When the Mo content is 0.1, 0.5, 1,
3, 5, and 8 wt%, the obtained TiO2/a-MoSx sample canbe expressed as TiO2/a-MoSx-Xp, where X represents
the mass ratio of the Mo element to TiO2.
The structure of TiO2 and amorphous MoSx can becharacterized by the XRD patterns (Fig. 7). The XRD
results showed the characteristic peaks of MoSx andTiO 2, indicating that the amorphous MoSx and TiO 2
successfully formed a composite.
To prove that the amorphous MoSx phase has beensuccessfully supported on the surface of the TiO 2material, we analyzed the surface morphology andm i c r o s t r u c t u r e o f t h e p r e p a r e d Ti O 2 / a - M o S x
photocatalyst by SEM, HRTEM and Mapping (Fig. 8). It
was determined from the SEM and TEM pictures that
MoSx was successfully loaded onto the TiO2 surface,and good contact was formed.
To prove the potential photocatalytic ability of thesamples, we studied the hydrogen production capacity of
the TiO2, a-MoSx, TiO2+a-MoSx mixed samples, TiO2/
c-MoSx and TiO2/a-MoSx-8p samples. In Figure 9, thepure TiO2 photocatalyst has almost no photocatalytic
activity. This is due to the high photo-generated carrier
recombination ability of TiO 2 , which limits its
photocatalytic performance. The performance of the
TiO2+a-MoSx mixed sample was slightly higher thanthat of the pure TiO2 sample, indicating that MoSx andTiO2 can form a certain charge transfer and improve thehydrogen evolution ability. After the surface of the TiO2
photocatalyst material is modified with the a-MoS xe l e c t r o n i c p r o m o t e r, t h e h y d r o g e n e v o l u t i o nperformance of the TiO2/a-MoSx sample was greatly
improved. Compared to the sample that simply mixes
a-MoSx and TiO2, the hydrogen evolution performanceof the TiO2/a-MoSx-8p sample is higher. This resultshows that the direct loading of amorphous molybdenum
sulfide on the surface of TiO2 forms a better interface― 21 ―

Xinxin Jiang, Masayoshi Fuji

Scheme 5 Schematic illustration showing the synthesis route of the TiO2/a-MoSx nanoparticles.

Fig. 7 (a,b) XRD results of the as-prepared samples

Fig. 8 SEM images of various samples: (a), (b), (c), (d), (e)EDS spectra of the TiO2/a-MoSx-8p (f) HRTEM images and
EDS elemental mapping images of the TiO2/a-MoSx-8p

contact and has a faster electron transfer rate than simple
m i x i n g , t h u s i m p r o v i n g t h e e ff i c i e n c y o f t h ephotocatalytic hydrogen evolution. Compared to theloaded crystalline molybdenum sulfide sample (TiO2/
c-MoSx), the TiO2/a-MoSx sample has a better hydrogen
evolution performance. This is due to the abundant
unsaturated S atoms on the surface of the amorphousmolybdenum sulfide sample, which has more active
sites. On the other hand, well-crystallized molybdenum
sulfide catalysts usually need to be annealed (about
400 °C), which can easily cause phase transitions
between the anatase TiO2 and amorphous MoS2, lessunsaturated S atoms[15] and a reduced specific surface
area[16], thus reducing the hydrogen evolution capacity of
the catalyst.
A possible mechanism was proposed to explain thereason for the increase in the efficiency of the TiO2/
a-MoSx hydrogen production (Scheme 6). When a-MoSx
is loaded on the surface of TiO2, the TiO2/a-MoSx hybrid
forms a typical metal-semiconductor system. The work
function of TiO2 (4.2eV) is lower than that of a-MoSx(5.7eV), which can force free electrons to migrate from
TiO2 to the amorphous MoSx until the Fermi level isequal. For the amorphous MoSx, it is obvious that due toits various lattice defects and irregular arrangements,
there are more unsaturated S atoms inside and on thesurface. These unsaturated S atoms can rapidly capture
the hydrogen protons (H+) in the solution, then obtain
photoelectrons and reduce H+ to H 2. During the UV
irradiation, the photoexcited electrons in the CB of TiO2

― 22 ―

Study on Facile Preparation of Composite Photocatalyst Based on Titanium Dioxide and Their Photocatalytic Hydrogen Evolution PerformanceFig. 9 Photocatalytic activity tests for H2 evolution by the as-prepared samples under UV light.

Scheme 6 Schematic diagrams illustrating the possible

photocatalytic mechanism of the TiO2/a-MoSx photocatalyst.

can be effectively transferred to the amorphous MoSx,
thereby promoting the interface charge transfer andsubsequent hydrogen evolution reaction.
Due to the low impedance between the TiO 2 anda-MoS x and the high-quality metal-semiconductor
system, the constructed TiO 2 /a-MoS x hybrid caneffectively separate photo-generated electrons and holes
and move them to the surface of the a-MoSx and TiO2
particles, respectively. This is the reason for the highlyenhanced photocatalytic hydrogen production activity.
Because of its high activity, easy preparation, low costand high stability, the in-situ growth of a-MoSx on thesemiconductor photocatalyst by the adsorptionphotodeposition conversion method is a very promising
way for the preparation of efficient HER catalysts.

mechanism was revealed by studying the morphology of
the catalyst, the combination mode, the separation
efficiency of the photogenerated carriers, and thephotocatalytic hydrogen production activity underultraviolet light. The result of this study provides
technical support and a theoretical basis for the design
and preparation of low-cost, simple and efficientphotocatalytic systems.
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5. Conclusion

encapsulated in N,P-codoped carbon: an efficient andIn this study, we used commercial TiO2 as the mainmaterial and aimed to simplify the synthesis method andreduce the experimental cost. Cu, MoSx and MoP areused to construct a catalytic system to improve thephotocatalytic hydrogen production ability of thematerial. Good loading methods, such as in-situ
deposition, ultrasonic adsorption, etc., were used to
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