Vanadium diboride as an efficient cocatalyst coupled with CdS for enhanced visible light photocatalytic H2 evolution

Exploiting active, stable, and cost-efficient cocatalysts is crucial to enhance the photocatalytic performance of semiconductor-based photocatalysts for H₂ evolution from water splitting. Herein, we report on using vanadium diboride (VB₂) as an efficient cocatalyst to enhance the photocatalytic H₂ evolution performance of CdS nanoparticles under visible light irradiation (λ ≥ 420 nm). The CdS/VB₂ composites prepared by a facile solution-mixing method exhibit much improved H₂ evolution activities in 10 vol% lactic acid (LA) solution relative to pristine CdS. The most efficient CdS/VB₂ composite with 20 wt% VB₂ (CB20) exhibits a H₂ evolution rate as high as 12.1 mmol h⁻¹ g⁻¹, which is about 11 times higher than that of CdS alone (1.1 mmol h⁻¹ g⁻¹). Moreover, the highest apparent quantum efficiency (AQE) of 4.4% is recorded on CB20 at 420 nm. The improved photocatalytic activity of CdS/VB₂ composite can be attributed to the excellent cocatalytic effect of VB₂, which can not only enhance the charge separation on CdS but also accelerate the H₂ evolution kinetics. This work demonstrates the great potential of using transition metal brodies (TMBs) as efficient cocatalysts for developing noble-metal-free and stable photocatalysts for solar photocatalytic H₂ evolution.     

The size and valence state effect of Pt on photocatalytic H2 evolution over platinized TiO2 photocatalyst

Photocatalytic hydrogen production from water or organic compounds is a promising way to resolve our energy crisis and environmental problems in the near future. Over the past decades, many photocatalysts have been developed for solar water splitting. However, most of these photocatalysts require cocatalyst to facilitate H₂ evolution reaction and noble metals as key cocatalysts are widely used. Consequently, the condition of noble metal cocatalyst including the size and valence state etc plays the key role in such photocatalytic system. Here, the size and valence state effect of Pt on photocatalytic H₂ evolution over platinized TiO₂ photocatalyst were studied for the first time. Surprisingly, it was found that Pt particle size does not affect the photoreaction rate with the size range of several nanometers in this work, while it is mainly depended on the valence state of Pt particles. Typically, TOFs of TiO₂ photodeposited with 0.1–0.2 wt% Pt can exceed 3000 h⁻¹.     

Light-induced confined growth of amorphous Co doped MoSx nanodots on TiO2 nanoparticles for efficient and stable in situ photocatalytic H2 evolution

Amorphous molybdenum sulfide (a-MoS_x) prepared by in situ photoreduction method with an abundance of exposed active sites has been identified as an efficient cocatalyst for catalyzing photocatalytic H₂ evolution reaction (HER). However, the intrinsic activity of the a-MoS_x cocatalyst toward HER is low due to the unfavorable electronic structures of the active sites. Herein, we report a facile light-induced method for the confined growth of transition metal (TM) doped MoS_x (a-TM-MoS_x) cocatalysts on TiO₂ nanoparticles and their catalytic activity for in situ photocatalytic HER. It is found that doping Co into a-MoS_x can greatly enhance the activity of resulted a-Co-MoS_x cocatalyst for photocatalytic H₂ evolution over TiO₂ among the transition metal dopants (Co, Ni, Fe, Cu, Zn) tested. The most efficient a-Co-MoS_x cocatalyst (Co/Mo = 1/4 and 4 mol% loading) loaded TiO₂ (TiO₂/a-Co-MoS_x) shows a H₂ evolution rate of 133.8 μmol h⁻¹, which is 3.3 times higher than that of a-MoS_x loaded TiO₂ (TiO₂/a-MoS_x). Moreover, the TiO₂/a-Co-MoS_x photocatalyst shows excellent recycling H₂ evolution stability. The characterization results reveal that a-Co-MoS_x cocatalyst can not only effectively capture the photogenerated electrons of TiO₂ to greatly enhance the separation efficiency of photogenerated charges but also significantly reduce the overpotential of HER due to the formation of highly active “CoMoS” sites, thus synergistically enhancing the catalytic activity of TiO₂/a-Co-MoS_x. Moreover, the light-induced growth of a-Co-MoS_x on TiO₂ is found to readily couple with the in situ photocatalytic HER. Therefore, this work provides a simple and efficient strategy for designing high-performance a-MoS_x-based cocatalysts for stable in situ photocatalytic H₂ evolution.     

Photodeposition of amorphous MoSx cocatalyst on TiO2 nanosheets with {001} facets exposed for highly efficient photocatalytic hydrogen evolution

Semiconductor-based photocatalytic hydrogen production is a promising approach to convert solar energy to renewable and clean hydrogen energy. However, development of cheap and efficient hydrogen evolution cocatalyst to replace noble metal based cocatalysts remains a challenge. Here, we report a MoS_x/TiO₂ nanohybrid prepared by a facile photo-assisted deposition method. The amorphous MoS_x grows intimately on the single-crystalline TiO₂ nanosheet with {001} facets exposed to form a heterojunction, which can not only facilitate the charge separation and transfer, but also provide plenty of active sites for hydrogen evolution reaction owing to abundant unsaturated S atoms on amorphous MoS_x. As a result, the MoS_x/TiO₂ nanohybrid shows a remarkable enhancement in photocatalytic hydrogen evolution performance in comparison to bare TiO₂ nanosheet. The best 0.5%-MoS_x/TiO₂ nanohybrid exhibits a hydrogen production rate at 1835.7 μmol g^?1 h^?1 under Xenon light irradiation, which is about 177 times higher than that of bare TiO₂ nanosheet. This work paves a way for the design and construction of low-cost and noble-metal-free photocatalysts for efficient photocatalytic hydrogen evolution.     

Metal (oxide) modified (M= Pd,Ag, Au and Cu) H2SrTa2O7 for photocatalytic CO2 reduction with H2O: The effect of cocatalysts on promoting activity toward CO and H2 evolution

Ag, Pd, Au, Cu₂O as cocatalysts were loaded on the layered H₂SrTa₂O₇ (HST) for photocatalytic CO₂ reduction with H₂O. The characterization revealed that cocatalysts loaded on the surface of HST can effectively promote the separation of photogenerated electrons and holes due to the formation of Schottky barrier or p-n junction, thus enhancing photocatalytic activity. Of note, Ag, Pd, Au, Cu₂O loading exhibited obviously different performance on promoting photocatalytic activity of HST toward CO evolution and H₂ evolution because of the different overpotentials of CO evolution and H₂ evolution on loaded photocatalysts. Cocatalysts with low overpotentials of CO or H₂ evolution act as active sites for CO or H₂ evolution, thus controlling the selectivity toward CO or H₂. The Au/HST exhibited high activity for only H₂ evolution (17.5 μmol g⁻¹ h⁻¹) due to relative low overpotential for H₂ evolution (0.67 V) while the Cu₂O/HST exhibited high activity only for CO evolution (0.23 μmol g⁻¹ h⁻¹) due to relative low overpotential for CO evolution (0.40 V). The Pd/HST sample exhibits high photocatalytic activity for both CO and H₂ evolution rates due to the low overpotential for CO and H₂ evolution, reaching 4.0 and 4.7 times of bare HST, respectively. This work here gives an in-depth understanding of the effect of cocatalysts on promoting photocatalytic activity and selectivity and can also give guidance to design photocatalysts with high activity and selectivity for photocatalytic CO₂ reduction with H₂O.     

Efficient photocatalytic hydrogen production from formic acid on inexpensive and stable phosphide/Zn3In2S6 composite photocatalysts under mild conditions

Developing an efficient, stable and low-cost photocatalytic hydrogen production from formic acid is a daunting challenge and has attracted the intense interest of many of researchers. In this paper, we report the synthesis of novel composite photocatalysts (Ni₂P/Zn₃In₂S₆ (ZIS6) and MoP/ZIS6) and their catalytic performance for H₂ production reaction from formic acid under visible light irradiation, in which Ni₂P and MoP were used as cocatalysts to enhance hydrogen generation activity of ZIS6. The photocatalytic hydrogen production rates of the optimized 1.5 wt% Ni₂P/ZIS6 (45.73 μmol·h⁻¹) and 0.25 wt% MoP/ZIS6 (92.69 μmol·h⁻¹) were 3.5 times and 7.2 times higher than that of the pure ZIS6 (12.88 μmol·h⁻¹), respectively. The apparent quantum efficiency at wavelength λ = 400 ± 10 nm for the two photocatalysts was about 1.8% and 6.4%, respectively. Significantly, it was found that the remarkable improvement of hydrogen production performance is attributed to the introduction of the phosphide cocatalysts, which can serve as a charge separation center and an active site for photocatalytic hydrogen production from the decomposition of formic acid. The reaction mechanism of photocatalytic hydrogen production from formic acid was also proposed.     

Edge-sulfonated graphene-decorated TiO2 photocatalyst with high H2-evolution performance

Graphene as a prospective cocatalyst can obviously promote the photocatalytic H₂-evolution performance of photocatalysts by rapidly transferring photogenerated electrons. For an efficient graphene-modified photocatalytic system for H₂ evolution, the fast H₂-evolution reaction is as important as the rapid photoelectron transfer via graphene. In this paper, edge-sulfonated graphene (rGO-SO₃H) with high H⁺-adsorbed activity was successfully synthesized by the formation of covalent bonds between graphene and benzenesulfonic acid through a diazotization reaction, which couples with TiO₂ nanoparticles to prepare rGO-SO₃H/TiO₂ photocatalyst for accelerating H₂-evolution reaction. The results showed that the rGO-SO₃H/TiO₂ displayed the highest H₂-production rate of 197.1 μmol h^?1 g^?1 as high as 5.38, 2.81, and 3.40 times of TiO₂, rGO/TiO₂, and SO₃H/TiO₂, respectively. The improved efficiency of rGO-SO₃H/TiO₂ can be attributable to the synergetic action of graphene as a photoelectron cocatalyst and sulfonate ions as H⁺-adsorbed active sites. This study provides a new insight for the efficient hydrogen-evolution graphene-based photocatalysts.     

Carbon intercalated MoS2 cocatalyst on g-C3N4 photo-absorber for enhanced photocatalytic H2 evolution under the simulated solar light

Despite MoS₂ being a promising non-precious-metal cocatalyst, poor electronic conductivity and low activity for hydrogen evolution caused by serious agglomeration have been identified as critical roadblocks to further developing MoS₂ cocatalyst for photocatalytic water splitting using solar energy. In this work, the density functional theory calculations reveal that carbon intercalated MoS₂ (C-MoS₂) has excellent electronic transport properties and could effectively improve catalytic activity. The experiment results show that the prepared tremella-like C-MoS₂ nanoparticles have large interlayer spacing along the c-axis direction and high dispersion because of intercalation of the carbon between adjacent MoS₂ layers. Furthermore, the heterostructure photocatalyst of C-MoS₂@g-C₃N₄ formed by loading the cocatalyst of C-MoS₂ onto g-C₃N₄ nanosheets exhibits the H₂ evolution rate of 157.14 μmolg⁻¹h⁻¹ when containing 5 wt% C-MoS₂. The high photocatalytic H₂ production activity of the 5 wt% C-MoS₂@g-C₃N₄ can be attributed to the intercalated conductive carbon layers in MoS₂, which leads to efficient charge separation and transfer as well as increased activities of the edge S atoms for H₂ evolution. We believe that the C-MoS₂ will offer great potential as a photocatalytic H₂ evolution reaction cocatalyst with high efficiency and low cost.     

Effect of liquid phase plasma on photocatalysis of water for hydrogen evolution

This study examined the effects of liquid phase plasma irradiation on the photocatalytic decomposition of water for hydrogen evolution. TiO₂ and metal-loaded TiO₂ nanocrystallites were introduced as photocatalysts. Na-Y zeolite was applied as a support for the TiO₂ nanocrystallites. The photocatalytic activities of the photocatalysts were estimated for hydrogen production from water. Hydrogen evolution appeared in the photodecomposition of water without photocatalysts. This was caused by the decomposition of water by plasma irradiation in water directly. The hydrogen evolution efficiency improved with increasing conductivity of water. The rate of hydrogen evolution was increased by the metal loading (Ni, Co, Fe) on the TiO₂ surface. Na-Y zeolite can be used as an efficient photocatalytic support for the fixation of TiO₂. The TiO₂ nanocrystallites were incorporated above 40 wt% on Na-Y support.     

Well-dispersed CoSx nanoparticles modified tubular sulfur doped carbon nitride for enhanced photocatalytic H2 production activity

Appropriate dispersion of cocatalyst on semiconductor for improving photocatalytic H₂ production efficiency is a challenging work in semiconductor photocatalysis. Herein, we constructed the noble-metal-free CoS_x modified tubular sulfur doped carbon nitride (SCN) photocatalysts by chemical precipitation process. The amorphous CoS_x well dispersed on SCN served as H₂ production sites, which reduced the overpotential and inhibited the recombination of photogenerated carriers by interfacial charge transfer. Maximized H₂ production rate of 573.06 μmol g⁻¹ h⁻¹ under visible light irradiation was obtained by optimizing the CoS_x loading proportion to 2.4%, which was higher than that of 0.75 wt% Pt/SCN. In addition, a possible mechanism for improved H₂ production activity was proposed based on the experiments and discussion. This work provides a new strategy to design rational structure of non-noble metal cocatalyst modified photocatalyst to further improve H₂ production performance.     

Mesoporous black TiO2 array employing sputtered Au cocatalyst exhibiting efficient charge separation and high H2 evolution activity

The separation and transfer of photogenerated carriers are the key issue in the design of high performance TiO₂ photocatalysts. In order to overcome the kinetic limitations and achieve rapid charge transfer, TiO₂-related multi-component catalysts have been extensively studied. Among all the TiO₂ supports, the impressive black TiO₂ (BT) with broad visible light absorption spectrum and oxygen vacancies are preferable, but still suffers from low quantum efficiency. Meanwhile, poor control of cocatalyst placement by conventional loading method can also severely impede photocatalytic efficiency. Herein a fast and simple metal magnetron sputter approach was used to place highly-uniformed Au nanoparticles cocatalyst on the top of the mesoporous TiO₂–BT nanotube array fabricated by in situ electrochemical anodization approach on a Ti film. This confined plasmonic photocatalyst with highly uniformly distributed Au cocatalysts exhibited greatly enhanced charge-separation and charge-transfer behavior, and a remarkable 10 times enhancement of the photocatalytic H₂ evolution reactivity over conventional TiO₂ nanotube. The TiO₂-BT-Au electron transfer cascade structure is proposed in which black TiO₂ acts as a buffer layer for TiO₂ conduction band electrons, allowing efficient photogenerated electrons to be transferred to Au nanoparticles and then into the TiO₂ pores that suitable for H₂ generation. Since the nanotube walls themselves are curved upwards, the short diffusion length allows electrons to be easily transferred to the cocatalyst, where recombination of photogenerated electron pairs is limited. The metal magnetron sputter technique for noble metal cocatalyst immobilization and the unique TiO₂–BT–Au electron-transfer system are promising and can be extended to the design of other supported catalysts.     

Enhanced surface electron transfer by fabricating a core/shell Ni@NiO cluster on TiO2 and its role on high efficient hydrogen generation under visible light irradiation

A Ni@NiO core/shell cluster was fabricated on TiO₂ surface (Ni@NiO/TiO₂) and its roles on surface electron transfer and the enhancement on hydrogen evolution under visible light irradiation were investigated. For a comparison, the Ni/TiO₂ and NiO/TiO₂ catalysts were fabricated, respectively. By photosensitization using Eosin Y as an antenna molecule, (1.6 wt%)Ni@NiO/TiO₂ exhibited the highest activity (364.1 μmol h⁻¹) in comparison with (1.6 wt%)Ni/TiO₂ and (1.6 wt%)NiO/TiO₂ and the corresponding apparent quantum efficiency reached 28.6% at 460 nm. The photoluminescence spectra and photoelectrochemical characterization results confirmed that the Ni@NiO core/shell structure could promote the photogenerated electrons transferring from TiO₂ conduction band to Ni@NiO clusters, resulting in the quicker separation of electron–hole pairs. In addition, part of NiO shell can be reduced into metallic Ni during the photoreaction and vice versa. Cyclic voltammogram characterization verified that the transformation between Ni and NiO was a dynamic balance process, which can not only provide reacting channels for electrons and protons but also ensure the photocatalytic hydrogen evolution proceeding continuously. This study discloses structure-dependent effect of non-noble metal cocatalyst on semiconductor photocatalysts in photocatalytic water reduction, and gives an insight into designing high-efficient non-noble metal/semiconductor hybrid photocatalysts.     

Efficient interfacial charge transfer of 2D/2D CoP/CdS heterojunction for extremely boosted photocatalytic H2 evolution performance

Constructing 2D/2D heterojunction photocatalysts has attracted great attentions due to their inherent advantages such as larger interfacial contact areas, short transfer distance of charges and abundant reaction active sites. Herein, 2D/2D CoP/CdS heterojunctions were successfully fabricated and employed in photocatalytic H₂ evolution using lactic acid as sacrificial reagents. The multiple characteristic techniques were adopted to investigate the crystalline phases, morphologies, optical properties and textual structures of heterojunctions. It was found that integrating 2D CoP nanosheets as cocatalysts with 2D CdS nanosheets by Co–S chemical bonds would significantly boost the photocatalytic H₂ evolution performances, and the 7 wt% 2D/2D CoP/CdS heterojunction possessed the maximal H₂ evolution rate of 92.54 mmol g^?1 h^?1, approximately 31 times higher than that of bare 2D CdS nanosheets. Photoelectrochemical, steady photoluminescence (PL) and time-resolved photoluminescence (TRPL) measurements indicated that there existed an effective charge separation and migration over 2D/2D CoP/CdS heterojunction, which then markedly lengthened the photoinduced electrons average lifetimes, retarded the recombination of charge carriers, and caused the dramatically boosted photocatalytic H₂ evolution activity. Moreover, the density functional theory (DFT) calculation further corroborated that the efficient charge transfer occurred at the interfaces of CoP/CdS heterojunction. This present research puts forward a promising strategy to engineer the 2D/2D heterojunction photocatalysts endowed with an appealing photocatalytic H₂ evolution performance.     

Nickel sulfide as co-catalyst on nanostructured TiO2 for photocatalytic hydrogen evolution

In this study, TiO₂ photocatalysts with nickel sulfide cocatalyst are prepared by loading nickel sulfide on TiO₂ with solvothermal synthesis approach. The materials were prepared by glycol solvothermal method using anatase, nickel nitrate, thiourea as precursor. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), ultraviolet–visible diffuse reflectance spectroscopy (UV–vis DRS), and X-ray photoelectron spectroscopy (XPS). This is the first time to report that NiS is used as a cocatalyst with TiO₂ for the photocatalytic production of H₂. The results revealed that the structure and the amount of the cocatalyst loaded on TiO₂ play important roles in the photocatalytic activity of NiS/TiO₂ composite. The maximum evolution of H₂ was obtained when NiS had hexagonal structure with content in the composite of 7 at% in relation to TiO₂. The rate of H₂ evolution was increased up to about 30 times than that of TiO₂ alone.     

CuS,NiS as co-catalyst for enhanced photocatalytic hydrogen evolution over TiO2

TiO₂ photocatalysts loaded CuS and NiS as co-catalyst were prepared by hydrothermal approach and characterized by XRD, UV–visible DRS, BET, XPS, SEM and TEM. When TiO₂ was loaded MS as co-catalyst, it showed higher photocatalytic activities for splitting water into hydrogen in methanol aqueous solution under 500 W Xe lamp. Among the photocatalysts with various compositions, the maximum evolution of H₂ obtained from 5 wt% CuS–5 wt% NiS–TiO₂ sample was about 800 μmol h⁻¹, which was increased up to about twenty-eight times than that of TiO₂ alone. It was proven that CuS, NiS can act as effective dual co-catalysts to enhance the photocatalytic H₂ production activity of TiO₂.     

Highly efficient thiomolybdate [Mo2S12]2- nanocluster cocatalyst decorated on TiO2 to boost photocatalytic hydrogen evolution

The exploitation of noble-metal-free photocatalysts with high solar-to-H₂ conversion efficiency is a hot topic in the photocatalysis field. Molybdenum sulfide materials, which have good physicochemical properties and excellent hydrogen evolution activity, have become an effective noble metal cocatalyst substitute and attracted widespread attention. In this work, a highly efficient photocatalyst constructed by decorating thiomolybdate [Mo₂S₁₂]^2- nanoclusters on TiO₂ is reported for the first time. The resultant [Mo₂S₁₂]^2-/TiO₂ photocatalyst shows a remarkable enhanced hydrogen evolution rate under the Xenon light irradiation. At the optimal loading amount of [Mo₂S₁₂]^2-, the photocatalyst exhibits a photocatalytic hydrogen evolution rate of 213.1 μmol h^?1 g^?1, which is about 51 times that of the pure TiO₂. Characterization results show that the intimate contact between [Mo₂S₁₂]^2- and TiO₂ promotes the separation of hole-electron pairs, prolongs the lifetime of carriers, and thereby increases the photocatalytic activity. Furthermore, abundant bridging S in the [Mo₂S₁₂]^2- acts as active sites for hydrogen evolution, which also contributes to the enhanced hydrogen production rate. This work demonstrates an efficient way for the construction of noble-metal-free hydrogen evolution photocatalyst and provides a useful reference for the development of low cost photocatalysts in the future.     

New evidence for the regulation of photogenerated electron transfer on surface potential energy controlled co-catalyst on TiO2 – The investigation of hydrogen production over selectively exposed Au facet on Au/TiO2

In this study, Au/TiO₂ samples with different exposed facets ({100}, {100/111}, and {111}) of Au were employed as catalysts for the examination of facet-dependent catalytic activity toward photocatalytic hydrogen evolution from water. By photosensitized using Eosin Y as antenna molecule, Au/TiO₂ series photocatalysts exhibited different photocatalytic hydrogen evolution performances under visible light irradiation. Au{111}/TiO₂ photocatalyst presented the highest photocatalytic hydrogen generation activity among Au/TiO₂ series samples. As evidenced by photoluminescence spectra, photocurrent, electrochemical impedance spectra, and Mott–Schottky characterizations, the difference in photocatalytic activities resulted from the different electron transfer rates from the conduction band of TiO₂ to Au nanoparticles. Au nanoparticles with exposed {111} facets were more effective in trapping electrons due to their higher Fermi level. In addition, the apparent activation energy of Au{111}/TiO₂ sample was the lowest, resulted from the biggest uncoordinated numbers of Au atoms on Au{111} nanoparticles, which was favor in forming the hydrogen–metal bond. This study discloses the facet-dependent effect of noble-metal cocatalyst on semiconductor photocatalysts in photocatalytic water reduction, and will give an insight into design and synthesis of high-efficient noble metal/semiconductor hybrid photocatalysts.     

A novel pathway toward efficient improvement of the photocatalytic activity and stability of CdS-based photocatalyst for light driven H2 evolution: The synergistic effect between CdS and SrWO4

It has been a research hot spot how to efficiently heighten the photocatalytic activity and stability of CdS-based photocatalysts for H₂ evolution. Here, SrWO₄/CdS nanoparticles which contained CdS/SrWO₄ heterojunctions were prepared. Meanwhile, their photocatalytic performance and stability were investigated in detail for H₂ evolution. At last, the photocatalytic mechanism of the SrWO₄/CdS nanoparticles was discussed roughly. The results show that the photocatalytic performance of CdS can be heightened significantly due to introduction of SrWO₄. The fastest evolution rate of H₂ over the SrWO₄/CdS nanoparticles is 392.5 μmol g⁻¹ h⁻¹, which is 5.8 times as high as that over the pure CdS nanomaterial. More interestingly, the SrWO₄/CdS nanoparticles possess excellent stability. The evolution rate of H₂ over the photocatalyst used 10 times can be up to 473 μmol g⁻¹ h⁻¹, which is the same as that over the once used sample, even is 37% higher than that over of the fresh one. In contrast, after used five times, the photocatalytic activity of the pure CdS nanomaterial is only 57% of that of the fresh sample. This study will supply a new idea for the design and development of highly stable and efficient CdS-based photocatalysts for H₂ evolution in the future.     

CoNi bimetallic alloy cocatalyst-modified TiO2 nanoflowers with enhanced photocatalytic hydrogen evolution

In terms of improving photocatalytic hydrogen production performance, inexpensive and earth-rich cocatalysts have become promising alternatives to precious metals. Herein, a novel CoNi–TiO₂ photocatalyst composed of TiO₂ nanoflowers and CoNi alloy was prepared by hydrothermal and chemical reduction methods. Various characterizations and test results have confirmed that the further improvement of the photocatalytic performance of the CoNi–TiO₂ photocatalyst is mainly due to the fact that the bimetallic CoNi alloy can accelerate charge transfer and inhibit the recombination of photo-induced carriers. The hydrogen production rate of the prepared CoNi–TiO₂ is about 24 times higher than that of the pristine TiO₂, and its hydrogen production rate value can reach 6580.9 μmol g^?1 h^?1, and showing comparable photocatalytic performance to 0.5 wt% Pt–TiO₂. In addition, combined with the characterization results, a probable mechanism for enhanced photocatalytic performance was proposed. This study provides favorable enlightenment for the design of a series of highly efficient non-precious metal TiO₂-based photocatalysts.     

In-situ photo-deposition CuO1−x cluster on TiO2 for enhanced photocatalytic H2-production activity

CuO_1?x cluster-modified TiO₂ (CuO_1?x/TiO₂) photocatalysts were prepared by an in-situ photoreduction deposition of Cu on TiO₂ powder support using copper acetate as a Cu source. The prepared samples without any Pt co-catalyst present an especially high photocatalytic H₂-evolution activity under solar light irradiation with 5% glycerol as sacrificial agent. The optimal CuO_1?x/TiO₂ catalyst with only 1 wt% CuO_1?x exhibits a high activity of 1725 μmol h^?1 g^?1 for H₂ evolution, which reaches 120 times that of TiO₂. The high photocatalytic activity of H₂ production is attributed to the highly dispersed CuO_1?x nano clusters on the surface of the TiO₂. In addition, Pt/CuO_1?x/TiO₂ was also prepared by loading Pt on CuO_1?x/TiO₂ sample, and its photocatalytic hydrogen evolution activity is enhanced 1.8 times compared with that of Pt/TiO₂ for overall water splitting reaction under solar light, demonstrating that a small amount CuO_1?x wondrously improves the photocatalytic activity of Pt/TiO₂ for overall water splitting reaction. This paper reports an economic and simple approach to prepare a photocatalyst with high hydrogen-production activity.