NiS2 Co-catalyst decoration on CdLa2S4 nanocrystals for efficient photocatalytic hydrogen generation under visible light irradiation

NiS₂ nanoparticles as noble metal-free co-catalysts were deposited onto the CdLa₂S₄ nanocrystals through a hydrothermal process. The loading of NiS₂ co-catalyst resulted in remarkable enhancement for H₂ production over the CdLa₂S₄ photocatalyst under visible light irradiation. The optimal hybrid photocatalyst with 2 wt% NiS₂ loading exhibited a H₂ production rate of 2.5 mmol h⁻¹ g⁻¹, which was more than 3 times higher than that of the pristine CdLa₂S₄ photocatalyst. The promoted photocatalytic H₂ production by NiS₂-loading is attributed to the enhanced separation of photogenerated electrons and holes as well as the activation effect of NiS₂ for H₂ evolution.     

Novel synthesis of graphene oxide/In2S3/TiO2 NRs heterojunction photoanode for enhanced photoelectrochemical (PEC) performance

Novel heterostructure photocatalyst built from titanium dioxide (TiO₂), graphene oxide (GO) and indium sulfide (In₂S₃) has been successfully prepared for photoelectrochemical hydrogen production. The stepwise introduction of three materials on conductive glass substrate has been realized through hydrothermal, electrochimical and spin coating deposition methods, respectively. The structure, morphology, composition, optical and photoelectrochemical properties of the resultant photoanodes were investigated in detail. The presence of GO in the heterostructure film was confirmed by Raman analysis with D and G band intensity. Surface morphology analysis of the GO/In₂S₃/TiO₂ NRs structure reveal the homogenous distribution of graphene oxide on In₂S₃/TiO₂ NRs surface. From UV–Vis analysis, band gap energy of the samples decreases gradually from 3.34 eV (TiO₂ NRs) to 3.12 eV, with In₂S₃ and GO addition. The electrochemical impedance spectroscopy (EIS) further confirmed that GO/In₂S₃/TiO₂NRs heterostructure possessed the lowest charge-transfer resistance, revealing that In₂S₃ and GO could significantly accelerate the electron mobility compared with bare TiO₂. From Mott-Schottky plots, several parameters such as flat-band potential and free carrier concentration were determined. Next, The GO/In₂S₃/TiO₂ NRs electrode achieved remarkably improved current density (0.45 mAcm² at 0.8 V vs Ag/AgCl) compared to pure TiO₂ NRs or In₂S₃/TiO₂ NRs electrodes, which attributes to the uniform structure and excellent electrical conductivity of GO, which could reduce the combination rate of the photo electron-hole pairs. These results reveal that GO/In₂S₃/TiO₂ NRs possesses great potential toward the development of newly synthesizable catalysts in the field of photoelectrochemical water splitting.     

Boosted photogenerated carriers separation in Z-scheme Cu3P/ZnIn2S4 heterojunction photocatalyst for highly efficient H2 evolution under visible light

Developing low-cost, highly efficient and robust photocatalystic hydrogen evolution system is a promising solution to environmental and energy crisis. Herein, a Z-scheme Cu₃P/ZnIn₂S₄ heterojunction photocatalyst was successfully constructed for the first time via a facile solution-phase hybridization method. The optimized Cu₃P/ZIS composite exhibited the highest H₂ production rate of 2561.1 μmol g⁻¹ h⁻¹ under visible light irradiation (>420 nm), which was 5.2 times greater than that of bare ZnIn₂S₄ and even exceeded the photocatalytic performance of Pt/ZIS composite. The apparent quantum yield of 10 wt% Cu₃P/ZnIn₂S₄ can reach 22.3% at 420 nm. The huge boost of photocatalytic hydrogen evolution activity is ascribed to the formation of heterojunction with the built in electric field within Cu₃P/ZnIn₂S₄ and Z-scheme charge carriers transfer pathway, which result in efficient separation and migration of charge carriers. In addition, both experimental and theoretical calculation confirmed that the charge-carriers transfer pathway of Cu₃P/ZnIn₂S₄ photocatalyst follows the Z-scheme mechanism instead of conventional type-Ⅱ heterojunction mechanism. This work is considered helpful for getting a great deal of insight into constructing high-activity and cost-effective transition metal phosphides (TMPs) based photcatalytic hydrogen production system and rationally designing Z-scheme heterojunction photocatalyst.     

In2Se3/CdS nanocomposites as high efficiency photocatalysts for hydrogen production under visible light irradiation

Hydrogen energy is an important clean energy. Using visible light to produce hydrogen by semiconductor photocatalysts is one of the current research hotspots. In this work, In₂Se₃/CdS nanocomposite photocatalysts with different mass content of CdS are prepared. The In₂Se₃/CdS photocatalyst with 85.25% CdS mass content exhibits the optimal photocatalytic hydrogen evolution activity (1.632 mmol g^?1 h^?1), which is much higher than that of CdS (0.715 mmol g^?1 h^?1) and In₂Se₃ (trace). Moreover, the In₂Se₃/CdS photocatalyst still maintains a high hydrogen evolution rate after five cycles. The high photocatalytic activity and stability of the In₂Se₃/CdS nanocomposite is due to the formation of heterojunction between In₂Se₃ and CdS. The existence of heterojunction is confirmed by high resolution transmission electron microscopy image and X-ray photoelectron spectra. Theoretical calculations and experimental results indicate that the electron transfer route at the heterojunction is step-scheme. The step-scheme helps the separation of photogenerated electrons and holes, and maximize the hydrogen evolution activity. This work provides a high efficiency step-scheme photocatalyst for hydrogen production.     

Elaboration and characterization of the brownmillerite Ca2Fe2O5 synthesized by citrate sol-gel method. Application for photocatalytic H2-Production under visible light over Ca2Fe2O5/ZnO hetero-system

The present work is devoted to the synthesis of the ferrite Ca₂Fe₂O₅ as photocatalyst crystallizing in the brownmillerite structure. The ternary oxide is prepared by sol-gel auto combustion and characterized by physical and electrochemical methods. The thermal analysis (TG/DSC) shows that, the formation of the brownmillerite is observed above 660 °C. The X-ray diffraction and BET analysis show respectively a single phase with an active surface area of ～6 m² g^?1. The SEM micrographs exhibit an inhomogeneous structure formed by agglomeration of irregular shaped grains, confirmed by the laser granulometry analysis. The forbidden band (～2.3 eV) determined from the diffuse reflectance, permits to explore ～ 30% of the sun spectrum into chemical energy. The p-type comportment of Ca₂Fe₂O₅ is demonstrated by the capacitance-potential (C^?2 - E) graph with a flat band potential (E_fb = 0.93 V_SCE), due to oxygen over-stoichiometry. The negative potential of the conduction band (?1.06 V_SCE) predicts the feasibility of the H₂ generation. Indeed, Ca₂Fe₂O₅ is chemical stable in a wide pH domain and is positively experimented as photocatalyst for the H₂-production under visible light. The best performance is obtained in alkaline medium (NaOH, 0.1 M) with a mean evolution rate of 18 μmol g^?1 min^?1. However, Ca₂Fe₂O₅ coupled to ZnO sol-gel (ZnO-SG) improves the catalytic performance. The H₂ evolution rate over (Ca₂Fe₂O₅/ZnO-SG) reached 24 μmol g^?1 min^?1 after 60 min. It has also been shown that ZnO–P, prepared by precipitation, is more efficient than that synthetized by sol-gel method (ZnO-SG) and TiO₂–P25.     

Facile fabrication of mesoporous In2O3/LaNaTaO3 nanocomposites for photocatalytic H2 evolution

The incorporation of In₂O₃ nanoparticles on mesoporous La_0.02Na_0.98TaO₃ photocatalysts is very interesting for promoting the H₂ production under UV illumination in the presence of [10%] glycerol as a hole scavenger. It is demonstrated that an outstanding mesoporous In₂O₃/La_0.02Na_0.98TaO₃ photocatalyst can be constructed by incorporating In₂O₃ nanoparticles (0-2 wt%) and mesoporous La_0.02Na_0.98TaO₃ nanocomposites for highly promoting photocatalytic H₂ evolution. The maximum yield of H₂ ~ 2350 μmol g⁻¹ was obtained over mesoporous 1%In₂O₃/La_0.02Na_0.98TaO₃ nanocomposite. The mesoporous 1%In₂O₃/La_0.02Na_0.98TaO₃ nanocomposite exhibited further enhancement H₂ production, in which the rate of H₂ evolution can be as high as 235 μmol g⁻¹ h⁻¹, 435 times higher than those of mesoporous La_0.02Na_0.98TaO₃. The results showed that the 1%In₂O₃/La_0.02Na_0.98TaO₃ photocatalyst possesses high stability and durability for H₂ evolution by implying almost no photoactivity reduce after five cycles for 45 h continuous illumination. The measurement of photoluminescence spectroscopy, transient photocurrent spectra and UV- diffuse reflectance spectra for all synthesized samples exhibited that the promoted H₂ production is mainly explained by its effective electron-hole separation and broaden photoresponse region due to its compositions and structures of the obtained heterostructures.     

Enhanced photocatalytic hydrogen production over In-rich (Ag–In–Zn)S particles

The ratio of ZnS to AgInS₂ is usually adjusted to tune the band gaps of this quaternary (Ag–In–Zn)S semiconductor to increase photocatalytic activity. In this study, the [Zn]/[Ag] ratio was kept constant. The hydrogen production rate was enhanced by increasing the content of indium sulfide. Compared to the steady H₂ evolution rate obtained with equal moles of indium and silver ([In]/[Ag] = 1, 0.64 L/m² h), that obtained with In-rich photocatalyst ([In]/[Ag] = 2, 3.75 L/m² h) is over 5.86 times higher. The number of nanostep structures, on which the Pt cocatalysts were loaded by photodeposition, increased with the content of indium. The indium-rich samples did not induce phase separation between Ag_xIn_xZn_yS_2x+y and AgIn₅S₈, instead forming a single-phase solid solution. Although the photocatalytic activity decreased slightly for bare In-rich photocatalysts, Pt loading played a critical role in the hydrogen production rate. This study demonstrates the significant effect of In₂S₃ on this unique (Ag–In–Zn)S photocatalyst.     

Oxidation co-catalyst modified In2S3 with efficient interfacial charge transfer for boosting photocatalytic H2 evolution

Constructing an efficient co-catalyst/photocatalyst system for charge separation boosting photocatalytic hydrogen generation is a vital challenge. Herein, highly-dispersed PdS nanoparticles (NPs) acting as an efficient hole co-catalyst has been decorated on the ultrathin In₂S₃ nanosheets. The strong interactions between PdS and In₂S₃ via Pd–S–In bonds enable an intimate interface junction. Due to the high capacity of PdS for the hole capture with the assistance of internal electric field, the photogenerated charge carriers are not only separated effectively, the semiconductor photocatalyst In₂S₃ is also protected from the photo-oxidation. As expected, a remarkable H₂ production rate of 142.27 μmol/h has been achieved for 3PdS/In₂S₃ nanocomposite, which is 149.8 times higher than that of the pristine In₂S₃ nanosheets, and 13.3 times superior to the In₂S₃ decorated with a reductive co-catalyst Pt. This work provides a new insight into the co-catalyst modification engineering for an efficient photocatalytic energy conversion.     

The pH effects on H2 evolution kinetics for visible light water splitting over the Ru/(CuAg)0.15In0.3Zn1.4S2 photocatalyst

Much progress has been made in the development of novel visible light photocatalysts that split water into hydrogen (H₂) and oxygen (O₂). In this study, we examine the impact of initial solution pH on H₂ production using an Ru/(CuAg)_0.15In_0.3Zn_1.4S₂ photocatalyst under visible light irradiation. In addition, the reaction mechanism was analyzed by examining the oxidation products of the electron donor (I‾) at different solution pH values. The results show that the initial pH significantly influenced the rate of H₂ production and quantum yield (QY). In particular, the photocatalyst yielded the highest apparent QY (∼12.8%) at 420 ± 5 nm and highest H₂ production rate (∼525 μmol h⁻¹) at pH 2; with increasing pH, the H₂ production and QY decreased significantly. The oxidation product of I‾ at pH < 6 was mainly I₃‾, whereas at pH > 6 water splitting did not occur at all, so no IO₃‾ or I₂ were observed.     

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.     

A new photosensitive coordination compound [RuL(bpy)2](PF6)2 and its application in photocatalytic H2 production under the irradiation of visible light

A new organic–inorganic photosensitive coordination compound [RuL(bpy)₂](PF₆)₂ (to represent by TM1) had been synthesized by reaction of L (L = 2-hydroxyl-5-(imidazo-[4,5-f]-1,10-phenanthrolin) benzoic acid) with bipyridyl ruthenium, and further characterized by UV–vis, IR, NMR MS and CV. The target photocatalyst 6 wt% TM1-0.5 wt% Pt-TiO₂ (Ⅰ) was obtained by sensitization of Pt-loaded TiO₂ with TM1. The H₂ production activity of target photocatalyst Ⅰ was systematically evaluated by the reaction of photocatalytic H₂ production from water under visible light irradiation. The maximum H₂ evolution of 386.7 μmol in irradiation 3 h and H₂ production rate of 2578 μmol · h⁻¹ · g⁻¹ was detected under the optimal conditions with pH 5, target photocatalyst Ⅰ 50 mg and 5% sacrificial reagent TEOA (v/v).     

Integration of ReS2 on ZnIn2S4 for boosting the hydrogen evolution coupled with selective oxidation of biomass intermediate under visible light

Challenge remains to develop a high activity of photocatalyst for large-scale industrial application in photocatalytic selective conversion of biomass alcohols into the value-added chemicals accompany with H₂ evolution in aqueous solution. Herein, ReS₂ as high efficiency co-catalyst is utilized to modify the flower-like ZnIn₂S₄ (ZIS) microspheres to obtain heterojunction composite, result in dramatically enhancements in photocatalytic oxidation of furfural alcohols cooperative with H₂ evolution. Further studies show that the optimal catalyst containing 4.08 wt% ReS₂ (RZIS-3) realize remarkably generation rates of H₂ and furfural at 3092.9 and 2981.1 μmol g^?1 h^?1, respectively, nearly 12 times faster than that of blank ZnIn₂S₄. Mechanism studies verify that the migration of the photogenerated carriers from ZnIn₂S₄ to ReS₂ leading to the remarkably photoactivity of the composite. Moreover, the typical photocatalysis not rely on a single model substrate, and high performance of the composite has been identified for the oxidation of other alcohols biomass intermediate to value-added aldehydes/ketones, providing a new insight for design and fabrication of the novel photocatalytic hydrogen evolution systems.     

Efficient photocatalytic H2 production using visible‐light irradiation and (CuAg)xIn2xZn2(1 − 2x)S2 photocatalysts with tunable band gaps

The band structures of semiconductor photocatalysts fundamentally determine the photocatalytic activity and the H₂ production from the visible‐light‐driven water‐splitting reaction. We synthesize a suite of multicomponent sulfide photocatalysts, (CuAg)_xIn_2xZn_{2(1 ? 2x)}S₂ (0 ≤ x ≤ 0.5), with tunable band gaps and small crystallite sizes to produce H₂ using visible‐light irradiation. The band gap of the photocatalysts decreases from 3.47 eV to 1.51 eV with the increasing x value. The (CuAg)_0.15In_0.3Zn_1.4S₂ (x = 0.15) photocatalyst yielded the highest photocatalytic activity for H₂ production owing to the broad visible‐light absorption range and suitable conduction band potential. Under the optimized reaction conditions, the highest H₂ production rate is 230 µmol m^?2 h^?1 with a visible‐light irradiation of 2.7 × 10^?5 einstein cm^?2 s^?1, and the quantum yield reaches 12.8% at 420 ± 5 nm within 24 h. Furthermore, the photocatalytic H₂ production is shown to strongly depend on their band structures, which vary with the elemental ratios and could be analyzed by the Nernst relation. Copyright © 2014 John Wiley & Sons, Ltd.     

Efficient photocatalytic H2 evolution over Cu and Cu3P co-modified TiO2 nanosheet

Schottky junction and p-n heterojunction are widely employed to enhance the charge transfer during the photocatalysis process. Herein, Cu and Cu₃P co-modified TiO₂ nanosheet hybrid (Cu–Cu₃P/TiO₂) was fabricated using an in situ hydrothermal method. The ternary composite achieved the superior H₂ evolution rate of 6915.7 μmol g^?1 h^?1 under simulated sunlight, which was higher than that of Cu/TiO₂ (4643.4 μmol g^?1 h^?1) and Cu₃P/TiO₂ (6315.8 μmol g^?1 h^?1) and pure TiO₂ (415.7 μmol g^?1 h^?1). The enhanced activity can be attributed to the collaboration effect of Schottky junction and p-n heterojunction among Cu/TiO₂ and Cu₃P/TiO₂, which can harvest the visible light, reduce the recombination of charge carriers and lower the overpotential of H₂ evolution, leading to a fast H₂ evolution kinetics. This work develops a feasible method for the exploration of H₂ evolution photocatalyst with outstanding charge separation properties.     

Novel 0D/1D ZnBi2O4/ZnO S-scheme photocatalyst for hydrogen production and BPA removal

Developing interfacial connections is one of the breakthrough strategies to improve the photocatalytic activity. Herein, ZnBi₂O₄ nanoparticles-ZnO nanorods heterojunction was successfully synthesized and used, as a dual-function photocatalyst, for photocatalytic degradation of Bisphenol A and hydrogen production with improved photocatalytic activity under simulated sunlight irradiation. The highest H₂ production (3.44 mmol g^?1 h^?1) was obtained for ZnO-20 wt% ZnBi₂O₄ sample, which is around 12.7 times higher than pure ZnO. According to the HRTEM result, the intimate interfacial connections are formed between ZnO and ZnBi₂O₄ which could act as trapping centers for charge carriers and results in the boosted photocatalytic activity. Further, a high aspect ratio of 1D ZnO nanorods and small size of 0D ZnBi₂O₄ nanoparticles (~10 nm) increases the number of interfacial contacts and thus the charge carriers’ recombination was suppressed more efficiently. Based on the trapping experiments, ESR and Mott-Schottky analysis, ZnBi₂O₄–ZnO hybrid photocatalyst followed the S-scheme charge transfer mechanism.     

In2S3/AgIO3 photoanode coupled I−/I3− cyclic redox system for solar-electrocatalytic recovery of H2 and S from toxic H2S

The abundant availability of toxic H₂S in many industrial and natural resources and its low thermodynamic decomposition makes it a viable economic source for the production of environmentally clean fuel (H₂). Here, a highly efficient In₂S₃/AgIO₃ photoanode and Pt/C–based waterproofed carbon fibre cathode were prepared for the recovery of H₂ and S from toxic H₂S in a cyclic redox system of I⁻/I₃⁻. The H₂S was oxidized to S by I₃⁻ in the photoanode compartment and H⁺ was efficiently reduced to H₂ in the photocathode region. A maximum H₂ and S production rate of ∼0.26 mmol h⁻¹ cm⁻² and ∼0.23 mmol h⁻¹ cm⁻² were achieved, respectively and the photocurrent density of ∼0.9 mA cm⁻² was attained during the entire operation. The In₂S₃/AgIO₃ photoanode exhibited high energy conversion efficiency and polysulfides were not detected after the reaction, suggesting that the toxic H₂S was completely converted into H₂ and S. The proposed system with I⁻/I₃⁻ redox provides an energy-sustaining method for simultaneous treatment of toxic H₂S and clean fuel production.     

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.     

Platinum deposition onto g-C3N4 with using of labile nitratocomplex for generation of the highly active hydrogen evolution photocatalysts

The chemisorption of the labile dimeric platinum nitratocomplex [Pt₂(μ-OH)₂(NO₃)₈]^2- onto graphene oxide doped graphitic C₃N₄ (g–C₃N₄–GO) was performed for the first time to prepare PtO_x/g–C₃N₄–GO composites with ionic platinum species (Pt(II)) bonded with N-donor groups of the g-C₃N₄. The thermal treatment of the obtained composites in the hydrogen atmosphere results in a gradual reduction of Pt(II) species with the formation of Pt/g–C₃N₄–GO photocatalysts. The Pt/g–C₃N₄–GO catalysts paired with TEOA sacrificing agent in an aqueous solution were tested in a photoinduced hydrogen evolution reaction under visible light (λ = 425 nm). The photocatalytic activity of prepared materials strongly influenced by the temperature of the reduction stage so that the maximal rate of H₂ evolution was revealed for the catalyst (0.5 wt% of Pt) reduced at 400 °C with a quantum efficiency of 3.0% and rate of HER of 5.1 mmol h^?1 per 1 g of photocatalysts. The photocatalytic activity of this sample was much higher than the activity of 0.5% Pt/g–C₃N₄–GO photocatalysts prepared by conventional photoreduction of H₂PtCl₆ or reduction of this precursor with NaBH₄. The Pt/g–C₃N₄–GO photocatalyst with Pt concentration of 0.1 wt% was prepared using the described protocol and shown specific activity of about 1.4 mol h^?1 per 1 g of Pt outperforming analogous material reported to date.     

Highly active FexCo1-xP cocatalysts modified CdS for photocatalytic hydrogen production

In this paper, we report a ternary Fe_xCo_1−xP co-catalyst, which can greatly improve the photocatalytic performance of CdS photocatalyst for hydrogen production under visible light irradiation. The high efficiency of ternary Fe_xCo_1-xP loaded CdS is mainly due to the high electrochemical activity and efficient charge transfer between Fe_xCo_1-xP cocatalyst and CdS. Experimental results have shown that the substitution of Fe ions for some Co ions in CoP can change the electrochemical properties of Fe_xCo_1-xP. The electrocatalytic performance of Fe_xCo_1-xP and the photocatalytic activity of Fe_xCo_1-xP/CdS are both dependent on the molar concentration x of Fe. When x = 0.4 the hydrogen generation rate (18.27 mmol h⁻¹ g⁻¹) and the quantum efficiency (50.6% at 420 nm) for 0.5 wt% Fe_0.4Co_0.6P/CdS photocatalyst is 5.85 times higher than that of pure CdS and 1.35 times higher than that of 0.5 wt% CoP/CdS. This new noble-metal-free Fe_xCo_1-xP cocatalyst is beneficial for the solar hydrogen economy.     

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.