H2 Evolution Activity Research Articles

Co3O4 Nanosheet/g-C3N4 Hybrid Photocatalysts for Promoted H2 Evolution

Co3O4 is an attractive semiconductor in the photocatalytic field due to its proper band gap; however, its energy level structure is mismatched for H2 evolution. Herein, the Co3O4-based photocatalysts, Co3O4 nanosheet/g-C3N4 hybrids, were successfully prepared by an ultrasonic self-assembly method for enhanced photocatalytic H2 evolution. The optimized hybrid with 20 wt % g-C3N4, 20-CNCo, displayed the best photocatalytic performances, and the average H2 evolution rate was 134.6 μmol·g–1·h–1. The enhanced photocatalytic H2 evolution activities of 20-CNCo were due to the formation of heterojunctions between Co3O4 nanosheets and g-C3N4, which can increase the optical absorption ability, promote the separation of photogenerated charges, accelerate the electron transfer, and prolong the lifetime of the excited electrons. Moreover, following the unique step-scheme (S-scheme) charge transfer mechanism, the strong redox ability of the Co3O4 nanosheet/ g-C3N4 hybrid was retained, which was beneficial to the H2 evolution. This work provides strategies for designing active catalysts for photocatalytic reactions.

Alkali-assisted deep-deamination to improve the crystallinity of poly(heptazine imide) for boosted photocatalytic H2 evolution

The poly(heptazine imide) (also known as heptazine-based crystalline carbon nitride, abbreviated as PHI) has drawn wide attention in solar energy conversion, which is profited from its improved photoinduced charge separation compared with melon-based carbon nitride. Nevertheless, the crystallinity of the samples synthesized by direct heat-treating precursors is low and further impede electron transport. This situation is especially prominent if precursors are used in large quantities and the reason is also unclear at present. Herein, this crucial issue was preliminarily revealed: the by-product HCl formed in the synthesis process has seriously restricted the deamination of PHI if it cannot be removed in time. Based on this, an original alkali-assisted method was proposed and demonstrated to realize deep-deamination for improving the crystallinity and extending π-conjugation of PHI. Benefit from this, alkali-assisted synthesized PHI illustrates significantly enhanced electron transport performance and further improved photocatalytic H2 evolution activity. The optimized PHI exhibits highly boosted photocatalytic H2 evolution activity of 2223 μmol h−1, which is 18 times that of original PHI synthesized without alkali-assistance. Additionally, the mechanism was further verified by density-functional theory (DFT) computations and the universality of alkali-assisted method was verified by using different kinds of alkali.

Ag decorated ZnO for enhanced photocatalytic H2 generation and pollutant degradation

In this study, Ag/ZnO photocatalyst is synthesized in ethylene glycol (EG) medium using a one-pot hydrothermal method, where EG serves as both a reaction medium for the synthesis and a reduction medium for silver. Standard analytical techniques such as XRD, XPS, SEM-EDX, TEM, HR-TEM FTIR, BET, and UV–Vis spectroscopy are used to characterize the synthesized samples. The XRD and HR-TEM results show that Ag has been decorated on the ZnO photocatalyst. The results show that spherical Ag/ZnO has the highest photocatalytic activity for H2 evolution (30.1 μmol h−1) and RhB degradation. The increased photocatalytic activity can be attributed to the formation of the Schottky barrier at the heterojunction interface of metal-semiconductor and the plasmonic resonance effect of silver, which results in efficient separation and transportation of photo-induced charge carriers. This research could open up new avenues for the development of advanced ZnO-based visible light photocatalytic materials to address energy and environmental challenges.

Carbon nitride quantum dots-modified cobalt phosphate for enhanced photocatalytic H2 evolution.

In the present work, carbon nitride quantum dots (CNQDs)-modified cobalt phosphate (CoPi) composites CNQDs/CoPi-x (x = 1, 2, 3) were prepared at room temperature and characterized by FTIR, XRD, UV-Vis DRS, EIS, SEM, TEM/HR-TEM, XPS, and N2 gas adsorption. The morphologies and surface areas of CNQDs/CoPi-x have no remarkable change after modification of CNQDs, compared with pure CoPi. The obtained CNQDs/CoPi-x shows enhanced activity and stability of photocatalytic H2 evolution compared to pure CoPi using Eosin Y (EY) as a sensitizer and triethanolamine as an electron donor. The CNQDs/CoPi-2 possesses the highest hydrogen evolution rate, 234.5 μmol h-1 g-1 , upon visible light, which outshines that of CoPi by 2.4 times. It was believed that the enhanced photocatalytic performances of the CNQDs/CoPi-2 could result from the boosted electron transfer from radical EY·- to CNQDs/CoPi-2 by the employment of CNQDs; in addition, the visible-light activity of CNQDs contributes to hydrogen evolution. The mechanism of photocatalytic hydrogen production was discussed. This study may contribute toward the development of production of "green hydrogen" using solar.

Modulating the bridging units of carbon nitride for highly efficient charge separation and visible-light-responsive photocatalytic H2 evolution

Carbon nitrides have attracted broad attention in the field of photocatalytic H2 evolution. However, the design and preparation of carbon nitrides with highly efficient charge separation and transfer are still challenging. Here, we synthesized a novel heptazine derivative-based photocatalyst, named as M+U-x to overcome the inherent limitations of carbon nitrides (C3N4 and C3N5). Experimental and theoretical calculation results reveal that the resultant M+U-x is composed by electron-withdrawing C3N4 and electron-donating C3N5 moieties, which are integrated into the conjugated framework via N-atoms and azo bridging units to form molecular heterojunctions. Among these, M+U-3 can dramatically facilitate the spatial separation of photoinduced charge carriers, delivering significantly high visible-light-responsive H2 evolution activity of 372 μmol h−1 with an AQY of 21.6% at 400 nm. This work provides a novel strategy for rationally modulating the bridging units of carbon nitrides to acquire enhanced charge-carrier mobility and efficient photocatalytic H2 evolution from the molecular level.

Phase Engineering of 2D Violet/Black Phosphorus Heterostructure for Enhanced Photocatalytic Hydrogen Evolution

Rapid charge recombination has limited the application of black phosphorus (BP) as a visible light‐responsive photocatalyst. Violet phosphorus (VP), another 2D phosphorus allotrope, has drawn extensive attention for its excellent semiconductor property. However, its photocatalytic activity for hydrogen (H2) evolution is yet to be studied. Herein, a VP/BP heterostructure using a phase engineering strategy is constructed, wherein few‐layered VP is interlaced with BP to create a well‐matched heterophase interface by virtue of their identical chemical compositions and different crystal phases. Experimental and theoretical calculations reveal that VP and BP exhibit strong interaction at the heterophase interface, which is found effective in accelerating photogenerated electron transfer from BP to VP for improved charge separation efficiency. After being decorated with a Rh cocatalyst, the VP/BP heterostructure with utilization of visible light up to 700 nm shows ≈3‐ and 210‐times greater photocatalytic H2 evolution activity with respect to its counterparts. This study highlights feasibility of phase engineering and provides an alternative strategy in promoting charge separation as well as performance of photocatalyst.

Weakened crystalline SnNb2O6 for enhanced performance in photocatalytic H2 production and CO2 reduction.

Low crystalline photocatalysts with the unsaturated active site, such as oxygen vacancy (Ov), is reported to exhibit enhanced adsorption and activation of oxygen-containing small molecules, such as H2O and CO2, thus boosting the activity in photocatalytic H2 evolution and CO2 reduction. However, numerous low-crystalline photocatalysts show unsatisfactory stability due to the easily repaired surface Ov. Herein, three SnNb2O6 with different crystallinity were prepared by hydrothermal approach with similar precursors. Compared with bulk SnNb2O6 and ultra-thin layered SnNb2O6, low-crystalline SnNb2O6 (SNA) exhibits optimal visible-light-driven evolution rates of H2 (86.04 μmolg-1h-1) and CO from CO2 (71.97 μmolg-1h-1), which is mainly ascribed to the fast separation of the photogenerated carriers and enhanced photoreduction power caused by the surface Ov. More importantly, the sharp decrease of photocatalytic activity of SNA after seven cycles is well restored by the hydrothermal treatment of recycled SNA, ascribed to the reactivated surface Ov with the recovered low-crystalline structure. These works thus offer a promising strategy for developing low-crystalline and amorphous photocatalysts with high activity and stability.

Improved Visible-Light Photocatalytic H2 Evolution of G-C3N4 Nanosheets by Constructing Heterojunctions with Nano-Sized Poly(3-Thiophenecarboxylic Acid) and Coordinating Fe(III).

It is highly desirable to enhance the photogenerated charge separation of g-C3N4 by constructing efficient heterojunctions, especially with an additional organic constitution for solar-hydrogen conversion. Herein, g-C3N4 nanosheets have been modified controllably with nano-sized poly(3-thiophenecarboxylic acid) (PTA) through in situ photopolymerization and then coordinated with Fe(III) via the -COOH groups of modified PTA, forming an interface of tightly contacted nanoheterojunctions between the Fe(III)-coordinated PTA and g-C3N4. The resulting ratio-optimized nanoheterojunction displays a ~4.6-fold enhancement of the visible-light photocatalytic H2 evolution activity compared to bare g-C3N4. Based on the surface photovoltage spectra, measurements of the amount of •OH produced, photoluminescence (PL) spectra, photoelectrochemical curves, and single-wavelength photocurrent action spectra, it was confirmed that the improved photoactivity of g-C3N4 is attributed to the significantly promoted charge separation by the transfer of high-energy electrons from the lowest unoccupied molecular orbital (LUMO) of g-C3N4 to the modified PTA via the formed tight interface, dependent on the hydrogen bond interaction between the -COOH of PTA and the -NH2 of g-C3N4, and the continuous transfer to the coordinated Fe(III) with -OH favorable for connection with Pt as the cocatalyst. This study demonstrates a feasible strategy for solar-light-driven energy production over the large family of g-C3N4 heterojunction photocatalysts with exceptional visible-light activities.

Confinement of Cu2O by in-situ derived NH2-MIL-125@TiO2 for synergetic photothermal-driven hydrogen evolution from aqueous-phase methanol reforming

Photothermal synergism can effectively activate methanol at low operating temperature and significantly reduce the activation energy of the reaction, achieving more efficiently H2 release from methanol reforming. Here, a novel hierarchical heterojunction that integrating photo- and thermal-active Cu2O catalytic species with in-situ derived NH2-MIL-125@TiO2 framework was specifically designed for photothermal-driven aqueous phase reforming of methanol into H2. The afforded Cu2O/NH2-MIL-125@TiO2 realized an outstanding photothermal H2 production activity (apparent quantum efficiency of 22.3 % at 365 nm), ca. 13-times higher than that of thermocatalytic condition. Interestingly, the photothermal effect did confer the Cu2O/NH2-MIL-125@TiO2 with unexpected activity at low temperature subsided to 100 °C and accelerated the activation of MeOH/H2O with an obvious reduction of activation energy from 82.62 kJ·mol−1 to 52.40 kJ·mol−1.The improvement of catalyst stability and the promotion of charge separation also contributed to a long-term photothermal H2 evolution activity with average rate of 1.49x106 μmolgCu-1h−1 and a total turnover number (TON) up to 5971 in 63 h, almost 125-fold promotion compared with Cu2O.

Mixed-valence molybdenum ion incorporated graphitic carbon nitride with high photocatalytic H2 evolution activity

The graphitic carbon nitride (CN) incorporated with mixed-valence molybdenum ion has been prepared via in-situ copolymerization to improve the photocatalytic H2 evolution performance. The introduced Mo species existed in mixed valence of Mo4+ and Mo2+ state and its content could be tuned by simply adjusting amount of added MoCl5 in the preparation procedure. The incorporated mixed-valence Mo ions contributed to narrowed band gap, increased electron density and elevated electron motion kinetics, resulting in extended visible light response, promoted separation and transportation of photoexcited charge carriers. The obtained CN–Mo photocatalyst with an optimal content of Mo ions (0.41 wt%) exhibited a robust H2 production activity up to 1.44 mmol h−1 g−1, 18 times higher than that of pristine counterpart.

Tremella-like Boron-doped hierarchical CN and dispersion Co phthalocyanine assembling heterojunction for photocatalytic hydrogen evolution

Semiconducting photocatalysts' electronic configuration significantly impacts their band gaps, charge carrier transport properties, and photocatalytic activities. Boron-doped tremella-like hierarchical CN and ultrathin Co phthalocyanine (CoPe) heterojunction (B1.5HCN-Co0.5%) formation via strengthened H-bonding interfacial connection possess excellent photocatalytic activities in water where the small amounts of catalysts exhibit a high photocatalytic H2 evolution activity with H2 evolution rate of 17818.82 μmol h−1 g−1 under simulated sunlight and 5558.81 μmol h−1 g−1 under visible light (≥420 nm). According to detailed characterization, the unique tremella-like hierarchical structure with abundant mesopores shortens the charge diffusion length. At the same time, incorporating CoPe improves the charge transport properties of B1.5HCN achieving effective spatial separation, which is primarily responsible for the improved performance. Both a significant amount of experimental data and theoretical calculations demonstrated the critical role of boron-doped and CoPe in photocatalytic H2 evolution. Heteroatom doping and heterojunction construction are essential in rationally regulating band structure to construct more efficient CN-based photocatalysts.

Facile fabrication of NiWO4/ZnIn2S4 p-n heterojunction for enhanced photocatalytic H2 evolution

Construction heterojunction has been demonstrated to be a potential strategy to facilitate the activity of single component photocatalyst due to the enhanced light absorption, accelerated charge separation and so on. Herein, a NiWO4/ZnIn2S4 p-n heterojunction was prepared via a facile physical solvent evaporation method. In the binary system, the p-n heterojunction formed between NiWO4 and ZnIn2S4 can boost the charge separation. Besides, the introduction of NiWO4 can induce more electrochemically active surface area and decrease the overpotential of H2 evolution. In addition, the water angle contact (WAC) of ZnIn2S4 was reduced from 58.6° to 12.1°, suggesting a better hydrophilic surface. The photocatalytic activity tests indicated that the obtained composite exhibited excellent H2 evolution activity than NiWO4 or ZnIn2S4 alone. 10.7 %-NiWO4/ZnIn2S4 has a superior H2 production rate of 30.51 mmol·g−1·h−1, 4.42 folds higher than that of pure ZnIn2S4 (5.63 mmol·g−1·h−1). Meanwhile, the microstructure of 10.7 %-NiWO4/ZnIn2S4 is well preserved after reaction. This work provides experimental basis for the development of ZnIn2S4 based heterojunction for high-efficiency photocatalytic H2 evolution.

SO42− mediated CO2 activation on metal electrode for efficient CO2 electroreduction

The most difficulty of efficient CO2 electroreduction lies in the activation step that turns CO2 into the CO2− radicals or other intermediates that can be further converted. To overcome this bottleneck, many efforts have been devoted to develop electrocatalysts to lower the overpotential of CO2 activation, but they inevitably involve complicated or/and unscalable synthesis methods. Here we reported that the SO42− ion modified metal foils, including Zn, Ag, Au and Cu, demonstrated ∼6.5, 1.4, 14 and 2.5 times of CO faradaic efficiency in K2SO4 electrolyte compared to KHCO3 electrolyte at −1.05 V vs. RHE. According to both experimental and DFT studies, the electron-rich metal-SO4 adlayer can activate CO2 by bending the linear molecule of CO2 through donating electrons to the antibonding orbital of CO2, thus facilitating the formation of key intermediate *CO2−. Moreover, the adsorption of H+ on metal sites is restrained by the metal-SO4 adlayer, leading to a suppressed H2 evolution activity. From a broader perspective, many catalysts can benefit from this approach to achieve more efficient CO2 electrochemical reduction.

G-C3N4/ZnWO4 nanocomposites as efficient and stable S-scheme photocatalysts for hydrogen evolution

The use of photocatalysis to decompose water and produce hydrogen (H2) is a promising green energy technology with numerous potential applications. In this study, the design of g-C3N4/ZnWO4 (CN/ZWO) accompanied by an “S-scheme” heterojunction mechanism is reported for the first time, along with a thorough investigation of their photocatalytic H2 evolution activity and mechanism. It was found that the CN/ZWO nanocomposites effectively address the inherent issues of band gap defects, instability, and poor H2-evolving photocatalytic performance of pure CN. The CN/ZWO-0.15 in particular exhibited particularly high photocatalytic activity (1.195 mmol g−1 h−1), being 17.57 and 7.71 times more effective than pure CN and ZWO, respectively. In addition, the CN/ZWO-0.15 displayed good stability over a period of 12 h (four cycles) while maintaining its high activity. The presence of the nanocomposites was confirmed using TEM and in situ irradiated XPS (ISI-XPS), and the mechanism at the heterojunction was determined to be the S-scheme via ISI-XPS, EPR and theoretical calculations. The S-scheme mechanism involves the effective utilization of the valence-conduction band gap width of the system and the efficient photoinduced charge separation, and is believed to be responsible for the superior H2 release ability of the nanocomposites. This work presents a novel approach involving an S-scheme heterojunction to overcome the intrinsic defects of CN-based photocatalysts.

Exploring the Sub-nanoscale Structure of Cobalt Molybdenum Sulfide and the Role of a Cobalt Promoter in Catalytic Hydrogen Evolution.

Cobalt-promoted molybdenum sulfide (CoMoS) is known as a promising catalyst for H2 evolution reaction and hydrogen desulfurization reaction. This material exhibits superior catalytic activity as compared to its pristine molybdenum sulfide counterpart. However, revealing the actual structure of cobalt-promoted molybdenum sulfide as well as the plausible contribution of a cobalt promoter is still challenging, especially when the material has an amorphous nature. Herein, we report, for the first time, on the use of positron annihilation spectroscopy (PAS), being a nondestructive nuclear radiation-based method, to visualize the position of a Co promoter within the structure of MoS at the atomic scale, which is inaccessible by conventional characterization tools. It is found that at low concentrations, a Co atom occupies preferably the Mo-vacancies, thus generating the ternary phase CoMoS whose structure is composed of a Co-S-Mo building block. Increasing the Co concentration, e.g., a Co/Mo molar ratio of higher than 1.12/1, leads to the occupation of both Mo-vacancies and S-vacancies by Co. In this case, secondary phases such as MoS and CoS are also produced together with the CoMoS one. Combining the PAS and electrochemical analyses, we highlight the important contribution of a Co promoter to enhancing the catalytic H2 evolution activity. Having more Co promoter in the Mo-vacancies promotes the H2 evolution rate, whereas having Co in the S-vacancies causes a drop in H2 evolution ability. Furthermore, the occupation of Co to the S-vacancies leads also to the destabilization of the CoMoS catalyst, resulting in a rapid degradation of catalytic activity.

Ru/Pt@BSA nanoparticles for efficient photo-catalytic oxidation of NAD(P)H and targeted cancer treatment under hypoxic conditions

Photo-catalytic oxidation of intracellular nicotinamide adenine dinucleotide (2′-phosphate) (NAD(P)H) has attracted much attention for cancer therapy. However, the general oxygen-dependent mechanism heavily depresses the efficacy in hypoxic tumors. To solve this problem, herein platinum nanoparticles (Pt NPs) with catalase-like (CAT-like) and catalytic H2 evolution activities were introduced as a powerful assistant to enhance the photo-catalytic NAD(P)H oxidation of Ru1 ([Ru(phen)2(PIP-OCH3)]2+, phen = 1,10-phenanthroline, PIP-OCH3 = 2-(4‑methoxy phenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) under hypoxic and even oxygen-free conditions. Firstly, Pt NPs can transform the original and in situ formed H2O2 once again into O2 by the CAT-like activity, thus relieving tumor hypoxia and realizing cyclic utilization (at least in part) of the precious oxygen in hypoxia. Secondly, Pt NPs can also be served as H2 evolution catalysts while using Ru1 as the photosensitizer and NAD(P)H as the electron and proton donor. In this process, NAD(P)H is oxidized without the participation of oxygen, which can provide an effective way even under oxygen-free conditions. Via co-encapsulation of Ru1 and Pt NPs in bovine serum albumin (BSA) with tumor targeting ability, the resultant Ru/Pt@BSA could photo-catalyze intracellular NAD(P)H oxidation under hypoxic conditions (3% O2), and exhibited an efficient and selective anticancer activity both in vitro and in vivo. Our results may provide new sights for efficient and targeted cancer treatment under hypoxic conditions.

Cu2O/2D COFs Core/Shell Nanocubes with Antiphotocorrosion Ability for Efficient Photocatalytic Hydrogen Evolution.

Photocorrosion of highly active photocatalysts is an urgent problem to be solved in the field of photocatalysis; however, searching for effective strategies for inhibiting photocorrosion of photocatalysts is still a grand challenge. Herein, we design and construct a class of Cu2O/2D PyTTA-TPA COFs (PyTTA: 1,3,6,8-Tetrakis(4-aminophenyl)pyrene, TPA: p-benzaldehyde) core/shell nanocubes to greatly boost the performance of photocatalytic hydrogen evolution and significantly inhibit the photocorrosion. The optimal Cu2O/PyTTA-TPA COFs core/shell nanocubes exhibit an excellent photocatalytic H2 evolution rate of 12.5 mmol h-1 g-1, which is ∼8.0-fold and ∼20.0-fold higher than those of PyTTA-TPA COFs and Cu2O nanocube, respectively, and also is the best in all the reported metal oxides catalytic materials. The mechanism studies demonstrate that the appropriate matching band gaps and tight integration of PyTTA-TPA COFs and Cu2O nanocubes can significantly facilitate the separation of photogenerated electron-hole pairs in the Cu2O/PyTTA-TPA COFs core/shell nanocube during the photocatalytic process, which ameliorates the photocatalytic H2 evolution activity. Most importantly, the 2D PyTTA-TPA COFs shell with outstanding intrinsic stability protects Cu2O nanocubes core from photocorrosion by showing no morphology and crystal structure change after 1000 times of photoexcitation.

Heterogeneous Supermolecule Aerogel for Ultraexcellent Photocatalytic Hydrogen Evolution

AbstractDeveloping an efficient strategy for recycling and reusing homogeneous photocatalysts while maintaining high activity and selectivity remains a significant challenge. Herein, a novel heterogenization approach is presented for a homogeneous photocatalyst assembled into a biomass‐based aerogel for photocatalytic performance that can be easily recycled and reused. The efficiency of light harvesting and H2O absorption is considerably higher because of the presence of multihydroxy groups in the aerogel and its high porosity, which further promotes the photocatalytic H2 evolution activity up to 30 mmol g−1 h−1, and 20 mmol g−1 h−1 in the actual sunlight reaction. The industrial application prospect of this approach for solar‐to‐chemical energy conversion is evident based on the facile and simple synthesis strategy, excellent photocatalytic performance, and easy recyclability.

Constructing an S-scheme heterojunction of 2D/2D Cd0.5Zn0.5S/CuInS2 nanosheet with vacancies for photocatalytic hydrogen generation under visible light

Exploring efficient and stable water-splitting photocatalysts is critical for realizing conversion solar energy into hydrogen energy. Herein, a unique 2D/2D S-scheme Cd0.5Zn0.5S/CuInS2 heterojunction with sulfur vacancies was rationally designed by chemically converting inorganic–organic hybrid ZnS(en)0.5 into inorganic Cd0.5Zn0.5S nanosheets and fabricating with CuInS2 at 350 °C under an N2 atmosphere. The final Cd0.5Zn0.5S/CuInS2 photocatalyst was composed of thin nanosheets with a substantial interfacial contact area, which enhanced light absorption and allowed directional charge transfer and separation. Under visible light irradiation, the photocatalytic H2 evolution activities of Cd0.5Zn0.5S nanosheets is 0.79 mmol·g−1·h−1, which is greater than other solid solution materials obtained by varying Cd and Zn ratios. The 2D/2D nanosheets with 8% CuInS2 exhibit excellent hydrogen evolution activity with yields of 7.73 mmol·g−1·h−1, which are 9.8 and 138 times higher than Cd0.5Zn0.5S and CuInS2. In addition, Cd0.5Zn0.5S/CuInS2 photocatalyst demonstrates outstanding stability and activity over the course of 24-hour period. Moreover, the transfer pathway of photogenerated charges were explored by the energy band bending, which proved that an S-scheme heterojunction is synthesized successfully.This work offers a useful methodology for analyzing S-scheme heterojunction with abundant sulfur vacancies, and improving the solar hydrogen evolution performance of Cd0.5Zn0.5S photocatalyst.

In situ cascade growth-induced strong coupling effect toward efficient photocatalytic hydrogen evolution of ReS2/ZnIn2S4

Optimizing electron structure of H2-evolution active sites to improve their catalytic efficiency is of great significance to develop efficient photocatalysts. Herein, an in situ cascade growth-induced strong coupling interface between ReS2 and ZnIn2S4 nanolayers was developed to realize the electron structure optimization of S-active sites in ReS2 cocatalyst, which can greatly improve the H2-evolution efficiency of ZnIn2S4 photocatalyst. The in situ cascade growth of ReS2/ZnIn2S4 includes initial formation of ZnIn2S4 nanolayers (ca. 200 °C) and their subsequent surface-induced production of ReS2 (ca. 300–380 °C) in molten system. The resulting ReS2/ZnIn2S4(3 wt%) shows a superior H2-production rate, which is ca. 20.6 and 2.0 times higher than that of ZnIn2S4 and ReS2-ZnIn2S4 (physical mixing), respectively. Besides the promoting transfer of photogenerated carriers, the cascade growth-induced strong coupling effect in the ReS2/ZnIn2S4 can induce the construction of electron-deficient Sδ+ site of ReS2, causing the optimized binding strength of S-H bond and excellent H2-evolution activity.