Photocatalytic Hydrogen Evolution Performance Research Articles

Bimetallic Porphyrin-Based Metal-Organic Framework as a Superior Photocatalyst for Enhanced Photocatalytic Hydrogen Production.

The meaningful and rational engineering of porphyrin-based catalysts with multimetallic active sites is very attractive toward photocatalytic hydrogen generation from water decomposition. Herein, three metal organic frameworks (MOFs) based on meso-tetrakis(4-carboxylphenyl)porphyrin (TCPP) were successfully constructed under solvothermal conditions. As a novel architectured photocatalyst (triclinic, C48H29N4O10PdYb), Pd/Yb-PMOF manifested diverse metal active sites, suitable bandgap positions, prominent visible light-collecting capacity, excellent carrier transfer efficiency, and obvious synergistic effect between ytterbium and palladium ions. Consequently, such a bimetallic MOF exhibited strengthened photocatalytic hydrogen evolution performance. Concretely, its hydrogen generation efficiency was up to 3196.42 μmol g-1 h-1 with 2 wt % Pt as a cocatalyst under visible light illumination. Our work demonstrates a promising strategy for highly efficient visible-light catalysts based on bimetallic-trimmed porphyrin MOFs.

Zinc-vacancy mediated Z-scheme photocatalyst of ZnS/LaTiO2N for hydrogen evolution under visible-light

Solar-powered photocatalytic water splitting for hydrogen evolution presents a promising solution to the energy crisis and contemporary environmental challenges. Herein, a Z-scheme ZnS/LaTiO2N heterojunction composite, incorporating zinc vacancies, has been successfully synthesized to enable photocatalytic hydrogen evolution under visible-light illumination. The optimized ZnS(VZn)/LaTiO2N composite demonstrates a hydrogen evolution activity 13 times higher than that of individual ZnS(VZn). The heterojunction between ZnS and LaTiO2N, in conjunction with zinc vacancies, expands the photoresponse spectrum and facilitates the spatial separation and transfer of photogenerated carriers. Consequently, this synergy significantly enhances the performance of photocatalytic hydrogen evolution. The collaborative action of the Z-scheme heterojunction and zinc vacancies paves the way for innovative approaches in designing future high-efficiency photocatalysts.

Carrier confinement activated explicit solvent dynamic of CdS/BiVO4/H2O and optimized photocatalytic hydrogen evolution performances

Herein, using an electrophoretic deposition strategy, a S-scheme CdS (cubic)/BiVO4 (monoclinic) heterostructured photocatalyst is fabricated. The as-synthesized photocatalysts exhibit high carrier separation efficiency, prominent hydrogen evolution ability and high stability. The results of the detailed density functional theory (DFT) prove that the photogenerated electrons and holes are located in BiVO4 and CdS components, respectively. Besides, an explicit solvent model based on the electron-enriched region in CdS/BiVO4 heterojunction is designed deliberately to investigate the solid/liquid interface issues. Intriguing findings demonstrate that the surface hydrogen diffusing rate in CdS/BiVO4/H2O is faster than that of BiVO4/H2O and is highly associated with the electron-enrich effect, which has a greater capacity to promote water decomposition, the possibility of proton collision and photocatalytic hydrogen evolution. Notably, the H p orbital can participate in the electron-enrich effect during solvation, thus reforming the orbital energy level and activating the HER of the BiVO4 component in the CdS/BiVO4 system.

Edge-engineering of donor-acceptor sp2-carbon-conjugated covalent organic frameworks for high-performance photocatalysts

Two-dimensional sp2-carbon-conjugated covalent organic frameworks (2D sp2c-COFs) featured with fully in-plane π-conjugated skeletons and tunable optoelectronic properties are appealing in photo-to-chemical energy conversion. Nevertheless, high-performance photocatalytic performance often suffers from easy carrier recombination and large band gaps. Herein, we reported the synthesis of a benzobisoxazole-linked donor-acceptor (D-A) 2D sp2c-COF (COF-TNOB-P2) via end-capping strategy to facilitate the carrier separation and migration as well as broaden the energy-harvesting capability. Due to the edge-engineered D-A structures, the COF-TNOB-P2 as the photoelectrode presents an excellent photocurrent density up to ∼88 μA/cm2 at 0 V vs. reversible hydrogen electrode, much higher than that of pristine COF-TNOB (56 μA/cm2). Moreover, the photocatalytic hydrogen evolution performance is enhanced from 1028 to 1824 μmol/h/g. Our work highlights the construction of D-A 2D sp2c-COF via lattice edge functionalization methodology for high-performance photocatalysts.

Artificial Photosynthetic System with Spatial Dual Reduction Site Enabling Enhanced Solar Hydrogen Production.

Although S-scheme artificial photosynthesis shows promise for photocatalytic hydrogen production, traditional methods often overly concentrate on a single reduction site. This limitation results in inadequate redox capability and inefficient charge separation, which hampers the efficiency of the photocatalytic hydrogen evolution reaction. To overcome this limitation, a double S-scheme system is proposed that leverages dual reduction sites, thereby preserving energetic photo-electrons and holes to enhance apparent quantum efficiency. The design features a double S-scheme junction consisting of CdS nanospheres decorated with anatase TiO2 nanoparticles coupled with graphitic C3 N4 . The as-prepared catalyst exhibits a hydrogen evolution rate of 26.84mmolg-1 h-1 and an apparent quantum efficiency of 40.2% at 365 nm. This enhanced photocatalytic hydrogen evolution is ascribed to the efficient charge separation and transport induced by the double S-scheme. Both theoretical calculations and comprehensive spectroscopy tests (both insitu and exsitu) affirm the efficient charge transport across the catalyst interface. Moreover, substituting the reduction-type catalyst CdS with other similar sulfides like ZnIn2 S4 , ZnS, MoS2 and In2 S3 further confirms the feasibility of the proposed double S-scheme configuration. The findings provide a pathway to designing more effective double S-scheme artificial photosynthetic systems, opening up fresh perspectives in enhancing photocatalytic hydrogen evolution performance.

Nature of the Active Ni State for Photocatalytic Hydrogen Generation

AbstractThermal treatments can have detrimental effects on the photocatalytic hydrogen (H2) evolution performance and impact the formation mechanism of the active state of surface‐supported co‐catalysts. In this work, a range of Ni‐based co‐catalysts is investigated immobilized on TiO2, evaluated their H2 evolution rates in situ over 21 h, and analyzed the samples at various stages with a comprehensive set of spectroscopic and microscopy techniques. It is found that achieving the optimal hydrogen evolution (HER) performance requires the right Ni0:Ni2+ ratio, rather than only Ni0, and that Ni needs to be weakly adsorbed on the TiO2 surface to create a dynamic state. Under these conditions, Ni can undergo an efficient redox shuttle, involving the transformation of Ni2+ to Ni0 and back after releasing the accumulated electrons for H+ reduction (i.e., Ni2+ ↔ Ni0). Yet, when the calcination temperature of the Ni/TiO2 photocatalysts increases, resulting in stronger coordination/adsorption of Ni on TiO2, this process is gradually inhibited, which ultimately leads to decreased HER performances. This work emphasizes the significance and influence of thermal treatments on the Ni active state formation – a process that can be relevant to other HER co‐catalysts.

Fabrication of S-scheme Zn1-xCdxS/NiO heterojunction for efficient photocatalytic hydrogen evolution

Establishing S-heterojunction was considered to be effective strategy to accelerate the speed of photocatalytic hydrogen evolution. In this study, we synthesized the S-scheme Zn1-xCdxS/NiO heterojunction by growing Zn1-xCdxS (ZCS) nanoparticles on NiO nanosheets for efficient photocatalytic hydrogen evolution. The photogenerated holes in ZCS could rapidly quenching with the photogenerated electrons of NiO though a S-scheme process, leaving the photogenerated electrons in the conduction band (CB) of ZCS for reduction of H+. The hydrogen evolution reactivity of the optimal ZCS/NiO was 259.2 mmol g−1 h−1, with the apparent quantum efficiency (AQE) of 15.8 % at 420 nm, which was 4.3 and 1728.0 times that of ZCS nanoparticle and NiO nanosheet, respectively. More importantly, the hydrogen evolution rate of ZCS/NiO was still 462.5 μmol g−1 h−1 without adding the sacrificial agent. This work provided a view for constructing S-scheme heterojunction to enhance photocatalytic hydrogen evolution performance.

Synthesize magnetic ZnFe2O4@C/Cd0.9Zn0.1S catalysts with S-scheme heterojunction to achieve extraordinary hydrogen production efficiency

Suppressing the electron-hole recombination rate of catalyst legitimately is one of the effective strategies to improve photocatalytic hydrogen evolution. Herein, carbon-coated metal oxide, ZnFe2O4@C (ZFO@C), nanoparticles were synthesized and employed to couple with quadrupedal Cd0.9Zn0.1S (CZS) via an ordinary ultrasonic self-assembly method combined with calcination to form a novel ZFO@C/CZS catalyst with step-scheme (S-scheme) heterojunction. The photocatalytic hydrogen evolution reaction (HER) was conducted to verify the enhanced photoactivity of ZFO@C/CZS. The optimal ZFO@C/CZS exhibits an extraordinary photocatalytic HER rate of 111.3 ± 0.9 mmol g-1 h−1 under visible-light irradiation, corresponding to an apparent quantum efficiency as high as (76.2 ± 0.9)% at 450 nm. Additionally, the as-synthesized ZFO@C/CZS composite exhibits high stability and recyclability. The excellent photocatalytic hydrogen evolution performance should arise from the formed S-scheme heterojunction and the unique ZFO@C core–shell structure, which inhibit electron hole recombination as well as provide more reactive sites. The pathway of S-scheme charge transfer was validated through density functional theory calculations and electrochemical measurements. This work provides a rational strategy for the synthesis of unique magnetic S-scheme heterojunction photocatalysts for water splitting under visible light irradiation.

Kinetic simulation of hydrogen production reaction parameters based on TiO2 photocatalyst

Hydrogen is a clean, efficient, and renewable energy source with significant potential to reduce greenhouse gases. Solar photocatalytic water splitting is a promising and sustainable route to produce hydrogen. Currently, the strategies to improve the efficiency of photocatalytic hydrogen production are mainly focused on the development of sustainable photocatalysts. However, the extent to which multiple working conditions affect photocatalytic hydrogen production efficiency is not yet clear. This paper established a TiO2-based photocatalytic phenomenological kinetic model and then validated it using experimental data to clarify the impact of the combined effects of various reaction conditions on the efficiency of photocatalytic hydrogen production. The effects of photocatalyst dosage, reaction temperature, sacrificial agent concentration, and other decisive parameters on TiO2-based photocatalytic hydrogen evolution performance were analyzed under light intensity of 365 nm. The optimization results revealed that the maximum STH efficiency of 5.30 % was observed, at the reaction temperature of 348.15 K and 0.25 g/L photocatalyst concentration. The model provides insights into the combined effects of different factors on photocatalytic efficiency. The identified optimal reaction conditions relationships are helpful to provide guidance for efficient designing of solar photocatalytic hydrogen evolution systems.

Remarkably enhanced hydrogen evolution of g-C3N4 nanosheet under simulated sunlight via AgPt alloy co-catalyst with low amount of Pt

The development of low-cost co-catalysts matched with proper photocatalysts to enhance the photocatalytic hydrogen evolution performance is highly demanded. Herein, the AgPt bimetallic alloy nanoparticles with small amounts of Pt were decorated on g-C3N4 nanosheets (AP-CN) via the NaBH4 reduction method, which were further used as catalysts towards photocatalytic hydrogen evolution from water under AM1.5 irradiation. Compared to mono-metallic co-catalysts, bimetallic AgPt alloy nanoparticles exhibited excellent co-catalytic performance. The optimum AP-CN photocatalyst with 0.5 wt% Pt exhibited photocatalytic hydrogen evolution rate of 3507.89 μmol g−1·h−1, which even surpassed that of the commonly-used photocatalyst 1.0 wt% Pt in-situ photo-deposited on g-C3N4. Meanwhile, the AP-CN showed excellent photocatalytic activity and durability after four experimental cycles. The enhanced activity and stability could be attributed to the synergistic effect between plasmonic metal Ag and Pt, which promoted the transfer and separation of photoinduced charge carriers. Besides, the theoretical results based on DFT calculation also verified that AgPt alloys have better performance of desorbing hydrogen and adsorbing H atoms. This work provides a feasible idea for the development of inexpensive and efficient bimetallic co-catalysts for photocatalytic hydrogen production through water splitting.

Effect of ESIPT-Induced Photoisomerization of Keto-Enamine Linkages on the Photocatalytic Hydrogen Evolution Performance of Covalent Organic Frameworks.

Photoexcitation of keto-enamine allows intramolecular proton transfer from C-NH to C=O, leading to tautomerization, while the photogenerated isomers are excluded from the study of photocatalytic applications. Herein, we demonstrate the photoisomerization of keto-enamine linkages on covalent organic frameworks (COFs) induced by excited-state intramolecular proton transfer (ESIPT). Partial enolization generates partially enolized photoisomers with a mixture of keto (C=O) and enol (OH) forms, conferring extended π-conjugation with an increase in electron density. The spatially separated D-A configuration is thus rebuilt with the enol-imine-linked branch as a donor and the keto-enamine-linked branch as an acceptor, and in turn, the photoinduced charges transfer between the two adjacent branches with a long lifetime. We further prove that the partially enolized photoisomer is a key transition instead of the keto-enamine form as an excited-state model to understand the photocatalytic behaviors. Therefore, ESIPT-induced photoisomerization must be considered for rationally designing keto-enamine-linked COFs with enhanced photocatalytic activity. Also, our study points toward the importance of controlling excited-state structures for long-lived separated charges, which is of particular interest for optoelectronic applications.

Efficient photocatalytic hydrogen evolution via interfacial engineering and charge carrier utilization with WSP/g-C3N4 S-scheme heterojunction

The practical implementation of photocatalytic hydrogen generation faces challenges due to the rapid recombination of photogenerated electron-hole pairs. This study reports the synthesis of a WSP/g- C3N4 S-scheme heterojunction catalyst featuring exposed hydrogen evolution active W sites, achieved through in-situ P introducing. Remarkably, the WSP/g-C3N4 catalyst exhibits a superior photocatalytic hydrogen evolution rate of 3.92 mmol h−1 g−1, surpassing g-C3N4 and attaining 112 times the performance of pristine C3N4. A series of characterization techniques and Density functional theory (DFT) reveal that WSP/C3N4 possesses the following advantages as a photocatalyst: 1) Under visible light irradiation, the distinctively ordered and well-crystallized structure generates potential differences, facilitates charge transfers, and enhances the hydrogen evolution activity. 2) The coupling between WSP and g-C3N4 interfaces effectively promotes the directional migration of photogenerated electrons. 3) The shallow bound energy level introduced near the conduction band of WSP effectively prolongs the carrier lifetime. These features collectively contribute to the improved performance of photocatalytic hydrogen evolution. These features collectively contribute to the improved performance of photocatalytic hydrogen evolution. This finding suggests new ways to create organic/inorganic heterojunction composite photocatalysts for efficient hydrogen generation.

Prussian blue analogues with tunable electron structure by different transition metal salts for wide spectrum photocatalytic hydrogen evolution

Photocatalytic hydrogen evolution is regarded as an efficient approach to fulfill future energy requirements. Prussian blue analogues (PBAs) serving as distinctive Metal-organic frameworks, feature a multi-electron, multi-core structure, as well as exceptional properties like structural stability and compositional adjustability. These attributes endow them with significant promise in the realm of photocatalytic hydrogen evolution. In this work, the six kinds of common transition metal salts were employed in synthesizing Prussian blue analogues (Cd–Co PBAs, Cu–Co PBAs, Co–Co PBAs, Ni–Co PBAs, Zn–Co PBAs and In–Co PBAs) featuring varying metal compositions through the chemical co-precipitation method. A comprehensive analysis was subsequently carried out to explore the connection between their structural features and properties. The six kinds of Prussian blue analogues were directly used as catalysts to evaluate their performance in photocatalytic hydrogen evolution, accompanied by a thorough investigation into the impact of their structural variations on their ability to facilitate photocatalytic hydrogen evolution. Among them, Ni–Co PBAs has the highest photocatalytic hydrogen evolution rate (6197.4 μmol h−1 g−1) and the highest apparent quantum efficiency (AQE) of 5.75 % at 475 nm due to the suitable band gap structure and the ideal MII/MIII atomic ratio (3:2). When explaining the correlation between electronic structure and properties of PBAs, the density functional theory (DFT) calculation gives further insight. This work provides a comprehensive understanding of the structure and properties of PBAs, which will provide a sustainable strategy for the development of photocatalysts based on PBAs for achieving high conversion efficiency of solar energy into hydrogen energy.

Evidence for an Interface of Hybrid Cocatalysts Favoring Photocatalytic Hydrogen Evolution Kinetics.

Hybrid cocatalysts have great application potential for improving the photocatalytic hydrogen evolution performance of semiconductors. The interfaces between components of hybrid cocatalysts make a great contribution to the improvement, but the associated mechanisms remain unclear. Herein, we prepared and tested three comparative CdS-based photocatalysts with NiS, NiS/Ni9S8, and Ni9S8 as the cocatalysts separately. The emphasis is placed on investigating the effect of the NiS/Ni9S8 interfaces on the photocatalytic hydrogen evolution performance of CdS. NiS/Ni9S8 exhibits a higher ability than NiS and Ni9S8 in making CdS a more active photocatalyst for water splitting. It shows that NiS, NiS/Ni9S8, and Ni9S8 perform similarly in terms of promoting the charge transfer and separation of CdS based on steady-state and time-resolved photoluminescence studies. At the same time, the linear sweep voltammetry and electrochemical impedance spectroscopy tests combined with the density functional theory calculations reveal that the component interfaces of NiS/Ni9S8 enable us to lower the water splitting activation energy, the charge-transfer resistance from the cocatalyst to sacrificial agent, and hydrogen adsorption Gibbs free energy. It is evidenced from this work that component interfaces of hybrid cocatalysts play a vital role in accelerating the dynamics of hydrogen evolution reactions.

Construction of Cu2S/Nv-C3N4 p-n heterojunctions for enhanced photocatalytic hydrogen production under visible light

The high photogenerated electron-hole complexation rate has been the main reason limiting the practical application of carbon nitride, while the construction of heterojunction can promote the separation of photogenerated carriers, broaden the light absorption range and effectively improve its photocatalytic activity. Therefore, in this work, Cu2S was loaded onto g-C3N4 nanosheets by in situ deposition, and a series of Cu2S/Nv-C3N4 p-n heterojunctions were prepared by varying the loading amount of Cu2S. The photocatalytic performance test results showed that the best photocatalytic hydrogen production performance of 10% Cu2S/Nv-C3N4 reached 197 μmolg−1h−1, which was 11.4 times that of pure Nv-C3N4 and 47.5 times that of pure Cu2S. The enhanced photocatalytic activity is attributed to the formation of Cu2S/Nv-C3N4 p-n heterojunction, which effectively promotes the separation and transfer of photogenerated electron-hole and enhances light absorption. This work constructs a novel type of C3N4 heterojunction composite, which provides a new way to improve the photocatalytic hydrogen evolution performance of C3N4.

Interfacial chemical bond regulating the electronic coupling of ZnIn2S4−x-WO3−x for enhancing the photocatalytic pollutions degradation coupled with hydrogen evolution

Constructing Z-scheme heterostructure photocatalysts with a staggered band structure holds great potential to realize synergistic oxidation and reduction reactions. However, the Z-scheme heterostructure with interfacial vacancies significantly disturbs the behaviors of charge transfer and remains a challenging as well as urgent issue to exploit. Here, the ultrathin ZnIn2S4−x-WO3−x Z-scheme heterostructure (ZW) was synthesized via a facile in situ hydrothermal strategy. Experimental results and DFT calculations unveiled that the dual vacancies induced the formation of interfacial bonds. Importantly, the interfacial bonds tremendously modulate the electronic structure of heterostructure for enlarging the built-in electric field and reducing the aggregation effect of charge in the interface vacancies, which contributed to promoting charge transfer through the interface as well as exciton dissociation. Ultimately, the optimized ZW-4 exhibited an exceptional photocatalytic hydrogen evolution performance of 737.75 μmol g−1 h−1 and a pollution degradation rate greater than 99.99% without using any cocatalyst under visible light irradiation. Our work offers a deep insight into the ideal charge migration paths in highly efficient Z-scheme heterojunctions with vacancies.

CdS/MoS2 nanoparticles anchored on oxygen-doped g-C3N4 nanosheets all-solid-state Z-scheme heterojunctions for efficient H2 evolution

Hydrogen evolution by photocatalysis is an ideal method to relieve the energy crisis. In this work, an all-solid-state Z-scheme photocatalytic system is developed via a simple hydrothermal strategy to anchor CdS–MoS2 hybrid nanoparticles onto oxygen-doped g-C3N4 nanosheets (OCN). The presence of MoS2 nanosheets serves as both an intermediary for electron transfer to enhance charge separation and enhance the durability of the CdS. Compared to the unmodified CdS, the H2 generation efficiency of the CdS–MoS2/OCN Z-scheme heterojunctions is significantly enhanced. Additionally, the optimized photocatalyst exhibits a remarkable 20.7-fold increase in H2 production rate compared to the pristine CdS. Based on the systematical characterization, the enhanced photocatalytic hydrogen evolution performance arises from the enhanced light absorption, the enlarged specific surface areas, as well as the improved charge separation. The systematic characterizations provided evidence for the demonstration of the Z-scheme photocatalytic mechanism. This work presents a novel perspective on the design of photocatalytic systems with an all-solid-state Z-scheme configuration.

Synthesis, characterization, and photocatalytic hydrogen evolution performance of neodymium iron composites: Influence of annealing temperature

Hydrogen is a highly sought-after and versatile energy carrier, as well as a crucial chemical with widespread applications. It can be produced from water through photocatalysis using sunlight or through electrolysis powered by solar or wind energy. However, the design of efficient photocatalytic systems for hydrogen production remains a significant challenge, necessitating the development of novel photocatalysts. In this study, we successfully synthesized neodymium iron composites with a platelet-like nanostructure using a sol–gel technique, followed by heat treatment at different annealing temperatures ranging from 750 to 900 °C. The analysis using Rietveld Refinements revealed the formation of a composite consisting of NdOCl/Fe2O3/NdFeO3. To investigate the effects of phase composition variations caused by different annealing temperatures, we applied various characterization techniques to explore the optical absorption properties, band structure, and photocatalytic hydrogen evolution ability. Among the samples, the one obtained at 800 °C exhibited the highest photocatalytic hydrogen evolution activity. It demonstrated a measured rate of 12.79 µmol/g/h when methanol was used as the sacrificial agent and 18.99 µmol/g/h when triethanolamine (TEOA) was applied as the sacrificial agent. To provide insight into the observed differential photocatalytic activity, we propose a possible mechanism based on the separation of photogenerated charge carriers through varied interfacial heterojunctions resulting from the phase composition change in each sample.

Enhancing photocatalytic hydrogen production of carbon nitride: Dominant advantage of crystallinity over mass transfer

Mass transfer enhancement and crystallinity engineering are two prevailing technologies for photocatalyst modification. However, their relative effectiveness in enhancing photocatalytic activity remains unclear due to the lack of rational probing catalysts. In this study, we synthesized two distinct carbon nitride (C3N4) catalysts: one with a high specific surface area (CN-HA) and the other with improved crystallinity (CN-HC). These catalysts served as probes to compare their respective impacts on photocatalytic activities. Comprehensive characterization techniques and density functional theory (DFT) calculation results unveiled that crystallinity played a dominant role in light absorption and charge dynamics, while surface area primarily influenced mass transfer in photocatalysis. Importantly, our findings revealed that crystallinity engineering of photocatalyst achieved a greater impact on photocatalytic hydrogen evolution than that from mass transfer enhancement. Consequently, CN-HC demonstrated a remarkable improvement in photocatalytic performance for hydrogen evolution (6465.4 μmol h−1 g−1), surpassing both C3N4 and CN-HA by 19.4- and 2.4-fold, respectively, accompanied by a high apparent quantum yield of 23.8 % at 420 nm. This study not only unveils the dominant factor influencing the activity of photocatalysts but also provides a modified approach for robust solar fuel production, shedding light on the path toward efficient and sustainable energy conversion.

Boosting the photocatalytic hydrogen evolution performance by fabricating the NiO/Zn3In2S6 p-n heterojunction

Photocatalytic water splitting for hydrogen evolution is viewed as a promising strategy to address the energyandenvironmentalissues. In this study, a series of NiO/Zn3In2S6 (NiO/ZIS6) p-n heterojunction photocatalysts have been prepared by the facile ultrasonic assisted deposition method. The as-obtained samples were systematically characterized employing various testing techniques. The photocatalytic performance of the p-n photocatalysts were evaluated by photocatalytic hydrogen production and the effect of different mass ratios of NiO to ZIS6 on photocatalytic hydrogen evolution performance was also explored. The results indicated that the 25% NiO/ZIS6 sample demonstrates optimal photocatalytic hydrogen evolution activity with a hydrogen evoluton rate of 21.79 mmol g−1h−1, which is 7.65 times higher than that of ZIS6. The mechanism exploration proves that the formation of NiO/ZIS6 p-n heterojunction effectively promotes the separation and migration of photoinduced electrons and holes. Meanwhile, the recombination of charge carriers was restrained observably. This work may shed light on the design and preparation of novel p-n heterojunction photocatalysts with efficient photocatalytic hydrogen evolution performance and high stability.