A novel direct Z-scheme heterojunction of CoTiO3/ZnIn2S4 for enhanced photocatalytic H2 evolution activity

The shortage of fossil energy has become a growing global concern. It is particularly important to make full use of the infinite solar energy resources, and transform them into sustainable and clean energy. The development of hydrogen energy has become a feasible solution to solve the energy shortage problem. The preparation of photocatalysts featuring efficient charge transfer channels and high hydrogen production activity provides a pathway for the development of hydrogen energy. In this paper, we report for the first time the direct assembly of 2D ZnIn₂S₄ (ZIS) nanosheets on the surface of CoTiO₃ (CTO). The synthesized CoTiO₃/ZnIn₂S₄ (CTO/ZIS) photocatalyst features a direct Z-scheme charge transfer channel, which enhances the separation rate of photogenerated carriers, and accelerates the photocatalytic H₂ evolution (PHE) rate. Without the assistance of any co-catalyst, the PHE rate of prepared CoTiO₃/ZnIn₂S₄ was as high as 5.21 mmol g^?1 h^?1. Moreover, the H₂ evolution rate of CoTiO₃/ZnIn₂S₄ almost did not decrease significantly after four consecutive 4 h cycles. This investigation provides a valuable approach for the exploitation of novel and efficient Z-scheme photocatalysts in the application of solar energy to hydrogen energy conversion.     

ZnIn2S4 modified CaTiO3 nanocubes with enhanced photocatalytic hydrogen performance

Novel ZnIn₂S₄/CaTiO₃ nanocubes were prepared by a two-step method and used as a visible light photocatalyst for efficient hydrogen production. The control of the content of CaTiO₃ could effectively change the photocatalytic H₂ production activity of ZnIn₂S₄/CaTiO₃ nanocubes, and the maximum H₂ evolution amount reached to 133116.43 μmol g⁻¹ in 6 h. The photocatalytic hydrogen production efficiency of ZnIn₂S₄/CaTiO₃ nanocubes was almost 4.5 times higher than that of pure ZnIn₂S₄. The electrochemical impedance spectrum of ZnIn₂S₄/CaTiO₃ exhibited the smallest arc radius, time-resolved PL spectrum showed that the carrier lifetime of ZnIn₂S₄/CaTiO₃ nanocubes was 3.29 ns, and the photocurrent density of ZnIn₂S₄/CaTiO₃ reached to 0.81 μA cm⁻². The prepared ZnIn₂S₄/CaTiO₃ nanocubes increased visible light absorption, improved the separation and transfer of photo-generated electrons and holes, and inhibited the recombination of photo-generated electron-hole pairs. ZnIn₂S₄/CaTiO₃ nanocubes exhibited the enhanced photocatalytic activity and high stability, and could be used as promising photocatalyst for hydrogen production application.     

ZIF-L-derived porous C-doped ZnO/CdS graded nanorods with Z-scheme heterojunctions for enhanced photocatalytic hydrogen evolution

This study presents a novel approach for synthesizing C–ZnO/CdS graded nanorods derived from metal–organic frameworks (MOFs) that can be applied as a catalyst for photocatalytic hydrogen evolution from pure water. Porous C-doped ZnO was prepared by a self-template method using imidazole-like metal–organic backbone (ZIF-L) as a precursor through a two-step calcination method. CdS nanoparticles were deposited on ZIF-L surface by chemical deposition. The two-step calcination method introduced elemental C, and the unique architecture of ZIF-L played an essential role in forming the hierarchical structure of the porous ZnO nanorods. Compared with other ZnO/CdS catalysts, the C-doped ZnO/CdS graded nanorods exhibited remarkable photocatalytic activity for hydrogen production. The highest hydrogen production rate of 20.25 mmol g^?1 h^?1 with an apparent quantum yield (AQY) of 24.7% at 365 nm obtained over C–ZnO/CdS with Pt as co-catalyst, which was 24.4 and 65.3 times higher than that over CdS (0.83 mmol g^?1 h^?1) and ZnO (0.31 mmol g^?1 h^?1), respectively. This outcome was attributed to (i) the formation of Z-scheme heterojunction that significantly promoted the separation and migration of photogenerated electron–hole pairs; (ii) C doping that reduced the bandgap of ZnO and broadened its spectral response range; and (iii) the ordered arrangement of porous nanorods that effectively reduced the recombination rate of the electron–hole pairs.     

Construction of 3D/3D heterojunction between new noble metal free ZnIn2S4 and non-inert metal NiMoO4 for enhanced hydrogen evolution performance under visible light

Promoting the separation of electron and hole plays an important role in photocatalytic hydrogen production. However, single semiconductor materials cannot fully realize their potential due to the rapid recombination of photogenerated carriers. Therefore, in this experiment, a new photocatalyst ZnIn₂S₄/NiMoO₄ was prepared by using an electrostatic self-assembly method, which greatly improved the electron-hole recombination phenomenon. After 5 h reaction under visible light irradiation, ZIS/NMO-3 composite catalyst prepared in ethanol showed the best photocatalytic activity, and the hydrogen evolution capacity reached 173.09 μmol. The hydrogen evolution capacity of ZIS/NMO-3 was 2.47 and 25.83 times that of short rod-like NiMoO₄ and microflower-like spherical ZnIn₂S₄, respectively. Through some physical characterization and electrochemical experiments, it can be seen that NiMoO₄ and ZnIn₂S₄ have good composability. Meanwhile, the composite catalyst ZnIn₂S₄/NiMoO₄-3 has high current response characteristics. It can be seen from the fluorescence emission spectra that the composite catalyst presents the lowest peak value, which indicates that ZIS/NMO-3 can effectively inhibit the recombination of photogenerated electrons and holes. When ZnIn₂S₄ is loaded on NiMoO₄, the separation of photogenerated carrier will be accelerated due to the formation of heterojunction, thus improving the photocatalytic activity. At the same time, the large specific surface area will also provide more abundant active sites for the composite catalyst, which provides a good condition for photocatalytic hydrogen production. This work provides an efficient, uncomplicated and feasible method for the synthesis of ZIS/NMO-3 composite catalyst with excellent properties.     

Design and fabrication of hollow structured Cu2MoS4/ZnIn2S4 nanocubes with significant enhanced photocatalytic hydrogen evolution performance

The unique architecture is very significant for photocatalysts to achieve high photocatalytic efficiency. Herein, hollow Cu₂MoS₄/ZnIn₂S₄ heterostructural nanocubes with intimate-contact interface have been prepared for the first time via a self-template way, which can promote the photocatalysis hydrogen evolution. First, novel hollow structured Cu₂MoS₄ nanocubes were successfully synthesized using Cu₂O as a precursor, then the ZnIn₂S₄ nanosheets were in-situ grew on the surface of hollow Cu₂MoS₄ nanocubes. The unique hollow heterostructures have markedly enhanced photocatalytic efficiency, and 15 wt% Cu₂MoS₄/ZnIn₂S₄ sample exhibits the highest hydrogen production rate of 8103 μmol·h⁻¹·g⁻¹, which is approximately four times higher than pure ZnIn₂S₄. The improved photocatalytic performance is mainly attributed to the following two points: (1) the hollow nanocube structure can provide rich active sites and increase light absorption; (2) forming a built-in electric field is conducive to transfer the holes generated by ZnIn₂S₄ to Cu₂MoS₄, which can effectively promote charge separation. This work may provide insights for the design of hollow architecture cage materials for high photocatalytic performance.     

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.     

Design of nanohoneycomb structured Ta3N5/WO3 Z-scheme for enhanced visible light photocatalytic hydrogen evolution

Ta₃N₅ has suitable band positions for visible light photocatalytic hydrogen production from water splitting. However, fast self-recombination of electrons and holes is a drawback for its low efficiency. A Ta₃N₅/WO₃ Z-scheme was therefore considered to solve this problem. Furthermore, a nanohoneycomb (nHC) structure was designed and fabricated based on solution-based nanosphere lithography to offer higher surface area for reaction. The cell size of the nHC was controlled by using 400-, 200-, and 100-nm polystyrene nanospheres as the mask. Under visible light irradiation, the hydrogen generation rates of Ta₃N₅@WO₃ film and Ta₃N₅@100-nm WO₃ nHC were measured to be 4.6 and 8.1 μmol/g·h, respectively, whereas that of pure Ta₃N₅ nHC was negligible. With deposition of Pt cocatalyst, the hydrogen generation rates for Ta₃N₅@WO₃ film and Ta₃N₅@100-nm WO₃ nHC were further raised to 9.9 and 16.6 μmol/g·h, confirming the effectiveness of the structure design.     

ZnCo2S4/Zn0.2Cd0.8 S Z-scheme heterojunction: Efficient photocatalytic H2 evolution coupling selective oxidation of benzyl alcohol

The Z-scheme heterojunction photocatalysts possess excellent photocatalytic activity benefitting from their properly matched edge potentials. In this work, ZnCo₂S₄ nanoparticles are anchored on Zn_0.2Cd_0.8S solid solution nanowires and assembled into binary ZnCo₂S₄/Zn_0.2Cd_0.8S nanocomposites. The as-synthesized ZnCo₂S₄/Zn_0.2Cd_0.8S nanocomposites act as bifunctional photocatalysts, which can be used for high-performance H₂ production coupling synthesis of high-value-added benzaldehyde in low concentration benzyl alcohol solution. Under visible light irradiation, 20%-ZnCo₂S₄/Zn_0.2Cd_0.8S nanocomposite shows the highest H₂ evolution rate of 23.02 mmol g^?1 h^?1 in the first photocatalytic cycle, which is 395.0 and 526.7 times higher than that of Zn_0.2Cd_0.8S and ZnCo₂S₄ under the same conditions. Eventually, after six-time cycles, the conversion rate and selectivity of benzyl alcohol oxidation to benzaldehyde are 54.3% and 92.2%, respectively. The enhancement of photocatalytic performance is mainly attributed to the Z-scheme heterojunction between ZnCo₂S₄ and Zn_0.2Cd_0.8S, which promote the separation and transfer of photogenerated charge carriers. This work provides strong support for the rational design of Z-scheme nano-heterojunction of highly efficient photocatalytic application in H₂ evolution and fine chemicals production.     

Fabrication of 1D/2D CdS/CoSx direct Z-scheme photocatalyst with enhanced photocatalytic hydrogen evolution performance

In this work, we fabricate a 1D/2D heterojunction photocatalyst composed of n-type CdS nanorods and p-type CoS_x nanoflake. This photocatalyst achieves a hydrogen evolution rate of 9.47 mmol g^?1 h^?1, which is 13.7 times higher than that of pure CdS nanorods. Scanning Kelvin Probe, Mott-Schottky plots, UV–Vis absorption spectra and surface photocarrier orienting reaction results indicate that the enhanced photocatalytic performance of CdS/CoS_x is owing to the fabrication of direct Z-Scheme heterojunction system which greatly improves the utilization, migration and separation rate of photo-generated carriers. To the best of our knowledge, this work is the first time to describe a CdS/CoS_x direct Z-scheme system with 1D/2D nanostructure, which can expedite the transfer process of photogenerated carriers with strong redox energy to participate in photocatalytic reactions.     

An anti-symmetric dual (ASD) Z-scheme photocatalytic system: (ZnIn2S4/Er3+:Y3Al5O12@ZnTiO3/CaIn2S4) for organic pollutants degradation with simultaneous hydrogen evolution

An anti-symmetric dual (ASD) Z-scheme ZnIn₂S₄/Er³⁺:Y₃Al₅O₁₂@ZnTiO₃/CaIn₂S₄ photocatalyst was prepared by isoelectric point and calcination methods. The photocatalytic activity is estimated via degradation of Acid Orange II as a target organic contaminant with simultaneous hydrogen evolution under simulated solar-light irradiation. The prepared ASD Z-scheme ZnIn₂S₄/Er³⁺:Y₃Al₅O₁₂@ZnTiO₃/CaIn₂S₄ photocatalyst has a high photocatalytic activity, which can be assigned to the enlarged photoresponse range, increased reduction surface and enhanced separation efficiency of photo-induced carriers. Furthermore, the cyclic experiment proves that the prepared ASD Z-scheme ZnIn₂S₄/Er³⁺:Y₃Al₅O₁₂@ZnTiO₃/CaIn₂S₄ photocatalyst still maintains a high photocatalytic activity within five repetitive cycles. Moreover, the mechanism on photocatalytic degradation of organic pollutants with simultaneous hydrogen evolution caused by ASD Z-scheme ZnIn₂S₄/Er³⁺:Y₃Al₅O₁₂@ZnTiO₃/CaIn₂S₄ photocatalyst is proposed. It is wished that this study could provide a promising pathway for effective degradation and rapid hydrogen production.     

Photocatalytic overall water splitting by Z-scheme g-C3N4/BiFeO3 heterojunction

Solar water splitting by photocatalysis in the absence of sacrificial agent has been identified as a promising approach to produce green hydrogen. Increasing photocatalytic efficiency is the core issue in this process. Forming heterojunctions is one potential solution to improve photoactivity. Herein, we successfully synthesized several g-C₃N₄/BiFeO₃ composites containing different mass ratio of g-C₃N₄ by an uncomplicated and cost-effective method. The composite samples exhibited remarkably enhanced photocatalytic performance compared with the bare BiFeO₃ and g-C₃N₄. The highest hydrogen production rate obtained is ~ 160.75 μmol h⁻¹.g-¹ under UV irradiation and ~23.31 μmol h⁻¹.g-¹ under visible light irradiation. This enhanced photocatalytic activity is attributed to the synergistic effect of the junction and Z-scheme charge transfer mechanism between BiFeO₃ and g-C₃N₄, which can effectively accelerate the separation of photogenerated electron-hole pairs and also capability of carrying out redox reaction.     

A perspective on the fabrication of heterogeneous photocatalysts for enhanced hydrogen production

This perspective provides an insight to the possibility of adopting hydrogen as a key energy-carrier and fuel source, through Photocatalytic water splitting in the near future. The need of green and clean energy is increasing to overcome the growing demand of sustainable energy throughout globe, owing to CO₂ emission using fossil fuels. To generate highly efficient and cost-competitive hydrogen, the semiconductor based heterojunction nanomaterials have gained tremendous consideration as a promising way. Currently, the efficiency for hydrogen generation through UV–Vis active photocatalysts is relatively low. The key issues are found to be poor separation of photogenerated electron/hole, less surface area, and low absorption region of electromagnetic spectrum. Such issues arise due to inappropriate band edge potentials and large bandgap of present catalyst. A lot of schemes has been devoted to design and fabricate efficient photocatalysts for improved photocatalytic performance in recent years. However, it seems still a challenge and imperative to greatly comprehend the fundamental aspects, photocatalysis and transfer mechanisms for complete deployment of electron/hole pairs. Further, to produce hydrogen to a larger extent through photocatalytic water splitting, the photocatalyst has been modified through co-catalysts/dopants using numerous techniques including the Z-scheme, hybridization, crystallinity, morphology, tuning of band edge positions, reduction of the band gap, surface structure etc., such that these heterogeneous photocatalysts may have ability to absorb enough light in the UV-VIS-IR region. This type of heterogeneous photocatalysts has the ability to improve the rate of efficiency for hydrogen evolution through absorption of sufficient light of solar spectrum and enhance the separation of charge-carriers by inhibiting recombination of electron/hole pairs. We surmise that taking into account the aforesaid factors should support in scheming an efficient photocatalysts for hydrogen production through water splitting, eventually prompting technological developments in this field.     

2D NiCo2S4 decorated on ZnIn2S4 formed S-scheme heterojunction for photocatalytic hydrogen production

The hydrothermal preparation of NiCo₂S₄/ZnIn₂S₄ photocatalysts with different mass ratios is studied. Ni-cobalt bimetallic sulfide nanosheets are grown on zinc-indium bimetallic sulfide to form a compact heterojunction. First, both NiCo₂S₄ and ZnIn₂S₄ exhibit N-type semiconductor characteristics, a heterojunction formed by both can reduce the surface reaction energy barrier and use its synergy, strengthening the charge self-diffusion between the two semiconductors, it means the formation of a strong electric field. From the electron transfer path and band structure, NiCo₂S₄/ZnIn₂S₄ has S-scheme heterojunction characteristics. NiCo₂S₄ is a reducing photocatalyst (RP), and ZnIn₂S₄ is an oxidative photocatalyst (OP). Under the action of built-in electric field (BIEF), strong photogenic electrons and holes exist in CB of RP (NiCo₂S₄) and VB of OP (ZnIn₂S₄). Thus, the overall redox capacity of the NiCo₂S₄/ZnIn₂S₄ heterojunction is enhanced. Using visible light, the composite material can be used for photocatalytic hydrogen production. It is further shown that the composite material has a good effect in photocatalytic hydrogen production under the sensitizer eosin Y (EY) system. The optimal hydrogen production is about 221.75 μmol when the mass ratios of NiCo₂S₄/ZnIn₂S₄ is 20%, and the photocatalytic activity of the composite is about 47 times that of ZnIn₂S₄. Notably, the stability of the composites is the better. A reasonable photo-catalytic mechanism is proposed based on the band gap and photoelectrochemical properties of heterojunction.     

Electron transfer via a carbon channel for efficient Z-scheme solar hydrogen production

Z-scheme photocatalysis provides a promising solution to photocatalytic solar water splitting, yet restricted by inferior interfacial charge transfer. Here, we demonstrate a Z-scheme composite photocatalyst made of Fe₂O₃, a carbon layer, and g-C₃N₄ that can achieve efficient hydrogen generation from solar water decomposition. The success relies on in-situ preparation of core-shell Fe₂O₃@C structure at the surface of g-C₃N₄. Carbon as an intermediate layer thus acts as a bridge that significantly accelerates the migration of photogenerated electrons from Fe₂O₃ conduction band to g-C₃N₄ valence band. As a result, the highest rate of H₂ generation reaches 5.26 mmol h⁻¹g⁻¹. This activity is approximately 33-time greater than that achieved over pristine g-C₃N₄ and about 4-time larger than that obtained over a Fe₂O₃/g-C₃N₄ heterojunction without internal carbon layer. This work explicates the potential insight of the composite and paves a promising way to engineer the charge transfer behavior.     

0D/3D ZnIn2S4/Ag6Si2O7 nanocomposite with direct Z-scheme heterojunction for efficient photocatalytic H2 evolution under visible light

Constructing heterojunction structure is a feasible way to realize an efficient and durable photocatalysts. Herein, a novel Z-scheme zero/three dimensional (0D/3D) ZnIn₂S₄/Ag₆Si₂O₇ (ZIS/ASO) composite was rationally designed, synthesized and analyzed. ZIS/ASO composite possesses a layer structure for increasing light response, a special 0D/3D structure for reducing the photo-induce carriers migration path, and numerous active sites for absorbing H₂O and producing H₂. This composite retains the high oxidation and reduction ability by facilitating separation and migration as well as limiting recombination of photo-induced carriers via the intimate interface between ZIS and ASO. Undoubtedly, the synthesized ZIS/ASO photocatalyst achieved a high photocatalytic H₂ activity, and the optimum sample shows a satisfactory H₂ evolution rate of 590.56 μmol g⁻¹ h⁻¹, distinctly better than that of pure ZIS. More importantly, this composite exhibits high stability and recyclability and is expected to be applied in practical application. Based on the H₂ evolution experimental results and electrochemical tests, the Z-scheme heterostructure construction of the composite was confirmed. This work expects to inspire a unique protocol for synthesizing Z-scheme photocatalysts for water splitting under visible light irradiation.     

Fabrication of rGO/CdS@2H, 1T,amorphous MoS2 heterostructure for enhanced photocatalytic and electrocatalytic activity

The synthesis of high efficiency noble metal free catalysts is an important target for H₂ production by water-splitting. In this work, rGO/CdS@MoS₂ heterostructure with two catalytic paths was successfully synthesized and as the first applied the heterostructure in the field of electrocatalysis. The MoS₂ structure is adjusted by controlling hydrothermal process. Moreover, the effects of structure and loading amount of 2H–MoS₂, 1T-MoS₂ and amorphous MoS₂ (A-MoS₂) on catalytic performance were also studied. The catalytic activity of rGO/CdS@MoS₂ heterostructure has been improved obviously. Compared with 2H–MoS₂, the distortion of 1T-MoS₂ and the defect of A-MoS₂ make it have more unsaturated S, so rGO/CdS@1T-MoS₂ and rGO/CdS@A-MoS₂ have better catalytic activity. For photocatalytic H₂ evolution, loading MoS₂ and rGO on catalysts changes the energy band structure, promotes the separation of electron-holes and provides a large number of active sites. Among them, the visible light photocatalytic H₂ production rate of rGO/CdS@1T-MoS₂ with 0.1 mol of 1T-MoS₂ (CT0.1-G1) is 18.26 mmol/g/h. During the electrocatalytic H₂ evolution, introducing MoS₂ and rGO improves electronic structure and increases active sites. rGO/CdS@1T-MoS₂ with 0.5 mol of 1T-MoS₂ (CT0.5-G1) shows the low overpotential (312 mV) and Tafel slopes (85 mV/dec).     

Z-scheme MoO3-2D SnS nanosheets heterojunction assisted g-C3N4 composite for enhanced photocatalytic hydrogen evolutions

In this work, the 2D SnS/g-C₃N₄ nanosheets have been successfully prepared by a facile ultrasonic and microwave heating approach, which formed intimate interfacial contact and suitable energy band structure. The optimized sample displayed enhanced photocatalytic hydrogen evolution from water assisted with Pt co-catalyst, which is much higher than that of pure g-C₃N₄. After loaded with MoO₃ particles, the stability of photocatalysts displayed significate improvement due to the formed Z-scheme heterojunction. With the characterization, the enhanced hydrogen evolution reaction (HER) performance might be ascribed to the improved light-harvesting capability of the composite, lowered charge-transfer resistance, increased electrical conductivity and the co-catalyst effect of SnS. This study provides insights about SnS assisted HER photocatalysts and a new strategy to improve the stability of metal sulfides photocatalysts.     

The ZnIn2S4/CdS hollow core-shell nanoheterostructure towards enhanced visible light photocatalytic H2 evolution via bimetallic synergism

The ZnIn₂S₄/CdS hollow core-shell nanoheterostructure with bimetallic synergism is synthesized via a hybrid chemical method. As revealed, the ZnIn₂S₄/CdS hollow core-shell nanoheterostructure (ZnIn₂S₄/CdS-3) exhibits remarkable visible light photocatalytic hydrogen evolution (～5209.43 μmol·g^?1·h^?1, AQE of ～20.26%) than that of single CdS (～40 folds) and single ZnIn₂S₄ (～12 folds), and achieves decent photocatalytic stability (average HER performance of ～5056.80 μmol·g^?1·h^?1), which is mainly ascribed to that, the formed ZnIn₂S₄/CdS heterostructure with appropriate potential gradient and Zn/In bimetallic synergism can improve carrier transportation, including increasing carrier transportation, prolonging lifetime and decreasing recombination, the hollow core-shell nanostructure can provide abundant active sites and increase solar efficiency, while can maintain a photocatalytic stability.     

Construction of hollow tubular Co9S8/ZnSe S-scheme heterojunctions for enhanced photocatalytic H2 evolution

Herein, ZnSe nanoparticles with good visible-light response were in-situ deposited on the surface of the hollow tubular Co₉S₈ to form compact Co₉S₈/ZnSe heterojunctions via hydrothermal and solvothermal methods. This architecture is beneficial to expose more active sites due to the uniform dispersion of ZnSe particles. Under visible light irradiation, the composites at the optimum Co₉S₈ amount (5 wt%) take on notably higher hydrogen evolution activity, 967.8 μmol/g/h, which is 3.1 times that of independent ZnSe (314.2 μmol/g/h). A series of tests manifested that the Co₉S₈–ZnSe heterojunction significantly promotes the separation of photo-induced electron-hole pairs, notably improves hydrogen evolution kinetics and reduces the electron transfer resistance, which is responsible for the enhanced photocatalytic activity of the composites. Furthermore, the photocatalytic mechanism of the S-scheme heterojunction was proposed based on the measured energy band potentials. This work provides a strategy in constructing inexpensive heterojunction photocatalysts for enhancing the hydrogen evolution performance.     

Construction of Au/g-C3N4/ZnIn2S4 plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture for visible-light-driven hydrogen production

In this paper, a novel Au/g-C₃N₄/ZnIn₂S₄ plasma photocatalyst heterojunction composite with 3D hierarchical microarchitecture has been successfully constructed by integrating Au/g-C₃N₄ plasmonic photocatalyst composite with 3D ZnIn₂S₄ nanosheet through a simple hydrothermal process. The Au nanoparticles were firstly anchored on the surface of pristine g-C₃N₄ material to get Au/g-C₃N₄ plasmonic photocatalyst. Ascribing to the surface plasmon resonance of Au nanoparticles, the obtained Au/g-C₃N₄ plasmonic photocatalyst shows a significant improved photocatalytic activity toward hydrogen production from water with visible light response comparing with pristine g-C₃N₄. Further combining Au/g-C₃N₄ plasmonic photocatalyst with 3D ZnIn₂S₄ nanosheet to construct a heterojunction composite. Owing to the synergistic effect of the surface plasmon resonance of Au nanoparticles in Au/g-C₃N₄ and the heterojunction structure in the interface of Au/g-C₃N₄ and ZnIn₂S₄, the prepared Au/g-C₃N₄/ZnIn₂S₄ plasma photocatalyst heterojunction composite shows an excellent photocatalytic activity toward hydrogen production from water with visible light response, which is around 7.0 and 6.3 times higher than that of the pristine C₃N₄ and Znln₂S₄ nanosheet, respectively. The present work might provide some insights for exploring other efficient heterojunction photocatalysts with excellent properties.