Developing a new composite photocatalyst is the key to achieving efficient photocatalytic decomposition of aquatic hydrogen. In this study, Cu-ZnIn2S4/WO3/WS2 nanostructures were prepared by a two-step hydrothermal method. The unique charge transfer mechanism of Cu-doped and mixed heterojunctions (Z-scheme heterojunctions and Type-I heterojunctions) significantly enhances charge transfer and separation, resulting in excellent photocatalytic hydrogen evolution performance of Cu-ZnIn2S4/WO3/WS2. The hydrogen evolution rate of Cu-ZnIn2S4/WO3/WS2 is 93032.29 µmol·g−1·h−1, 37.82 and 3.33 times that of ZnIn2S4 and Cu-ZnIn2S4, respectively, and the quantum efficiency at 430nm is 37.04 %. It is also superior to Pt-modified Cu-ZnIn2S4 (71654.39 µmol·g−1·h−1) and most reported ZnIn2S4-based photocatalysts. In addition, the density functional theory (DFT) calculation results further show that the absolute value of ΔGH* of the composite photocatalyst is significantly reduced to 0.08 eV, and the adsorption–desorption potential barrier is reduced considerably, indicating that the Cu-ZnIn2S4/WO3/WS2 photocatalytic system is more favorable to H* adsorption. This excellent performance is attributed to the unique transfer mechanism of Cu doping and mixed heterojunctions. This study provides a new idea for photocatalytic hydrogen production and can provide a valuable reference for future research on photocatalytic hydrogen production technology.

中文翻译：

---

三元异质结构Cu-ZnIn2S4/WO3/WS2花状微球在可见光照射下实现高效光催化析氢


开发新型复合光催化剂是实现水生氢高效光催化分解的关键。本研究采用两步水热法制备了 Cu-ZnIn2S4/WO3/WS2 纳米结构。Cu 掺杂和混合异质结（Z 型异质结和 I 型异质结）独特的电荷转移机制显着增强了电荷转移和分离，从而使 Cu-ZnIn2S4/WO3/WS2 具有优异的光催化析氢性能。Cu-ZnIn2S4/WO3/WS2 的析氢速率为 93032.29 μmol·g−1·h−1，分别是 ZnIn2S4 和 Cu-ZnIn2S4 的 37.82 倍和 3.33 倍，430nm 处的量子效率为 37.04 %。它也优于 Pt 修饰的 Cu-ZnIn2S4 （71654.39 μmol·g-1·h-1） 和大多数报道的基于 ZnIn2S4 的光催化剂。此外，密度泛函理论 （DFT） 计算结果进一步表明，复合光催化剂的 ΔGH* 绝对值显著降低至 0.08 eV，吸附-脱附势垒显著降低，表明 Cu-ZnIn2S4/WO3/WS2 光催化体系更有利于 H* 吸附。这种优异的性能归功于 Cu 掺杂和混合异质结的独特转移机制。本研究为光催化制氢提供了新思路，可为未来光催化制氢技术的研究提供有价值的参考。