Atom doping and defect construction are effective strategies to enhance the performance of photocatalysts. Herein, zirconium (Zr) doping and sulfur vacancies (Vs) are introduced on marigold-like ZnInS (Zr-ZIS-Vs) by controlling the amount of sulfur precursors and ZrCl via a one-pot hydrothermal process. Remarkably, the optimized Zr-ZIS-Vs catalyst exhibits excellent photocatalytic activity, giving a photocatalytic hydrogen evolution rate of 9.44 mmol g h, which is 10.73, 4.39 and 2.37 times higher than pure ZnInS (ZIS, 0.88 mmol g h), ZnInS with sulfur vacancies alone (ZIS-Vs, 2.15 mmol g h), and ZnInS with Zr doping alone (Zr-ZIS, 3.98 mmol g h). The apparent quantum efficiency (AQE) of Zr-ZIS-Vs achieves 27.15 % and 4.90 % at λ = 370 and 456 nm, respectively. Experimental results and theoretical simulations reveal the behavioral mechanisms of the deletion of S atoms and the tendency of Zr to replace In, indicating that the defective and reference strategies can narrow the band gap, provide abundant active sites, enhance the effective transport and separation of photogenerated carriers, and modulate the transfer of active sites to empirical site S atoms to achieve the synergistic thermodynamic and kinetic interactions, which effectively enhances the performance of photocatalytic hydrogen production.

中文翻译：

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万寿菊状 Zn​​3In2S6 中原子掺杂和缺陷构建的协同作用改善光催化产氢


原子掺杂和缺陷构建是提高光催化剂性能的有效策略。在此，通过一锅水热过程控制硫前驱体和 ZrCl 的量，在万寿菊状 Zn​​InS (Zr-ZIS-Vs) 上引入锆 (Zr) 掺杂和硫空位 (Vs)。值得注意的是，优化后的Zr-ZIS-Vs催化剂表现出优异的光催化活性，光催化析氢速率为9.44 mmol gh，分别是纯ZnInS（ZIS，0.88 mmol gh）、含硫空位的ZnInS的10.73、4.39和2.37倍。单独的（ZIS-Vs，2.15 mmol gh）和单独掺杂 Zr 的 ZnInS（Zr-ZIS，3.98 mmol gh）。 Zr-ZIS-Vs 在 λ = 370 和 456 nm 时的表观量子效率 (AQE) 分别达到 27.15 % 和 4.90 %。实验结果和理论模拟揭示了S原子缺失的行为机制和Zr取代In的趋势，表明缺陷和参考策略可以缩小带隙，提供丰富的活性位点，增强光生物质的有效传输和分离。载体，并调节活性位点向经验位S原子的转移，实现协同热力学和动力学相互作用，有效增强光催化产氢的性能。