It is always interesting but challenge to reasonably design efficient and stable hierarchical photocatalyst for H evolution from water. In this paper, we synthesized ZnInS/TiO (ZIS/TiVo) heterojunction by adjusting the ratio of ZIS to TiVo and Vo concentration. Importantly, the results from various characterizations such as HRTEM, STEM/EDS, XPS, EPR, and Raman proved the existence of strong interaction between sulfur sites and Ti/Vo by charge attraction. Such interaction along the interface of heterojunction generated the synergy, which extended light response to visible-infrared range, significantly facilitated charge separation and transfer through Z-scheme, stabilized S and Vo sites without sacrifice during reaction, but also provided active sites for water activation. As result, the optimal 30ZIS/TiVo-B showed over 20 and 4 times higher H production activity than TiO and ZnInS, respectively. 30ZIS/TiVo-B also demonstrated excellent long-term stability without deactivation, while the activity of 30ZIS/TiO decreased by 90 % after 56 h. Findings from this work can open a new avenue to design photocatalyst with high activity and stability by controlling active sites and their interaction.

中文翻译：

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Z型ZnIn2S4/TiO2-x异质结中硫位点和氧空位之间的强相互作用可提高光催化氢产率和稳定性


合理设计高效稳定的多级光催化剂用于从水中析氢一直是有趣但具有挑战性的。在本文中，我们通过调整ZIS与TiVo的比例和Vo浓度合成了ZnInS/TiO（ZIS/TiVo）异质结。重要的是，HRTEM、STEM/EDS、XPS、EPR 和拉曼等各种表征的结果证明了硫位点和 Ti/Vo 之间通过电荷吸引存在强相互作用。沿着异质结界面的这种相互作用产生了协同作用，将光响应扩展到可见光-红外范围，显着促进了Z型电荷的分离和转移，稳定了S和Vo位点而不会在反应过程中牺牲，而且还为水活化提供了活性位点。结果，最佳的 30ZIS/TiVo-B 的产氢活性分别比 TiO 和 ZnInS 高 20 倍和 4 倍。 30ZIS/TiVo-B 还表现出优异的长期稳定性而不会失活，而 30ZIS/TiO 的活性在 56 小时后下降了 90%。这项工作的发现可以为通过控制活性位点及其相互作用来设计具有高活性和稳定性的光催化剂开辟一条新途径。