Efficient Holes Abstraction by Precisely Decorating Ruthenium Single Atoms and RuOx Clusters on ZnIn2S4 for Photocatalytic Pure Water Splitting

• Published in: Small (Weinheim an der Bergstrasse, Germany) Germany), 2024-11, Vol.20 (45), p.e2405153-n/a
• Main Authors: Wu, Shuangzhi, Zhang, Shengyu, Zhang, Qingsheng, Liu, Guowei, Yang, Jianjun, Guan, Zhongjie, Zou, Zhigang
• Format: Article
• Language: English
• Subjects: Atomic structure; Basal plane; Clusters; Electric fields; Electronic structure; Electrons; holes abstraction; Hydrogen peroxide; Hydrogen production; Light irradiation; Oxidation; Photocatalysis; Photocatalysts; pure water splitting; Quantum efficiency; Ru single atom; RuOx cluster; Ruthenium; Surface water; Water splitting; ZnIn2S4
• ISSN: 1613-6810; 1613-6829; 1613-6829
• DOI: 10.1002/smll.202405153

Developing efficient photocatalysts for two‐electron water splitting with simultaneous H2O2 and H2 generation shows great promise for practical application. Currently, the efficiency of two‐electron water splitting is still restricted by the low utilization of photogenerated charges, especially holes, of which the transfer rate is much slower than that of electrons. Herein, Ru single atoms and RuOx clusters are co‐decorated on ZnIn2S4 (RuOx/Ru‐ZIS) to employ as multifunctional sites for efficient photocatalytic pure water splitting. Doping of Ru single atoms in the ZIS basal plane enhances holes ion from bulk ZIS by regulating the electronic structure, and RuOx clusters offer a strong interfacial electric field to remarkably promote the out‐of‐plane migration of holes from ZIS. Moreover, Ru single atoms and RuOx clusters also serve as active sites for boosting surface water oxidation. As a result, an excellent H2 and H2O2 evolution rates of 581.9 µmol g−1 h−1 and 464.4 µmol g−1 h−1 is achieved over RuOx/Ru‐ZIS under visible light irradiation, respectively, with an apparent quantum efficiency (AQE) of 4.36% at 400 nm. This work paves a new way to increase charge utilization by manipulating photocatalyst using single atom and clusters. Ru single atoms and RuOx clusters efficiently holes from bulk ZnIn2S4, thus improving charge separation and prolonging the lifetime of holes. In addition, Ru single atoms and RuOx clusters also serve as active sites for boosting surface water oxidation. Consequently, the photocatalytic pure water splitting performance of ZnIn2S4 is significantly improved.