Yang Chengdong, Gao Yun, Xing Zhengyu, Shu Xinxin, Zhuang Zechao, Wang Yueqing, Zheng Yijuan, Li Shuang, Cheng Chong, Wang Dingsheng, Zhang Jintao
Key Laboratory for Colloid and Interface Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shandong University, Jinan, China.
Department of Chemistry, Engineering Research Center of Advanced Rare Earth Materials, Tsinghua University, Beijing, China.
Nat Commun. 2025 Jul 12;16(1):6459. doi: 10.1038/s41467-025-61871-2.
Uncovering the dynamic structures of water at the electrode-solution interface is crucial for various electrocatalysis processes, where water acts as a proton and electron source. However, precisely controlling the state of water on complex interfaces remains challenging. Inspired by the metalloproteins in natural enzymes, we herein demonstrate that the hydrophilic sulfo-oxygen bridging between Co and Ru sites (Co-SO-Ru) optimizes interfacial water structure via a favorable hydrogen-bond network, promoting hydrogen oxidation and evolution reactions. Mechanistic studies reveal that the stereoscopic sulfo-oxygen bridges enhance the connectivity of hydrogen-bond network to promote the proton transfer process via repelling cations from the electrode surface. Furthermore, electron donating Co sites reduce the surface oxophilicity of Ru to optimize the adsorption-desorption behaviors of hydroxyl, governing the timely refreshed Ru sites to enhance catalytic performances. Such bioinspired active sites offer a different pathway for the precise design of interfacial water structure to improve electrocatalysis.
揭示电极-溶液界面处水的动态结构对于各种电催化过程至关重要，在这些过程中，水充当质子和电子源。然而，精确控制复杂界面上的水状态仍然具有挑战性。受天然酶中金属蛋白的启发，我们在此证明，钴和钌位点之间的亲水性硫氧桥（Co-SO-Ru）通过有利的氢键网络优化界面水结构，促进氢氧化和析氢反应。机理研究表明，立体硫氧桥增强了氢键网络的连通性，通过排斥电极表面的阳离子促进质子转移过程。此外，供电子的钴位点降低了钌的表面亲氧性，以优化羟基的吸附-解吸行为，控制钌位点的及时更新以提高催化性能。这种受生物启发的活性位点为精确设计界面水结构以改善电催化提供了一条不同的途径。
