文献类型：期刊文献

英文题名：Synergistic Chalcogenate and Fluorine Engineering on Metal Oxyhydroxides Breaks the OER Scaling Relationship

作者：Wang, Keyu[1];Li, Shiyi[1];Li, Jiankun[1];Liang, Chen[1];Li, Jiayu[1];Lei, Linfeng[1,4];Zhu, Minghui[1];Zhuang, Linzhou[1];Chen, Jun[5];Xu, Zhi[1];Yao, Xiangdong[2,3]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Sun Yat Sen Univ Shenzhen, Sch Adv Energy, Shenzhen 518107, Peoples R China;[3]Sun Yat Sen Univ Shenzhen, IGCME, Shenzhen 518107, Peoples R China;[4]Suzhou Lab, Suzhou 215000, Peoples R China;[5]Univ Wollongong, Intelligent Polymer Res Inst, Innovat Campus,Squires Way, North Wollongong, NSW 2500, Australia

年份：2025

卷号：64

期号：42

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20253419031532);WOS:【SCI-EXPANDED(收录号:WOS:001593800000020)】；

基金：This work was supported by the research funding provided by National Key R&D Program of China (Grant No. 2021YFB3801301), National Natural Science Foundation of China (Grant Nos. 22378119, 22075076, and 22208092),Shanghai Pilot Program for Basic Research (22TQ1400100-4), and Australian Research Council (DP220101290). X.Y. also thanks the support from Guangdong Province Introduced Innovative and Entrepreneurial Team Program(2023ZT10L061) and National Natural Science Foundation of China (U24A20564). We thank the staff from BL07Ubeamline of Shanghai Synchrotron Radiation Facility (SSRF)for assistance with XMCD/XAFS data collection.

语种：英文

外文关键词：Hydrogen bonds; NiFeOOH; Oxygen evolution reaction; Proton transfer kinetics; Scaling relationship

摘要：The oxygen evolution reaction (OER), a bottleneck in electrochemical water splitting, is fundamentally limited by a scaling relationship between the binding energies of key intermediates (OH* and OOH*), imposing a minimum theoretical overpotential of 0.37 eV. Breaking this scaling relationship is crucial for enhancing OER activity, yet effective strategies remain scarce. We demonstrate that the introduction of high-electronegativity fluorion on chalcogenate-adsorbed nickel-iron oxyhydroxide (NiFeOOH) significantly shortens hydrogen bonds between the chalcogenate and OER intermediates (*OH and *OOH). This shortening promotes proton transfer kinetics and lowers the theoretical overpotential to 0.27 eV. Guided by these calculations, the co-adsorption of chalcogenate and fluorion on metal oxyhydroxide (NiFeSF-R) catalyst is synthesized, and it achieves 1.0 A cm(-2) at an ultralow overpotential of 304 mV in 1.0 M KOH, a substantial improvement of 106 and 182 mV compared to NiFeS-R and NiFe, respectively. Notably, NiFeSF-R exhibits exceptional stability, sustaining 1.0 A cm(-2) for over 500 h with negligible degradation. In an anion exchange membrane water electrolyzer, the NiFeSF-R anode stably achieves 1.0 A cm(-2) at 1.73 V for 700 h at 50 degrees C. This work highlights the potential of local coordination environment tuning to break scaling relationships for high-performance OER catalysts.