近日，中山大学姚向东团队揭示了金属氢氧化物协同硫原酸氟工程打破OER结垢关系。相关论文于2025年8月21日发表于在《德国应用化学》杂志上。

析氧反应（OER）是电化学水分解的瓶颈，主要受关键中间体（OH*和OOH*）结合能之间的标度关系的限制，理论过电位最小为0.37 eV。打破这种比例关系对于提高OER活动至关重要，但有效的策略仍然很少。

研究组证明了在硫原吸附的镍铁氢氧化物（NiFeOOH）上引入高电负性的氟显著缩短了硫原和OER中间体（*OH和*OOH）之间的氢键。这种缩短促进了质子转移动力学，并将理论过电位降低到0.27 eV。在这些计算的指导下，合成了硫原酸盐和氟在金属氢氧化物（NiFeSF-R）催化剂上的共吸附，在1.0M KOH中，其在304mV的超低过电位下达到1.0 A cm^-2，与NiFeS-R和NiFe相比分别大幅提高了106和182 mV。

值得注意的是，NiFeSF-R具有出色的稳定性，可保持1.0 A cm^-2超过500小时，降解可以忽略不计。在阴离子交换膜水电解槽中，NiFeSF-R阳极在1.73 V下，在50°C下加热700小时，可稳定达到1.0 A cm^-2。这项工作强调了局部协调环境调整的潜力，以打破高性能OER催化剂的缩放关系。

附：英文原文

Title: Synergistic Chalcogenate and Fluorine Engineering on Metal Oxyhydroxides Breaks the OER Scaling Relationship

Author: Keyu Wang, Shiyi Li, Jiankun Li, Chen Liang, Jiayu Li, Linfeng Lei, Minghui Zhu, Linzhou Zhuang, Jun Chen, Zhi Xu, Xiangdong Yao

Issue&Volume: 2025-08-21

Abstract: 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 cm2 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 cm2 for over 500 h with negligible degradation. In an anion exchange membrane water electrolyzer, the NiFeSF-R anode stably achieves 1.0 A cm2 at 1.73 V for 700 h at 50 °C. This work highlights the potential of local coordination environment tuning to break scaling relationships for high-performance OER catalysts.

DOI: 10.1002/anie.202511112

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202511112