近日，北京大学马丁团队报道了尖晶石中Ir单原子诱导5d自旋极化增强析氧。相关论文发表在2026年5月11日出版的《德国应用化学》杂志上。

精确调控单原子中心的配位环境，对于揭示局域对称性如何决定电子结构与催化行为至关重要。

研究组开发了一种锂辅助的空位工程策略，将Ir单原子选择性嵌入尖晶石ZnCo₂O₄的四面体位点和八面体位点，从而制备出配位环境精确可控、结构明确的单原子催化剂。理论计算与实验结果表明，八面体嵌入通过增强Ir 5d态与周围Co-O框架之间的杂化，诱导了Ir的5d电子重构和自旋极化。这种由配位控制的电子态重塑了氧中间体的结合能，从而提升了本征反应活性。

因此，位于八面体位的Ir在300 mV过电位下表现出卓越的析氧反应（OER）质量活性，达5520 A/gIr，是IrO₂的920倍，并在阴离子交换膜电解槽中稳定运行超过200小时。这些发现突显了晶体位点选择在调控5d单原子电子结构中的关键作用，并为配位控制下的OER反应活性提供了机理层面的认识。

附：英文原文

Title: Site-Specific Ir Single Atoms in Spinel Induce 5d Spin Polarization for Enhanced Oxygen Evolution

Author: Yong Wang, Zijian Yuan, Zeyan Cen, Shixiang Yu, Chengyu Li, Haoyi Tang, Ao Cao, Tianze Wu, Xiao Ren, Ding Ma

Issue&Volume: 2026-05-11

Abstract: Precise control of the coordination environment of single-atom centers is essential to reveal how local symmetry governs electronic structure and catalytic behavior. Here, we develop a Li-assisted vacancy-engineering strategy to selectively embed Ir single atoms into tetrahedral and octahedral sites of spinel ZnCo2O4, producing well-defined single-atom catalysts with precisely controlled coordination environments. Theoretical calculations and experiments reveal that octahedral incorporation induces 5d electronic reconfiguration and spin polarization in Ir, driven by strengthened hybridization between Ir 5d states and the surrounding Co-O framework. This coordination-controlled electronic state reshapes oxygen-intermediate binding energetics, thereby enhancing intrinsic reactivity. Consequently, octahedral-site Ir exhibits an exceptional oxygen evolution reaction (OER) mass activity of 5520  A/gIr at 300 mV, which is 920 times higher than that of IrO2, and maintains stability for over 200 h in an anion-exchange membrane electrolyzer. These findings highlight the key role of crystallographic site selection in tuning 5d single-atom electronic structure and offer mechanistic insight into coordination-controlled OER reactivity.

DOI: 10.1002/anie.2500154

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.2500154