The development of high‐performance oxygen evolution reaction (OER) catalysts is crucial to achieve the clean production of hydrogen via water splitting. Recently, Co‐based oxides have been intensively investigated as some of the most efficient and cost‐effective OER catalysts. In particular, compositional tuning of Co‐based oxides via doping or substitution is shown to significantly affect their catalytic activity. Nevertheless, the origin of this enhanced catalytic activity and the reaction mechanism occurring at catalytic active sites remain controversial. Theoretical investigations are performed on the electrocatalytic properties of pristine and transition metal (Fe, Ni, and Mn)‐substituted Co oxides using first‐principle calculations. A comprehensive evaluation of the doping effects is conducted by considering various oxygen local environments in the crystal structure, which helps elucidate the mechanism behind the doping‐induced enhancement of Co‐based catalysts. It is demonstrated that the local distortion induced by dopant cations remarkably facilitates the catalysis at a specific site by modulating the hydrogen bonding. In particular, the presence of Jahn–Teller‐active Fe(IV) is shown to result in a substantial reduction in the overpotential at the initially inactive catalysis site without compromising the activity of the pristine active sites, supporting previous experimental observations of exceptional OER performance for Fe‐containing Co oxides.

中文翻译：

---

掺杂对氧化钴水氧化电催化性能影响的原子研究

高性能析氧反应（OER）催化剂的开发对于实现水分解清洁制氢至关重要。最近，钴基氧化物作为一些最有效和最具成本效益的 OER 催化剂得到了深入研究。特别是，通过掺杂或取代来调整钴基氧化物的成分可显着影响其催化活性。然而，这种增强的催化活性的起源和催化活性位点发生的反应机制仍然存在争议。使用第一原理计算对原始和过渡金属（Fe、Ni 和 Mn）取代的 Co 氧化物的电催化性能进行了理论研究。通过考虑晶体结构中的各种氧局域环境对掺杂效果进行综合评估，这有助于阐明掺杂诱导Co基催化剂增强的机制。结果表明，掺杂剂阳离子引起的局部变形通过调节氢键显着促进了特定位点的催化。特别是，Jahn-Teller 活性 Fe(IV) 的存在被证明会导致最初非活性催化位点的过电势大幅降低，而不会影响原始活性位点的活性，这支持了之前关于优异 OER 性能的实验观察结果对于含铁钴氧化物。