The principle of how the active sites of catalysts match the reaction intermediates has long been sought after. Herein, we report a theory-guided atomic design and fabrication strategy of a C-based catalyst with diatomic Fe–Ni and N,P co-doping for the oxygen evolution reaction (OER). The configuration matching (with O∗ on the Ni site and OH∗ on the adjacent Fe site) and the local electron engineering by P doping significantly facilitate the rate-determining step of OOH∗ formation. Such diatomic Fe–Ni is demonstrated to be thermodynamically stable and is precisely constructed through the pyrolysis of Fe³⁺/Ni²⁺-adsorbed ZIF-8 under NaH₂PO₂ co-feeding. The synergistic effects endow the catalyst with a low overpotential and high turnover frequency, exceeding all transition-metal N-based catalysts so far as we know, which provides a deep understanding of the OER mechanism on heteroatomic metal-based catalysts. This strategy will pave the way for novel catalyst design and the replacement of noble-metal-based catalysts.

催化剂的活性位点如何与反应中间体匹配的原理一直是人们所追求的。在此，我们报告了一种基于理论指导的原子设计和制造策略，该催化剂具有双原子 Fe-Ni 和 N,P 共掺杂用于析氧反应 (OER)。配置匹配（在 Ni 位点上有 O*，在相邻的 Fe 位点上有 OH*）和 P 掺杂的局部电子工程显着促进了 OOH* 形成的速率决定步骤。这种双原子 Fe-Ni 被证明是热力学稳定的，并且是通过在 NaH ₂ PO ₂下吸附Fe ³⁺ /Ni ^{2+ 的}ZIF-8的热解而精确构建的共同喂养。协同效应使催化剂具有较低的过电位和较高的转换频率，超过了目前已知的所有过渡金属 N 基催化剂，这为对杂原子金属基催化剂的 OER 机理提供了深刻的理解。该策略将为新型催化剂设计和贵金属基催化剂的替代铺平道路。