AI 中文总结
本研究通过密度泛函理论分析不同金属配位的有机金属单原子催化剂，发现MO₄配位结构（如M₄(OHPTP)₂，M为Zn、Co）可平衡ORR/OER的活性与稳定性，为电催化剂设计提供理论依据。
AI 中文摘要
有机金属层状材料已成为氧还原反应（ORR）和氧析出反应（OER）极具潜力的单原子催化剂，但其实际应用受限于电化学稳定性不足。本文采用密度泛函理论研究，阐明含金属-N₄（MN₄）和金属-O₄（MO₄）配位的有机金属单原子催化剂中催化活性与稳定性的关系。对比了嵌入石墨烯的MN₄结构、酞菁类框架与含MO₄配位的框架，包括M₄(OHPTP)₂和M₃(HHTP)₂（M为Mn、Fe、Co、Ni、Cu、Zn）。稳定性通过表面Pourbaix分析评估，活性采用计算氢电极法评价。MN₄体系表现出有竞争力的过电位，但存在强pH依赖的不稳定性；相比之下，MO₄框架在宽pH范围内展现出更高的稳定性，同时保持良好的催化性能。所提出的稳定性描述符可实现不同体系间的直接比较，确定MO₄配位结构，尤其是M₄(OHPTP)₂（M为Zn、Co）是实际电催化中平衡活性与稳定性的最优选择。
英文摘要
Organometallic layered materials have emerged as promising single-atom catalysts for oxygen reduction and evolution reactions, but their practical use has been limited by insufficient electrochemical stability. Here, we present a density functional theory study clarifying the relationship between catalytic activity and stability in organometallic single-atom catalysts with metal-N$_4$ (MN$_4$) and metal-O$_4$ (MO$_4$) coordination. We compare graphene-embedded MN$_4$ motif and phthalocyanine-like frameworks with MO$_4$-coordination frameworks, including M$_4$(OHPTP)$_2$ and M$_3$(HHTP)$_2$ (M = Mn, Fe, Co, Ni, Cu, Zn). Stability is assessed by surface Pourbaix analysis, while activity is evaluated using the computational hydrogen electrode method. MN$_4$ systems show competitive overpotentials but suffer strong pH-dependent instability. In contrast, MO$_4$ frameworks exhibit enhanced robustness across wide pH ranges while maintaining good catalytic performance. A proposed stability descriptor enables direct comparison across systems, identifying MO$_4$ coordination structures, particularly M$_4$(OHPTP)$_2$ (M = Zn, Co) as optimal for balancing activity and stability in practical electrocatalysis.
