Local symmetry breaking of catalysts has emerged as an effective strategy for finely tuning oxygen evolution reaction (OER) activity, yet the fundamental comprehension regarding asymmetric structure-activity relationships remains limited. Here, we propose the energy band engineering to bridge the correlation between established asymmetric electronic structure and adsorption/desorption ability of reaction intermediates within metal-organic frameworks (MOFs). The deliberate synthesis of CoM-MOFs (M=Cu, Ni, and Fe) with distinct coordination microenvironments enables the customization of asymmetric Co-O-M electronic structure. A volcano-shaped relationship can be revealed between calculated OER overpotential and average d‐band center (E) energy level for both active Co sites and substituted M. The CoFe-MOF, located close to the summit, showcases the balanced reaction intermediate behavior and thus for enhanced OER activity. This work presents a promising approach to thoroughly understand asymmetric electronic structure-activity relationships from the perspective of energy band engineering and further guide the discovery of high-efficiency MOF-based OER catalysts.

中文翻译：

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通过能带工程揭示不对称构型金属有机框架OER中的火山趋势


催化剂的局部对称性破缺已成为微调析氧反应（OER）活性的有效策略，但对不对称结构-活性关系的基本理解仍然有限。在这里，我们提出了能带工程来弥合已建立的不对称电子结构与金属有机框架（MOF）内反应中间体的吸附/解吸能力之间的相关性。具有独特配位微环境的 CoM-MOF（M=Cu、Ni 和 Fe）的有意合成使得能够定制不对称 Co-O-M 电子结构。计算出的 OER 超电势与活性 Co 位点和取代 M 的平均 d 带中心 (E) 能级之间可以揭示火山形关系。CoFe-MOF 位于靠近峰顶的位置，展示了平衡反应中间行为和从而增强开放教育资源活动。这项工作提出了一种从能带工程角度彻底理解不对称电子结构-活性关系的有前途的方法，并进一步指导高效基于 MOF 的 OER 催化剂的发现。