Unraveling volcano trend in OER of metal–organic frameworks with asymmetric configuration through energy band engineering

Abstract

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 (Ed) 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.