Evoking Cooperative Geometric and Electronic Interactions at Nanometer Coherent Interfaces toward Enhanced Electrocatalysis

Integrating high‐valence metal sites into transition metal‐based oxygen evolution reaction (OER) catalysts turns out to be a prevailing solution to replacing noble metal‐based electrocatalysts. However, stabilizing the thermodynamically unfavorable high‐valence metal sites within the electrocatalyst remains challenging. Hereby, a general strategy is proposed that evokes cooperative geometric and electronic interactions at nanometer coherent interfaces, which effectively stabilizes interfacial high‐valence metal sites within homogeneously distributed heterostructures and significantly enhances electrocatalytic activity. As a proof‐of‐concept study, by derivatizing multicomponent isoreticular hybridized metal–organic frameworks with separated σ‐ or π‐bonded moieties, bimetal Ni–Fe selenides heterostructures with nanoscopic compositional and structural homogeneity are grafted. Such heterostructures entail nanometer‐sized coherent interfaces that accommodate large geometric distortions and cooperatively stabilize the energetically unfavorable Jahn–Teller active electronic states of high‐valence interfacial Ni sites. The presence of high‐valence interfacial Ni sites and associated collective Jahn–Teller distortions greatly facilitate the Ni oxidation cycling through Ni3+/Ni4+ transition and stabilizes the *O key intermediate at Ni‐Se dual sites, both of which synergistically lowers down the overall OER overpotential. Evoking cooperative geometric and electronic interaction at the interface of coherently registered NiSe2/FeSe2 heterostructures are derived from hybrid metal‐organic frameworks. Such interfacial interactive stabilizes the thermodynamically unfavorable high‐valence Ni3+ sites, greatly facilitates the Ni oxidation cycling through Ni3+/Ni4+ transition and stabilizes the *O key intermediate at Ni‐Se dual sites, which synergistically enhance the electrocatalytic activity toward oxygen evolution reaction.