Spin‐State Modulation on Metal–Organic Frameworks for Electrocatalytic Oxygen Evolution

Abstract Electrochemical oxygen evolution reaction (OER) kinetics are heavily correlated with hybridization of the transition metal d‐orbital and oxygen intermediate p‐orbital, which dictates the barriers of intermediate adsorption/desorption on the active sites of catalysts. Herein, a strategy is developed involving strain engineering and coordination regulation to enhance the hybridization of Ni 3d and O 2p orbitals, and the as‐synthesized Ni‐2,6‐naphthalenedicarboxylic acid metal–organic framework (DD‐Ni‐NDA) nanosheets deliver a low OER overpotential of 260 mV to reach 10 mA cm⁻². By integrating an alkaline anion exchange membrane electrolyzer and Pt/C electrode, 200 and 500 mA cm⁻² current densities are reached with cell voltages of 1.6 and 2.1 V, respectively. When loaded on a BiVO₄ photoanode, the nanosheet enables highly active solar‐driven water oxygen. Structural characterizations together with theoretical calculations reveal that the spin state of the centre Ni atoms is regulated by the tensile strain and unsaturated coordination defects in DD‐Ni‐NDA, and such spin regulation facilitates spin‐dependent charge transfer of the OER. Molecular orbital hybridization analysis reveals the mechanism of OH* and OOH* adsorption energy regulation by changes in the DD‐Ni‐NDA spin state, which provides a deeper understanding of the electronic structure design of catalysts for the OER.