Topology‐Sensitive Spin‐Selecting Super‐Exchange Interactions at Half‐Antiperovskites with Orderly‐Oxidized Semimetals for Acidic Water Oxidation

Abstract

Abstract Developing inexpensive catalysts for acidic water oxidation plays a critical role in energy conversions and storages, but which have to trade off their catalytic activity and electrochemical stability. Different from traditional nano‐engineering, herein we focus onto manipulating the spin‐dependent topological quantum interactions to facilitate acidic water splitting at half‐antiperovskite (Ni 2 Co 1 In 2 S 2 ) with orderly‐oxidized Kagome lattices, in which spatial wave functions of the triangular metal units (M 3 ) are spontaneously converted to the anti‐symmetry feature due to the symmetry breaking from controllable bridged‐oxygen decorations (M 3 O), leading to a spin‐selecting‐dependent electronic reconfiguration. This topology‐sensitive symmetry breaking makes the super‐exchange interactions among neighboring metal sites switch to the indirect out‐plane configuration (M─O─M) from the direct in‐plane form (M─M), meanwhile the spin‐dependent transformation from antiferromagnetic states to ferromagnetic states causes these metal sites to demonstrate a semi‐metallic property for optimizing their bonding interactions with reactants. As a result, the capacity of carrier migration and intermediate diffusion in the inner Helmholtz region is significantly improved, which makes mass activity increase to 20.5 A g −1 at an overpotential of ≈356 mV, demonstrating an obvious superiority over the other state‐of‐the‐art catalysts without noble metals. This work provides a new insight for designing topology‐dependent catalysts to better understand spin‐related reaction kinetics.