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

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 (Ni₂Co₁In₂S₂) with orderly-oxidized Kagome lattices, in which spatial wave functions of the triangular metal units (M₃) are spontaneously converted to the anti-symmetry feature due to the symmetry breaking from controllable bridged-oxygen decorations (M₃O), 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.