Navigating surface reconstruction of spinel oxides for electrochemical water oxidation

Abstract

Understanding and mastering the structural evolution of water oxidation electrocatalysts lays the foundation to finetune their catalytic activity. Herein, we demonstrate that surface reconstruction of spinel oxides originates from the metal-oxygen covalency polarity in the M_T–O–M_O backbone. A stronger M_O–O covalency relative to M_T–O covalency is found beneficial for a more thorough reconstruction towards oxyhydroxides. The structure-reconstruction relationship allows precise prediction of the reconstruction ability of spinel pre-catalysts, based on which the reconstruction degree towards the in situ generated oxyhydroxides can be controlled. The investigations of oxyhydroxides generated from spinel pre-catalysts with the same reconstruction ability provide guidelines to navigate the cation selection in spinel pre-catalysts design. This work reveals the fundamentals for manipulating the surface reconstruction of spinel pre-catalysts for water oxidation.

Precise control of water oxidation activity calls for the mastery of surface reconstruction of electrocatalysts. Here, the authors identify the structural origin of surface reconstruction on spinel oxides and report a criterion to evaluate the reconstruction degree, which enable the design of spinel pre-catalyst with controlled reconstruction ability.