Spin Effect to Regulate the Electronic Structure of IrDFe Aerogels for Efficient Acidic Water Oxidation

"Spin" has been recently reported as an important degree of electronic freedom to promote catalysis, yet how it influences electronic structure remains unexplored. This work reports the spin-induced orbital hybridization in IrFe bimetallic aerogels, where the electronic structure of Ir sites is effectively regulated by tuning the spin property of Fe atoms. The spin-optimized electronic structure boosts oxygen evolution reaction (OER) electrocatalysis in acidic media, resulting in a largely improved catalytic performance with an overpotential of as low as 236 mV at 10 mA cm-2. Furthermore, the gelation kinetics for the aerogel synthesis is improved by an order of magnitude based on the introduction of a magnetic field. Density functional theory calculation reveals that the increased magnetic moment of Fe (3d orbital) changes the d-band structure (i.e., the d-band center and bandwidth) of Ir (5d orbital) via orbital hybridization, resulting in optimized binding of reaction intermediates. This strategy builds the bridge between the electron spin theory with the d-band theory and provides a new way for the design of high-performance electrocatalysts by using spin-induced orbital interaction. This work bridges the gap between spin property and electronic structure by demonstrating spin-induced orbital hybridization in IrFe aerogels. The electronic structure of Ir sites can be effectively manipulated by tuning the spin property of the Fe site, thus leading to optimized binding of the reaction intermediates and electrocatalytic performances. This study holds great potential for the development of spin-related heterogeneous catalysis. image