Electronic engineering of spinels for advanced electrocatalysis

Abstract

Spinels represent promising candidates for clean energy electrocatalysis due to their abundance and electronic structure adjustability. However, their intrinsic catalytic activ-ity remains limited. This review analyzes the fundamental correlations between elec-tronic structure and catalytic performance in spinel-based electrocatalysts. It elucidates the critical roles of coordination geometry e.g. tetrahedral vs. octahedral sites, and the electronic configuration of active metal centers, including d-band center position and spin state. The applications of these electronic structure modulation strategies across in electrocatalytic reactions, encompassing the oxygen evolution reaction, oxygen reduc-tion reaction, hydrogen evolution reaction, nitrogen reduction reaction, nitrate reduction reaction, carbon dioxide reduction reaction, and urea oxidation reaction were further analyzed. Synthesizing insights from these diverse reaction systems, this review pro-poses a universal design paradigm for efficient spinel electrocatalysts: coordination en-gineering-d-band center optimization-spin state modulation. Finally, challenges in electronic-state control and future research frontiers are outlined, providing a robust mechanistic framework for the rational design of spinel electrocatalysts for sustainable energy technologies.