Spatially extended asymmetry directs electron transfer and modulates water oxidation deprotonation behavior on dual-atom catalysts

Abstract

Introducing local coordination asymmetry through heteroatom substitution in homonuclear dual-atom catalysts (DACs) is an effective strategy to modulate the electronic state of metal centers. However, this approach often results in chaotic and unpredictable changes in electron transfer between the metals and coordinating atoms, which limits precise adjustment of the intermediate adsorption. In this study, we propose a spatially extended asymmetric coordination design strategy that enables simultaneous and precise regulation of electron transfer and differentiation of metal electronic states. Based on first-principles calculations, the constructed homonuclear DACs embedded in a hexagonal boron nitride/graphene (h-BN/Gra) heterostructure demonstrate well-defined electron transfer. The electronegativity differences among B, N, and C coordination atoms lead to distinct d-orbital configurations at the metal centers, which in turn modulate the *OH–*OH deprotonation behavior, following the trend of N coordination > C coordination > B coordination. The constructed volcano plot using the descriptor of ΔG_*O–*OH − ΔG_*OH–*OH provides clear theoretical guidance and design principles for optimizing oxygen evolution reaction activity. This work establishes a conceptual transition from local to spatially extended asymmetric coordination, offering a new theoretical framework for the rational design of asymmetric DACs.