Rational Design of Transition‐Metal Dual‐Atom Catalysts: Exploiting Neighboring Effects for Efficient CO 2 Reduction

ABSTRACT Harnessing the synergistic interactions between adjacent bimetallic atoms, dual‐atom catalysts (DACs) emerge as promising candidates for the CO 2 reduction reaction (CO 2 RR). However, precise regulation of neighboring effects at dual‐atom sites to optimize and enhance CO 2 RR performance remains highly challenging. This review focuses on Fe‐, Co‐, Ni‐, and Cu‐based DACs, systematically elucidating how proximity effects modulate reaction intermediates and product selectivity in both homonuclear and heteronuclear systems. The distinct electronic configurations of homonuclear and heteronuclear DACs lead to diversified CO 2 RR pathways and product distributions. When the two metal atoms are spatially separated, the weakened electronic coupling primarily lowers the energy barrier for C 1 intermediates, thereby improving the selectivity toward C 1 products. In contrast, a reduced metal–metal distance strengthens interatomic electronic interactions through the formation of N/O‐coordinated or direct metal–metal structures, facilitating C─C coupling and thus enhancing C 2 product formation. A mechanistic understanding of C─C coupling serves as a fundamental basis for directing CO 2 RR toward multi‐carbon products with higher energy density and practical relevance. Additionally, theoretical investigations provide valuable insights into structure–activity relationships, offering guidelines for the rational design of efficient DACs for CO 2 RR.