Abstract
Abstract Electrocatalytic carbon dioxide reduction reaction (CO2RR), driven by renewable energy sources, has provided a promising route to convert CO2 into value-added fuels and feedstocks for carbon neutrality. However, its selectivity and conversion efficiency are severely constrained by the chemical inertness of CO2, the complexity of reaction pathways, and the competing hydrogen evolution reaction, thus hindering widespread commercial deployments. Emerging research into atomically precise interfacial catalysis offers new opportunities to overcome these hurdles, enabling precise control over the reaction pathway and product selectivity. This review surveys recent advances in atomic-level interface engineering, focusing on the relationships among catalyst structure, reaction pathways, and CO2RR performance and mechanism. The rational design and construction of atomic-level catalytically active interfaces are highlighted, including strategies such as creating and modulating interfacial asymmetric sites, surface atomic arrangements, and reaction microenvironments. We also offer a forward-looking perspective on exploring these interfacial engineering approaches. We contend that understanding and harnessing interfacial effects through atomic-level catalyst modulation is central to advancing practical CO2RR technologies.