Interfacial Electronic Interactions in Ni1Cu Single-Atom Alloys Enhance Carbon Dioxide Electrocatalytic Conversion.

Copper-based single-atom alloys (SAAs) exhibit unique capabilities to catalyze the conversion of CO2 into valuable fuels and chemicals, yet their high polarization often induces surface reconstruction, limiting their stability under practical conditions. Here, a novel SAA catalyst, Ni1Cu/NC, featuring atomically dispersed Ni on ∼3 nm Cu nanoparticles anchored on a nitrogen-doped carbon substrate was developed. Density functional theory suggests that energy-aligned and symmetry-compatible mixing of Ni 3d with Cu 4s/4p states enhances s/p-d hybridization on the Cu sites and induces partial delocalization of Cu d-band electrons, modulating the adsorption of key intermediates. As a result, Ni1Cu/NC achieved near-unity CO Faradaic efficiency (FECO) and remarkable durability of 160 h. Furthermore, coupling the catalyst with an anode for the 5-hydroxymethylfurfural oxidation reaction in a solar-driven system renders a high 2,5-furandicarboxylic acid yield of 97.3%. This work provides a comprehensive framework for the rational design of supported SSA catalysts.