From Dopant Periodicity to Asymmetric Sites: Steering C─C Coupling in Single‐Atom Alloy Catalysts for Electrochemical CO 2 Reduction

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Abstract The electrochemical reduction of CO 2 into multicarbon (C 2⁺ ) products is a promising strategy for producing sustainable fuels and chemicals, but conventional Cu catalysts suffer from poor selectivity and limited efficiency. Single‐atom alloys (SAAs), in which isolated dopants are incorporated into a Cu host, offer an atomic‐scale platform to modulate surface chemistry. Here we report a systematic theoretical investigation of 29 Cu‐based SAAs, combining grand‐canonical density functional theory, surface Pourbaix diagrams, and constant‐potential ab initio molecular dynamics with explicit solvation. We uncover a general non‐monotonic periodic trend in adsorbate binding strength—strong → weak → strong—arising from dopant‐induced perturbations of the Cu electronic structure. This universal trend provides a guiding principle: asymmetric active sites, formed by the coexistence of strong‐ and weak‐binding motifs, enable more favorable *CO–*CO coupling and thereby enhance selectivity toward C 2⁺ products. Importantly, we identify net electron transfer from dopant to host as an effective and easily computable descriptor for rapidly screening SAA candidates with low C─C coupling barriers. Guided by this framework, we highlight ScCu, VCu, ZrCu, NbCu, and TaCu as promising SAAs, exhibiting suppressed hydrogen evolution, electrochemical robustness, and efficient C─C bond formation. In particular, NbCu(111) displays a low C─C coupling barrier of 0.87 eV and a thermodynamically viable pathway to ethanol, confirmed under realistic electrolyte conditions. These findings establish atomic‐scale asymmetry as a general design paradigm for advancing SAAs catalysts in CO 2 electroreduction.

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