Reconstruction-Dependent Coordination Descriptor for Selectivity toward C 2+ Products of CO 2 Electroreduction over Cu Catalysts

作者：Xuning Wang, Haoxiang Xu, Daojian Cheng · 发表于：ACS Catalysis · 年份：2025 · DOI：10.1021/acscatal.5c03702 · 被引用次数：10 · 研究领域：CO2 Reduction Techniques and Catalysts、Ionic liquids properties and applications、Catalysis and Oxidation Reactions

The electroreduction of CO 2 (CO 2 ER) to multicarbon chemicals (C 2+ ) catalyzed by copper (Cu) is a pivotal initiative for achieving carbon neutrality and green chemical production. However, a lack of quantitative structure-selectivity relationship hampers further advancement of Cu catalysts. Moreover, the inherent structural fluidity of Cu catalysts, which facilitates its surface reconstruction during the CO 2 ER reaction, complicates the mutual verification and self-consistency between theoretical and experimental results. In this study, we employ grand-canonical first-principles calculations under solvent and cation effects to elucidate the negative correlation between C 2+ selectivity in CO 2 ER and the coordination saturation of monometallic Cu catalysts. Through systematic analysis of CO-induced reconstruction of various Cu surfaces, we introduce the concept of degree of reconstruction (DOR) to quantitatively characterize the dynamic behavior of Cu surfaces. Additionally, we propose reconstruction-dependent generalized coordination numbers (RD-GCNs) as a descriptor to accurately capture the C 2+ selectivity trends observed in electrocatalytic environments. The identified negative correlation between RD-GCNs and C 2+ selectivity demonstrates that a lower RD-GCN notably enhances C 2+ selectivity, accurately reproducing the relative order of experimental Faradaic efficiency (FE) for C 2+ products among Cu single-crystal slabs and rationalizing the C 2+ selectivity trend ...