Understanding Electrochemical CO 2 Reduction Selectivity of Cu Binary Alloys from Electronic Structure Descriptors

作者：Yujin Jung, Hafiz Ghulam Abbas, Soeun Kim, Beomil Kim, Junsic Cho, Sunghoon Han, Hakhyeon Song, Yuta Takaoka, Jun Tae Song, Tatsumi Ishihara, Chang Hyuck Choi, Stefan Ringe, Jihun Oh · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c14093 · 被引用次数：31 · 研究领域：CO2 Reduction Techniques and Catalysts、Ionic liquids properties and applications、Advanced Thermoelectric Materials and Devices

We investigate the electrochemical reduction of carbon dioxide (CO 2 RR) using Cu-M (M = Ni, Pd, Ag, Au, Zn, Cr) binary alloys. Through experimental and theoretical analysis, we explore the structural and electronic properties of these alloys and their impact on CO 2 RR product selectivity. Our findings reveal that the d-band center of Cu-M alloys serves as a crucial descriptor, influencing product distribution. As the d-band center increases, more CO is produced, while the formation of C 2 products (ethylene and ethanol) follows a volcano-like trend. We also observe a linear scaling relationship between the d-band center and ethylene/ethanol selectivity, providing opportunities for fine-tuning product selectivity. The observation is explained by theoretical calculations that suggest that the d-band center effectively changes the relative binding of *CCH vs *CHCHOH, thereby controlling product selectivity into ethylene vs ethanol formation. We also find that this d-band center dependence is what makes the *CCH vs *CHCHOH adsorption energy, when properly corrected for alloy composition-dependencies, the most reliable theoretically accessible descriptor for ethylene/ethanol selectivity, while the *O adsorption energy does not show a clear correlation with experimental results. This study enhances our understanding of CO 2 RR catalysis and offers guidelines for designing Cu-based alloy electrocatalysts with improved activity and selectivity for sustainable CO 2 conversion.