Selectivity roadmap for electrochemical CO2 reduction on copper-based alloy catalysts.

Due to the complex reaction network of the electrochemical CO 2 reduction reaction (CRR), developing highly selective electrocatalysts for desired products remains a major challenge. In this study, a series of Cu-based single atom alloys (M@Cu) with multiple active sites are modelled to investigate their CRR selectivity trends by evaluating various adsorption configurations and energetics. The hydrogen (H) and oxygen (O) affinity of the secondary metals in the M@Cu model catalysts are found to be effective descriptors in determining CRR selectivity. The observed product grouping offers valid theoretical elucidation for available reports of CRR selectivity trends for Cu-based alloy catalysts. It also provides further mechanistic insight into the CRR product selectivity for an extensive range of Cu-based bimetallic materials. The selectivity trend based on the intrinsic catalyst properties provides a rational design strategy for highly selective CRR electrocatalysts. Image 1 • A novel descriptor-based approach to predict CRR selectivity of catalysts is developed. • A series of Cu-based alloy models (M@Cu) are employed to explore their CRR selectivity by extensive thermodynamic analysis. • The M-H and M-O affinity in M@Cu catalysts are found to be effective descriptors in determining CRR selectivity. • The product distribution in our study matches well with the reported CRR selectivity trends in Cu-based bimetallic catalysts. • The selectivity based on intrinsic properties offers a rational design strategy for highly selective CRR electrocatalysts. [ABSTRACT FROM AUTHOR]