Cu Based Dilute Alloys for Tuning the C2+ Selectivity of Electrochemical CO2 Reduction

Electrochemical CO2 reduction is a promising technology for replacing fossil fuel feedstocks in the chemical industry but further improvements in catalyst selectivity need to be made. So far, only copper‐based catalysts have shown efficient conversion of CO2 into the desired multi‐carbon (C2+) products. This work explores Cu‐based dilute alloys to systematically tune the energy landscape of CO2 electrolysis toward C2+ products. Selection of the dilute alloy components is guided by grand canonical density functional theory simulations using the calculated binding energies of the reaction intermediates CO*, CHO*, and OCCO* dimer as descriptors for the selectivity toward C2+ products. A physical vapor deposition catalyst testing platform is employed to isolate the effect of alloy composition on the C2+/C1 product branching ratio without interference from catalyst morphology or catalyst integration. Six dilute alloy catalysts are prepared and tested with respect to their C2+/C1 product ratio using different electrolyzer environments including selected tests in a 100‐cm2 electrolyzer. Consistent with theory, CuAl, CuB, CuGa and especially CuSc show increased selectivity toward C2+ products by making CO dimerization energetically more favorable on the dominant Cu facets, demonstrating the power of using the dilute alloy approach to tune the selectivity of CO2 electrolysis. Electrochemical CO2 reduction promises to replace fossil fuel feedstocks in the chemical industry. Cu‐based dilute alloys allow tuning of the energy landscape of CO2 electrolysis toward desired C2+ products. A physical vapor deposition catalyst testing platform enables the decoupling of the effect of alloy composition on the C2+/C1 product branching ratio from effects related to catalyst morphology and catalyst integration.