Breaking the Linear Scaling Relationship by Compositional and Structural Crafting of Ternary Cu–Au/Ag Nanoframes for Electrocatalytic Ethylene Production

Abstract Electrocatalytic conversion of carbon dioxide into high‐value multicarbon (C 2+ ) chemical feedstocks offers a promising avenue to liberate the chemical industry from fossil‐resource dependence and eventually close the anthropogenic carbon cycle but is severely impeded by the lack of high‐performance catalysts. To break the linear scaling relationship of intermediate binding and minimize the kinetic barrier of CO 2 reduction reactions, ternary Cu–Au/Ag nanoframes were fabricated to decouple the functions of CO generation and C−C coupling, whereby the former is promoted by the alloyed Ag/Au substrate and the latter is facilitated by the highly strained and positively charged Cu domains. Thus, C 2 H 4 production in an H‐cell and a flow cell occurred with high Faradic efficiencies of 69±5 and 77±2 %, respectively, as well as good electrocatalytic stability and material durability. In situ IR and DFT calculations unveiled two competing pathways for C 2 H 4 generation, of which direct CO dimerization is energetically favored.