Solvent Mediated Interfacial Microenvironment Design for High‐Performance Electrochemical CO2 Reduction to C2+ Products

Electrochemical CO2 reduction (CO2RR) in membrane electrode assembly (MEA) represents a viable strategy for converting CO2 into value-added multi-carbon (C2+) compounds. Therefore, the microstructure of the catalyst layer (CL) affects local gas transport, charge conduction, and proton supply at three-phase interfaces, which is significantly determined by the solvent environment. However, the microenvironment of the CLs and the mechanism of the solvent effect on C2+ selectivity remains elusive. Herein, a tailored interfacial structure is designed by introducing a solvent-mediated catalyst-ionomer-solvent microenvironment. The acetone surface promotion strategy is beneficial for the unfolded ionomers to uniformly coat the catalysts, which contributes to enhancing interfacial hydrophobicity and inhibiting hydrogen evolution. Furthermore, molecular dynamics (MD) simulation and in situ ATR-SEIRAS are employed to elucidate the appropriate interfacial network with a balanced distribution of CO2 and H2O. The uniform and continuous network in acetone is advantageous for CO2-to-C2+. The optimized structure favors the production of C2+ products in Cu-based MEA, exhibiting a high C2+ faradaic efficiency (FE) of 80.27% at 400 mA cm-2.