Selective and energy-efficient electrosynthesis of ethylene from CO2 by tuning the valence of Cu catalysts through aryl diazonium functionalization

Abstract

Although progress has been made in producing multi-carbon products from the electrochemical reduction of CO2, the modest selectivity for ethylene (C2H4) leads to low energy efficiency and high downstream separation costs. Here we functionalize Cu catalysts with a variety of substituted aryl diazonium salts to improve selectivity towards multi-carbon products. Using computation and operando spectroscopy, we find that Cu surface oxidation state (δ+ where 0 < δ < 1) can be tuned by functionalization and that it influences the selectivity to C2H4. We report a Faradaic efficiency and a specific current density for C2H4 as large as 83 ± 2% and 212 mA cm−2, respectively, on partially oxidized Cu0.26+. Using a CO gas feed, we demonstrate an energy efficiency of ~40% with a C2H4 Faradaic efficiency of 86 ± 2%, corresponding to a low electrical power consumption of 25.6 kWh Nm−3 for the CO to C2H4 conversion reaction. Our findings provide a route towards practical electrosynthesis of C2H4 using valence engineering of copper.