Rational Design of Local Reaction Environment for Electrocatalytic Conversion of CO2 into Multicarbon Products

The electrocatalytic conversion of CO2 into multi‐carbon (C2+) products provides an attractive route for storing intermittent renewable electricity as fuels and feedstocks with high energy densities. Although substantial progress has been made in selective electrosynthesis of C2+ products via engineering the catalyst, rational design of the local reaction environment in the vicinity of catalyst surface also acts as an effective approach for further enhancing the performance. Here, we discuss recent advances and pertinent challenges in the modulation of local reaction environment, encompassing local pH, the choice of the species and concentrations of cations and anions as well as local reactant/intermediate concentrations, for achieving high C2+ selectivity. In addition, mechanistic understanding in the effects of the local reaction environment is also discussed. Particularly, the important progress extracted from in situ and operando spectroscopy techniques provides insights into how local reaction environment affects C‐C coupling and key intermediates formation that lead to reaction pathways toward a desired C2+ product. The possible future direction in understanding and engineering the local reaction environment is also provided.