Phase‐Inversion Induced 3D Electrode for Direct Acidic Electroreduction CO2 to Formic acid

Abstract Direct electrochemical CO 2 reduction to formic acid (FA) instead of formate is a challenging task due to the high acidity of FA and competitive hydrogen evolution reaction. Herein, 3D porous electrode (TDPE) is prepared by a simple phase inversion method, which can electrochemically reduce CO 2 to FA in acidic conditions. Owing to interconnected channels, high porosity, and appropriate wettability, TDPE not only improves mass transport, but also realizes pH gradient to build higher local pH micro‐environment under acidic conditions for CO 2 reduction compared with planar electrode and gas diffusion electrode. Kinetic isotopic effect experiments demonstrate that the proton transfer becomes the rate‐determining step at the pH of 1.8; however, not significant in neutral solution, suggesting that the proton is aiding the overall kinetics. Maximum FA Faradaic efficiency of 89.2% has been reached at pH 2.7 in a flow cell, generating FA concentration of 0.1 m . Integrating catalyst and gas–liquid partition layer into a single electrode structure by phase inversion method paves a facile avenue for direct production of FA by electrochemical CO 2 reduction.