Self-Cleaning CO2 Reduction Systems: Unsteady Electrochemical Forcing Enables Stability

The electrochemical conversion of CO2 produces valuable chemicals and fuels. However, operating at high reaction rates produces locally alkaline conditions that convert reactant CO2 into cell-damaging carbonate salts. These salts precipitate in the porous cathode structure, block CO2 transport, reduce reaction efficiency, and render CO2 electrolysis inherently unstable. We propose a self-cleaning CO2 reduction strategy with short, periodic reductions in applied voltage, which avoids saturation and prevents carbonate salt formation. We demonstrate this approach in a membrane electrode assembly (MEA) with silver and copper catalysts, on carbon and polytetrafluoroethylene (PTFE)-based gas diffusion electrodes, respectively. When operated continuously, the C2 selectivity of the copper–PTFE system started to decline rapidly after only ∼10 h. With the self-cleaning strategy, the same electrode operated for 157 h (236 h total duration), maintaining 80% C2 product selectivity and 138 mA cm–2 of C2 partial current density, at a cost of <1% additional energy input.