Enabling Stable and Salt-Free Formic Acid Production via Reactive Interface Optimization in Forward-Bias Bipolar-Membrane CO ₂ Electrolyzers

High Resolution Image Download MS PowerPoint Slide Electrochemical conversion of CO 2 to liquid products is limited by parasitic reactions that consume products and destabilize operation. Here, we show that salt-free formic acid synthesis in a forward-bias bipolar-membrane CO 2 electrolyzer is governed by a coupled reaction-transport instability driven by parasitic anode formic acid oxidation. Operando mass spectrometry reveals that this process proceeds through CO-mediated poisoning, identifying catalyst tolerance to CO as a key descriptor of anode selectivity. Among the catalysts examined, PtRu/C preferentially promotes hydrogen oxidation over formic acid oxidation. Coupling this catalyst with transport-interface engineering improves product removal, enhances Faradaic and energy efficiency, and enables stable operation at 200 mA/cm 2 for 190 h with a voltage decay of 0.64 mV/h. Techno-economic analysis indicates an 18% reduction in minimum selling price and highlights product concentration as the dominant cost lever. These results establish a general framework for suppressing product oxidation in liquid-product electrolyzers.