High‐Concentration Alcohol Generation in Bipolar Membrane CO Electrolyzer

Electrochemical reduction of carbon dioxide and carbon monoxide offers an electricity-powered route to make multicarbon liquid products. However, in conventional systems employing anion exchange membranes (AEMs), significant liquid product crossover leads to dilute product streams, increasing separation costs; and also produces unwanted anodic oxidation, further decreasing overall efficiency. Here, we report a forward-biased bipolar membrane (FB-BPM) system that achieves <10% liquid product crossover while sustaining a highly alkaline environment near the cathode, suppressing ethylene and hydrogen and favoring liquid products. By tuning catalyst composition to modulate the adsorption of *H and *OH, we steer selectivity toward acetate and alcohols. Using the FB-BPM system, we achieve >25 wt% acetate on CuZn and >15 wt% alcohols on CuSn directly from the cathode outlet stream.