Continuous flow pH ‐asymmetric paired electrosynthesis enabled by bipolar membrane electrolyzer

Abstract Paired electrosynthesis enables simultaneous electrocatalytic oxidation (ECO) and hydrogenation (ECH) of cinnamyl alcohol. However, the pH‐asymmetric configuration between alkaline ECO and acidic ECH limits integration. Herein, a bipolar‐membrane (BPM) electrolyzer was constructed using Ni‐loaded porous carbon nanobowls graphite felt (Ni/PCBs/GF) and Pd‐loaded PCBs (Pd/PCBs/GF) to perform ECO and ECH in their respective optimal environments. The hollow PCB structure improves mass transport and active‐site exposure, enhancing catalytic activity. The Ni/PCBs/GF achieved a cinnamaldehyde yield of 98.0%, while Pd/PCBs/GF attained 99.0% selectivity toward 3‐phenylpropanol. In situ spectroscopy and DFT indicated Ni heterointerface reconstruction that promotes (4‐acetamido‐2,2,6,6‐tetramethylpiperidin‐1‐oxyl) ACT adsorption and electron–hole mediation, and Pd electronic redistribution that activates Pd sites for CC hydrogenation. The scaled‐up BPM electrolyzer reached space–time yields of 12.79 and 7.02 kg·m −3 ·h −1 at the alkaline anode and acidic cathode, demonstrating effective co‐production under disparate conditions. This study advances paired electrosynthesis by harmonizing anodic–cathodic conditions, enabling energy‐efficient co‐production of value‐added chemicals.