Efficient Ethanol Dehydrogenation to Acetaldehyde and H ₂ via Synergistic Thermocatalysis and Electrocatalysis

Abstract The dehydrogenation of ethanol to acetaldehyde and H 2 represents an attractive synthetic route, owing to the versatile applications of acetaldehyde and the high atom economy. In this work, efficient ethanol dehydrogenation was achieved at the anode of a high‐temperature polymer electrolyte membrane electrolyzer by integrating thermocatalytic ethanol dehydrogenation (EDHR) with electrochemical hydrogen oxidation (HOR) over Ru/C and PdAu/C composite catalytic layer. The Ru/C serves as a bifunctional catalyst for the EDHR and HOR, and the PdAu/C could rapidly electrooxidize retained acetaldehyde of the catalyst layer into acetic acid, thereby effectively promoting the dehydrogenation of ethanol. Under the conditions of 200 °C and 0.6 V, this reaction enabled high production rates of acetaldehyde (1479 mmol g −1 h −1 with 99.06% selectivity) at the anode and H 2 (1728 mmol g −1 h −1 ) at the cathode, substantially outperforming traditional thermal catalytic and electrocatalytic processes. This work provides a novel strategy for efficient alcohol dehydrogenation and facilitates the sustainable synthesis of value‐added products.