Efficient Ethanol Dehydrogenation to Acetaldehyde and H2 via Synergistic Thermocatalysis and Electrocatalysis.

The dehydrogenation of ethanol to acetaldehyde and H2 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 H2 (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.