Electrochemical Oxidative Dehydrogenation of Ethane to Ethylene in a Solid Oxide Electrolyzer

Abstract Oxidative dehydrogenation of ethane to ethylene is an important process in light olefin industry; however, the over‐oxidation of ethane leads to low ethylene selectivity. Here, we report a novel approach to electrochemical oxidative dehydrogenation of ethane in anode in conjunction with CO 2 reduction at cathode in a solid oxide electrolyser using a porous single‐crystalline CeO 2 electrode at 600 °C. We identify and engineer the flux and chemical states of active oxygen species that evolve from the lattice at anode surface to activate and dehydrogenate ethane to ethylene via the reaction of epoxy species. Active oxygen species (O 2− , O 2 2− and O 2 − ) at the anode surface effectively dehydrogenate ethane to ethylene, but O − species tend to induce deep oxidation. We demonstrate exceptionally high ethylene selectivity of 95 % and an ethane conversion of 10 % with a durable operation of 300 h.