Recently, a joint team led by Associate Professor Li Jun from the Frontiers Science Center for Transformative Molecules at Shanghai Jiao Tong University and Associate Professor Yao Zhenpeng from the School of Materials Science and Engineering published a research paper titled “Electrosynthesis of ethanol via CO–CHx cross-coupling on copper alloy catalysts with engineered oxygen affinity” in Nature Synthesis. The study proposes a novel approach to promote CO–CHx cross-coupling by modulating the oxygen affinity of catalysts, enabling highly efficient and stable electrosynthesis of ethanol. This breakthrough significantly improves energy and carbon efficiency while demonstrating feasibility for long-term operation.

Article abstract:

Electroreduction of CO2 or CO can produce renewable ethanol—a valuable industrial chemical. However, the limited energy and carbon efficiencies of reported systems present practical challenges. Here we introduce p-block elements into copper catalysts, enabling electrosynthesis of ethanol from CO for 200 h and delivering a full-cell energy efficiency of 22% and a carbon efficiency of 50%, seven-fold better than state-of-the-art. Density functional theory calculations indicate that the lead-doped copper catalyst enhances the cleavage of C–O bonds in *OCHx molecules formed during CO hydrogenation. This enhances the cross-coupling reaction between *CO and *CHx species favouring ethanol production, as opposed to the conventional *CO dimerization pathway that primarily yields ethylene. Using a set of in situ spectroscopic techniques, we show that the addition of lead to copper catalysts expedites the generation of *OCHx species and increases the coverage of *CHx species, thereby enhancing their coupling with *CO and improving ethanol production, in agreement with our theoretical predictions.