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.
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The datasets analysed and generated during the current study are included in the paper and its Supplementary Information. Source data are provided with this paper.
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Acknowledgements
This work was financially supported by the National Key Research and Development Program of China (2023YFA1507500 and 2022YFA1505100 to J.L.), the National Natural Science Foundation of China (BE3250011 to J.L. and 52373228 to Z.Y), the Fundamental Research Funds for the Central Universities (23×010301599 and 24×010301678 to J.L.), the Shanghai Pilot Program for Basic Research—Shanghai Jiao Tong University (21TQ1400227 to J.L.), Shanghai Municipal Science and Technology Major Project to J.L., the Ontario Research Foundation: Research Excellence Program to D.S., the Natural Sciences and Engineering Research Council (NSERC) of Canada to D.S., and TOTAL SE to D.S. A.O. gratefully acknowledges the financial support of Khalifa University for this work through the grant FSU-2025-006. Part of the XAS described in this paper was performed in May 2022 at the Canadian Light Source, a national research facility of the University of Saskatchewan, which is supported by NSERC, the Canada Foundation for Innovation (CFI), the National Research Council (NRC), the Canadian Institutes of Health Research (CIHR), the Government of Saskatchewan and the University of Saskatchewan. We acknowledge the Shanghai Synchrotron Radiation Facility, China, for the provision of synchrotron radiation beamtime at beamlines BL13SSW and BL02B01. Support from Canada Research Chairs Program is gratefully acknowledged.
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J.L. conceived the idea and supervised the project. P.L., N.S. and Y.W. carried out all the electrochemical experiments. P.P., A.O., R.K.M. and Y.X. contributed to electrode fabrication and assisted with the electrochemical testing. J.S. performed DFT calculations under the supervision of Z.Y., in which H.W., X.W. and Z.W. assisted with calculations and data analysis. P.L., N.S., H. Liu, Z.P. and Y.Z. performed XAS, NAP-XPS and Raman measurements, in which M.S., J.Z. and Y.H. assisted with the XAS testing, and S.S. and H.Z. assisted with the NAP-XPS testing. S.C. assisted with transmission electron microscopy characterizations. J.L. wrote the paper. D.S., Z.Y., H. Liang, A.O. and P.L. contributed to paper editing. All authors discussed the results and assisted during the paper preparation.
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Nature Synthesis thanks Miho Yamauchi, Tao Yao and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary Handling Editor: Alexandra Groves, in collaboration with the Nature Synthesis team.
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Liu, P., Sun, N., Su, J. et al. Electrosynthesis of ethanol via CO–CHx cross-coupling on copper alloy catalysts with engineered oxygen affinity. Nat. Synth 4, 1462–1472 (2025). https://doi.org/10.1038/s44160-025-00868-7
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DOI: https://doi.org/10.1038/s44160-025-00868-7
