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Copper/alkaline earth metal oxide interfaces for electrochemical CO2-to-alcohol conversion by selective hydrogenation

Nature Catalysis volume 5, pages 1081–1088 (2022)Cite this article

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Abstract

Multicarbon alcohols produced by electrochemical CO2 reduction (CO2RR) are attractive alternatives to fossil fuels; however, the selectivity towards alcohols in CO2RR remains low, a result of competing hydrocarbon (that is, ethylene) production. Here we report on Cu catalysts decorated with different alkaline earth metal oxides (MOs). We found that BaO delivers a Faradaic efficiency of 61% towards C2+ alcohols. At an industry-relevant current density of 400 mA cm−2, the ratio of alcohols to hydrocarbon reached 3:1. Mechanistic studies, including in operando X-ray absorption spectroscopy, in situ Raman spectroscopy and density functional theory calculations, suggested that the increased selectivity towards alcohols originates from sites at the MO/Cu interface. Furthermore, computational studies indicated that the incorporation of MOs favours a hydroxy-containing C2 intermediate (*HCCHOH) over the hydrocarbon intermediate (*HCC) at interfacial Cu sites on the path to alcohol products. We also propose that the relative bond strengths of Cu–COH and C–OH correlate with the selectivity for alcohol over hydrocarbon.

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Fig. 1: Characterization of the as-prepared BaO/Cu electrocatalysts.
Fig. 2: CO2RR performance of the BaO/Cu catalyst.
Fig. 3: Surface states of the BaO/Cu catalyst under CO2RR conditions.
Fig. 4: DFT calculations of hydrogenation reactions and design principle.

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Data availability

All data can be found in the public GitHub repository (https://github.com/onealshu/CO2_alcohol_BaOCu.git) or from the corresponding authors upon reasonable request.

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Acknowledgements

This work was financially supported by Suncor Energy, the Natural Sciences and Engineering Research Council (NSERC) of Canada and the CIFAR Bio-Inspired Solar Energy program. S.-F.H. acknowledges support from the Ministry of Science and Technology, Taiwan (contract nos MOST 110-2113-M-009-007-MY2, MOST 110-2628-M-A49-002 and MOST 111-2628-M-A49-007) and from the Yushan Young Scholar Program, Ministry of Education, Taiwan. This research used the synchrotron resources of the Advanced Photon Source (APS), an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science by Argonne National Laboratory, and was supported by the US DOE under contract no. DE-AC02-06CH11357. The authors thank T. Wu and G. Sterbinsky for technical support at the 9BM beamline of the APS. All DFT computations were performed on the Niflheim supercomputer at the Department of Physics, Technical University of Denmark.

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  1. These authors contributed equally: Aoni Xu, Sung-Fu Hung, Ang Cao, Zhenbin Wang.

Authors and Affiliations

  1. Department of Electrical and Computer Engineering, University of Toronto, Toronto, Ontario, Canada

    Aoni Xu, Sung-Fu Hung, Jianan Erick Huang, Yu Yan, Armin Sedighian Rasouli, Fengwang Li, Mingchuan Luo, Yuhang Wang, Xue Wang, Jehad Abed, Ziyun Wang, Dae-Hyun Nam, Yuguang C. Li, Alexander H. Ip & Edward H. Sargent

  2. Beijing Advanced Innovation Center for Materials Genome Engineering, Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing, China

    Aoni Xu & Chaofang Dong

  3. Catalysis Theory Center, Department of Physics, Technical University of Denmark, Lyngby, Denmark

    Aoni Xu, Ang Cao, Zhenbin Wang & Naiwrit Karmodak

  4. Department of Applied Chemistry, National Yang Ming Chiao Tung University, Hsinchu, Taiwan

    Sung-Fu Hung, Feng-Yi Wu, Zih-Yi Lin, Hsin-Jung Tsai & Tsung-Ju Lee

  5. Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, Canada

    Adnan Ozden & David Sinton

  6. Department of Materials Science and Engineering, University of Toronto, Toronto, Ontario, Canada

    Jehad Abed

  7. Department of Chemistry, University at Buffalo, Buffalo, NY, USA

    Yuguang C. Li

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Contributions

E.H.S. supervised the project. A.X. designed and carried out the experiments and some of the DFT calculations, analysed the data and wrote the paper. S.-F.H., F.L. and J.A. performed the synchrotron X-ray spectroscopy measurements. A.C., Zhenbin Wang and N.K. contributed to the DFT calculations and data analysis. J.E.H. and Y.Y. contributed to the in situ Raman measurements. Y.Y. conducted SEM and TEM characterizations. A.S.R. carried out XPS measurements. A.O. worked on substrate design. F.-Y.W., Z.-Y.L., H.-J.T. and T.-J.L. contributed to performance repeating. The other authors contributed to the preparation of the manuscript.

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Correspondence to Chaofang Dong or Edward H. Sargent.

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Xu, A., Hung, SF., Cao, A. et al. Copper/alkaline earth metal oxide interfaces for electrochemical CO2-to-alcohol conversion by selective hydrogenation. Nat Catal 5, 1081–1088 (2022). https://doi.org/10.1038/s41929-022-00880-6

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