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Electrochemical acetate production from high-pressure gaseous and liquid CO2

Nature Catalysis volume 6, pages 1151–1163 (2023)Cite this article

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Abstract

Electroreduction of CO2 (CO2RR) to high-value chemicals is important to environmental and energy landscapes, with one of the challenges being direct and efficient acetate production. Here we demonstrate a Cu(OH)2-derived Cu/CuOx catalyst that achieves 87% Faradaic efficiency for the CO2RR to acetate in KOH electrolytes with borate additives under 58 atm CO2(g). Dynamic electrolytic speciation reveals high and low concentrations of dissolved CO2(aq) and proton donor HCO3−, respectively, as the key to acetate. In situ Raman spectroscopy suggests that the oxygen-bound bidentate intermediate *OC•O* formed as the acetate precursor on Cu(I) under high pressures. Introducing CO2(l) to the interface between CO2(g) and the electrolyte by melting CO2(s) further increases [CO2(aq)] and boosts the acetate partial current density to 86 mA cm–2 with 71% Faradaic efficiency. A Cu2+ cross-linked alginate coating layer on the cathode surface drastically enhances the durability of Cu/CuOx catalyst over a 20 h reaction, affording a potassium acetate yield of 30 mg h−1 cm−2 directly from the CO2RR.

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Fig. 1: Synthesis and characterization of SW-Cu(OH)2/Cu.
Fig. 2: CO2RR of SW-Cu(OH)2/Cu under 58 atm CO2(g).
Fig. 3: CO2RR selectivity between formate, acetate and ethanol.
Fig. 4: CO2RR mechanism on a Cu/CuOx catalyst explored by in situ Raman spectroscopy.
Fig. 5: CO2RR selectivity trend on a Cu(I)/Cu(0) catalyst.
Fig. 6: Boosting CO2RR performance by introducing CO2(l).

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All data supporting the findings of this study are available from the authors on request.

Code availability

All the MATLAB codes supporting the findings of this study are available in the Supplementary Information.

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Acknowledgements

The authors thank J. Guo, Y. Jung and H. Gong for their warm help. This work was supported by Deng Family Gift Fund and the Stanford Bits and Watts Program. Part of this work was performed at Stanford Nano Shared Facilities (SNSF), supported by National Science Foundation under award ECCS-2026822.

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Authors and Affiliations

  1. Department of Chemistry and Bio-X, Stanford University, Stanford, CA, USA

    Jiachen Li, Yun Kuang, Xiao Zhang, Wei-Hsuan Hung, Guanzhou Zhu, Feifei Wang, Peng Liang & Hongjie Dai

  2. Department of Materials Science and Engineering, Stanford University, Stanford, CA, USA

    Jiachen Li & Gan Chen

  3. Institute of Materials Science and Engineering, National Central University, Taoyuan, Taiwan

    Wei-Hsuan Hung

  4. National Synchrotron Radiation Research Center, Hsinchu, Taiwan

    Ching-Yu Chiang

  5. Department of Chemical Engineering, Stanford University, Stanford, CA, USA

    Gan Chen

  6. Department of Electrical and Electronic Engineering, The University of Hong Kong, Hong Kong, China

    Feifei Wang

  7. Department of Chemistry, The University of Hong Kong, Hong Kong, China

    Hongjie Dai

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  1. Jiachen Li
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Contributions

H.D. and J.L. designed the study. J.L., Y.K., X.Z., W.H., C.C., G.Z., G.C. and P.L. performed material synthesis and characterizations. J.L., Y.K., X.Z., F.W. and P.L. performed electrochemical and spectroscopic experiments. J.L. performed calculations and derivations. J.L. and H.D. prepared the paper. All authors participated in data analysis and result discussions.

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Correspondence to Hongjie Dai.

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Supplementary Methods, Notes 1–5, Figs. 1–8, Tables 1–4 and References.

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Li, J., Kuang, Y., Zhang, X. et al. Electrochemical acetate production from high-pressure gaseous and liquid CO2. Nat Catal 6, 1151–1163 (2023). https://doi.org/10.1038/s41929-023-01046-8

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