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A silver–copper oxide catalyst for acetate electrosynthesis from carbon monoxide

Nature Synthesis volume 2, pages 448–457 (2023)Cite this article

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Abstract

Acetic acid is an important chemical feedstock. The electrocatalytic synthesis of acetic acid from CO2 offers a low-carbon alternative to traditional synthetic routes, but the direct reduction from CO2 comes with a CO2 crossover energy penalty. CO electroreduction bypasses this, which motivates the interest in a cascade synthesis approach of CO2 to CO followed by CO to acetic acid. Here we report a catalyst design strategy in which off-target intermediates (such as ethylene and ethanol) in the reduction of CO to acetate are destabilized. On the optimized Ag–CuO2 catalyst, this destabilization of off-target intermediates leads to an acetate Faradaic efficiency of 70% at 200 mA cm−2. We demonstrate 18 hours of stable operation in a membrane electrode assembly; the system produced 5 wt% acetate at 100 mA cm−2 and a full-cell energy efficiency of 25%, a twofold improvement on the highest energy-efficient electrosynthesis in prior reports.

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Fig. 1: Acetic acid electrosynthesis.
Fig. 2: Synthesis and characterization of Ag–Cu2O catalysts.
Fig. 3: Electrochemical performance measurement of Ag–Cu2O series.
Fig. 4: Computational studies of C2 pathways on AgCu slabs.
Fig. 5
Fig. 6: Acetate production activity of an Ag–Cu2O catalyst and concentrated acetate production in MEA applications.

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Data availability

Source data are provided with this paper. All the other relevant data supporting the findings of this study, which include techno-economic assessment methodologies, computational details and other experimental, microscopic and spectroscopic analyses, are available within the article and its Supplementary Information.

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Acknowledgements

We acknowledge the support of this work by the Ontario Research Foundation—Research Excellence Program (no. ORF-RE08-034, E.H.S.), the Natural Sciences and Engineering Research Council (NSERC) of Canada (no. RGPIN-2017-06477, E.H.S.) and Suncor Canada. I.G. acknowledges the European Union’s Horizon 2020 research and innovation programme under a Marie Sklodowska-Curie grant (agreement no. 846107). DFT calculations were performed on the Niagara supercomputer at the SciNet HPC Consortium. We acknowledge the computational resources supported by SciNet, which is funded by the University of Toronto, the Ontario Research Fund—Research Excellence Program, the Government of Ontario and the Canada Foundation for Innovation. This research used resources of the Advanced Photon Source, 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, and the Canadian Light Source and its funding partners. This research used resources of the European Synchrotron Radiation Facility at beamline ID26 during the experimental session MA5352 (https://doi.org/10.15151/ESRF-ES-744180074). We thank D. Motta Meira from the 20BM beamline for assistance in collecting the XAS data. We thank R. Wolowiec and D. Kopilovic for their kind technical assistance, S. Boccia from the Ontario Centre for the Characterization of Advanced Materials (OCCAM) of the University of Toronto for the electron microscopy imaging and A. Ip for general input on the paper. We thank Y.-C. Chu and H. M. Chen in the National Taiwan University for conducting in situ XAS experiments. We thank C.-W. Bao in TPS 44A1, National Synchrotron Radiation Research Center, Taiwan, for help with tuning the incident beam of the XAS. We acknowledge support from the Ministry of Science and Technology, Taiwan (contract nos. MOST 110-2628-M-002-001-RSP and 110-2113-M-153-001).

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Author notes

  1. These authors contributed equally: Roham Dorakhan, Ivan Grigioni, Byoung-Hoon Lee.

Authors and Affiliations

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

    Roham Dorakhan, Ivan Grigioni, Byoung-Hoon Lee, Pengfei Ou, Jehad Abed, Armin Sedighian Rasouli, Erfan Shirzadi, Joshua Wicks, Sungjin Park, Geonhui Lee, Jinqiang Zhang & Edward H. Sargent

  2. Dipartimento di Chimica, Università degli Studi di Milano, Milan, Italy

    Ivan Grigioni

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

    Colin O’Brien, Rui Kai Miao & David Sinton

  4. ScopeM, ETH-Zürich, Zürich, Switzerland

    Milivoj Plodinec

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Contributions

E.H.S. supervised the project. R.D., I.G. and B.-H.L. conceived the idea. R.D., B.-H.L. and I.G. designed and performed the experiments. R.D., with the help of P.O., carried out the DFT calculations. J.A. performed the XAS experiments. J.A., I.G. and R.D. analysed the XAS data. A.S.R. performed the XPS experiments. A.S.R. and I.G. analysed the XPS data. M.P., B.-H.L. and R.D. performed the TEM and SEM measurements. R.K.M., E.S., J.W., S.P., G.L. and J.Z. contributed to the data interpretation, material synthesis and characterization. R.K.M., C.O. and D.S. assisted with the electrochemical system design. R.D., I.G., B.-H.L., P.O. and E.H.S. wrote the manuscript. All the authors commented on the manuscript.

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Correspondence to Edward H. Sargent.

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Nature Synthesis thanks Dehui Deng 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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Supplementary notes 1–4, Figs. 1–38 and Tables 1–11.

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Operando and post catalysis characterization data.

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Electrochemical testing data.

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Dorakhan, R., Grigioni, I., Lee, BH. et al. A silver–copper oxide catalyst for acetate electrosynthesis from carbon monoxide. Nat. Synth 2, 448–457 (2023). https://doi.org/10.1038/s44160-023-00259-w

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