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Mechanism-guided realization of selective carbon monoxide electroreduction to methanol

Nature Synthesis volume 2, pages 1194–1201 (2023)Cite this article

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Abstract

Cobalt phthalocyanine can effectively convert CO2 or CO to methanol. However, this reaction is hampered by low selectivity (a methanol Faradaic efficiency of less than 40%) and poor understanding of the kinetics and mechanism. In this work, we use a mechanism-guided reaction design approach based on systematic kinetic studies to overcome these limitations. pH-dependent Tafel analysis and kinetic isotopic effect experiments explain that methanol production from CO electroreduction is pH independent and limited by the *CO hydrogenation to *CHO step with H2O as the major proton source. Proton donor comparisons show that bicarbonate can promote the reaction at its optimal concentration of 0.1 M and CO reaction order studies confirm a Henry type isotherm for CO adsorption on the catalyst surface. These mechanistic findings lead us to carry out CO reduction in a 0.1 M bicarbonate electrolyte, under 10 atm CO pressure and with a microporous layer on the electrode to enhance reactant transport. Our reaction achieves a high methanol Faradaic efficiency of 84% with a partial current density of more than 20 mA cm−2 at −0.98 V versus the reversible hydrogen electrode, making the electrochemical CO-to-methanol conversion a selective process viable for practical application.

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Fig. 1: CO-to-CH3OH conversion catalysed by CoPc-NH2/CNT, and the current challenges and progress made in this work.
Fig. 2: Improving methanol selectivity by enhancing CO mass transport.
Fig. 3: Kinetic analysis for methanol production from CO electroreduction catalysed by CoPc-NH2/CNT.
Fig. 4: Proton donor effect on methanol production from CO electroreduction catalysed by CoPc-NH2/CNT.
Fig. 5: Mechanism-guided realization of high methanol selectivity.

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Data availability

Source data are provided with this paper. All experimental data supporting the findings of this study are available in Supplementary Information.

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Acknowledgements

This work was supported by US National Science Foundation (grant no. CHE-2154724; mechanistic and kinetic studies) and the Yale Center for Natural Carbon Capture (performance and device work).

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Authors and Affiliations

  1. Department of Chemistry, Yale University, New Haven, CT, USA

    Jing Li, Bo Shang, Yuanzuo Gao, Seonjeong Cheon, Conor L. Rooney & Hailiang Wang

  2. Energy Sciences Institute, Yale University, West Haven, CT, USA

    Jing Li, Bo Shang, Yuanzuo Gao, Seonjeong Cheon, Conor L. Rooney & Hailiang Wang

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  1. Jing Li
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Contributions

J.L. and H.W. conceived this project, designed the experiments and wrote the manuscript. J.L. and C.L.R. synthesized the catalyst materials. J.L. performed the electrochemical measurements and analysed the data. B.S., Y.G., S.C. and C.L.R. contributed to data analysis and edited the manuscript. H.W. supervised the project.

Corresponding author

Correspondence to Hailiang Wang.

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Peer review information

Nature Synthesis thanks Zhimin Liu 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 information

Source data

Source Data Fig. 2

Electrochemical testing data.

Source Data Fig. 3

Electrochemical testing data.

Source Data Fig. 4

Electrochemical testing data.

Source Data Fig. 5

Electrochemical testing data.

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Li, J., Shang, B., Gao, Y. et al. Mechanism-guided realization of selective carbon monoxide electroreduction to methanol. Nat. Synth 2, 1194–1201 (2023). https://doi.org/10.1038/s44160-023-00384-6

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