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Molecular-scale CO spillover on a dual-site electrocatalyst enhances methanol production from CO2 reduction

Nature Nanotechnology volume 20, pages 515–522 (2025)Cite this article

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Abstract

Cobalt phthalocyanine (CoPc) is recognized for catalysing electrochemical CO2 reduction into methanol at high Faradaic efficiency but is subject to deactivation. Cobalt tetraaminophthalocyanine (CoPc-NH2) shows improved stability, but its methanol Faradaic efficiency is below 30%. This study addresses these limitations in selectivity, reactivity and stability by rationally designing a dual-site cascade catalyst. Here we quantify the local concentration of CO, a key intermediate of the reaction, near a working CoPc-NH2 catalyst and show that co-loading nickel tetramethoxyphthalocyanine (NiPc-OCH3) with CoPc-NH2 on multiwalled carbon nanotubes increases the generation and local concentration of CO. This dual-site cascade catalyst exhibits substantially higher performance than the original single-site CoPc-NH2/carbon nanotube catalyst, reaching a partial current density of 150 mA cm−2 and a Faradaic efficiency of 50% for methanol production. Kinetic analysis and in situ sum-frequency generation vibrational spectroscopy attribute this notable performance improvement to molecular-scale CO spillover from NiPc-OCH3 sites to methanol-active CoPc-NH2 sites.

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Fig. 1: Room for methanol production improvement by increasing local CO concentration.
Fig. 2: Dual-site cascade catalyst.
Fig. 3: CO2 reduction performance of dual-site versus single-site catalysts.
Fig. 4: Effect of intersite distance on CO spillover.
Fig. 5: In situ SFG spectroscopy probing *CO intermediates.

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Data availability

Data supporting the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

Electrocatalysis work was supported by the US National Science Foundation (grant number CHE-2154724, H.W.). Flow cell work was supported by the Yale Center for Natural Carbon Capture (H.W.). SFG work was supported by the US National Science Foundation (grant number CBET-2129963, L.R.B. and H.W.). We thank C. Ow-Yang from Thermo Fisher Scientific for the assistance in the collection of the STEM and EDS data.

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Author notes

  1. These authors contributed equally: Jing Li, Quansong Zhu.

Authors and Affiliations

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

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

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

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

  3. Department of Chemistry and Biochemistry, The Ohio State University, Columbus, OH, USA

    Quansong Zhu & L. Robert Baker

  4. School of Mechanical, Industrial, and Manufacturing Engineering, Oregon State University, Corvallis, OR, USA

    Alvin Chang

  5. Shenzhen Key Laboratory of Printed Electronics and Department of Materials Science and Engineering, Southern University of Science and Technology, Shenzhen, P. R. China

    Huan Li, Zhan Jiang & Yongye Liang

  6. School of Chemical, Biological, and Environmental Engineering, Oregon State University, Corvallis, OR, USA

    Zhenxing Feng

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Contributions

J.L. and H.W. conceived this project and designed the experiments. J.L. and Z.J. synthesized the catalyst materials. J.L. performed the electrochemical measurements and analysed the data. Q.Z. and L.R.B. conducted the SFG measurements. H.L., L.R., S.Y. and Y.L. performed the STEM and EDS characterization. A.C. and Z.F. performed the XAS experiments. J.L. and H.W. wrote the paper with input from Q.Z. and L.R.B. B.S., Y.G., S.C. and C.L.R. contributed to data analysis and edited the paper. H.W. supervised the project.

Corresponding authors

Correspondence to Shize Yang, L. Robert Baker or Hailiang Wang.

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Nature Nanotechnology thanks Qinggong Zhu and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–21 and Tables 1 and 2.

Source data

Source Data Fig. 1

Electrochemical testing data.

Source Data Fig. 3

Electrochemical testing data.

Source Data Fig. 4

Electrochemical testing data.

Source Data Fig. 5

In situ SFG testing data.

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Li, J., Zhu, Q., Chang, A. et al. Molecular-scale CO spillover on a dual-site electrocatalyst enhances methanol production from CO2 reduction. Nat. Nanotechnol. 20, 515–522 (2025). https://doi.org/10.1038/s41565-025-01866-8

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