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The solvation environment of molecularly dispersed cobalt phthalocyanine determines methanol selectivity during electrocatalytic CO2 reduction

Nature Catalysis (2024)Cite this article

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Abstract

Heterogenized molecular electrocatalysts are a promising group of materials that can electrocatalytically convert waste molecules into higher-value products. However, how the dispersion state of molecules affects the catalytic process is not well understood. Using cobalt phthalocyanine (CoPc) dispersed on carbon nanotubes (CNTs) as a model system, here we show that increasing the direct interaction of the molecular catalyst with cations notably enhances the CO2 reduction reaction. Specifically, molecularly dispersed CoPc on CNTs yields an eightfold increase in methanol selectivity compared with aggregated CoPc on CNTs. In situ spectroscopic studies confirm the presence of two intermediates located at different positions of the double layer. Density functional theory calculations further reveal that CoPc molecules inside the Stern layer are active for methanol production due to the direct interaction with cations. Similar enhancement effects are also observed for other reactions, showing that dispersing molecular catalysts into monomeric states is a general design parameter.

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Fig. 1: Electrocatalytic performance of differently dispersed CoPc electrodes.
Fig. 2: AFM-IR measurement of differently dispersed CoPc electrodes.
Fig. 3: SFG measurement of differently dispersed CoPc electrodes.
Fig. 4: Schematics of interfacial structures.
Fig. 5: DFT calculations of the cation coordination effect.
Fig. 6: SFG spectra, kinetics results and interfacial structures from the cation-dependent study.

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All of the experimental data supporting the findings of this study are available within the supplementary materials. Source data are provided with this paper.

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Acknowledgements

This work was supported by the United States National Science Foundation (NSF)–United States–Israel Binational Science Foundation (BSF) International Collaboration programme in the Division of Chemical, Bioengineering, Environmental, and Transport Systems (NSF grant number 2129963 and BSF grant number 2021671). The catalyst preparation, kinetic studies and SFG measurements were supported by grant number 2129963 (to Q.Z., C.L.R., H.W. and L.R.B.) from the NSF. The AFM and AFM-IR measurements were supported by grant number 2021671 (to H.S. and E.G.) from the BSF. The DFT calculations were supported by grant number 2154724 (to C.Z. and J.A.P.) from the NSF. We also thank the Spiedie cluster at Binghamton University for performing electronic structure calculations.

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Author notes

  1. These authors contributed equally: Quansong Zhu, Conor L. Rooney, Hadar Shema, Christina Zeng.

Authors and Affiliations

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

    Quansong Zhu & L. Robert Baker

  2. Department of Chemistry and Energy Sciences Institute, Yale University, West Haven, CT, USA

    Conor L. Rooney & Hailiang Wang

  3. Institute of Chemistry and Center for Nanoscience and Nanotechnology, Hebrew University, Jerusalem, Israel

    Hadar Shema & Elad Gross

  4. Department of Chemistry, State University of New York at Binghamton, Binghamton, NY, USA

    Christina Zeng & Julien A. Panetier

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  1. Quansong Zhu
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Contributions

C.L.R. prepared the catalysts and conducted the electrocatalytic tests. Q.Z. conducted the SFG measurements. H.S. conducted the AFM-IR measurements. C.Z. performed the DFT calculations. Q.Z., C.L.R., H.S. and C.Z. analysed the results and participated in writing the manuscript. All authors reviewed the manuscript.

Corresponding authors

Correspondence to Julien A. Panetier, Elad Gross, Hailiang Wang or L. Robert Baker.

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Nature Catalysis thanks Julien Bonin, Ali Seifitokaldani 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 methods, notes, Figs. 1–27 and Tables 1–15.

Supplementary Data 1

Atomic coordinates of the optimized computational mod

Source data

Source Data Fig. 1

Statistical source data for the electrochemical measurements shown in Fig. 1.

Source Data Fig. 2

Unprocessed infrared spectra data for Fig. 2.

Source Data Fig. 3

Unprocessed SFG spectra data for Fig. 3.

Source Data Fig. 6

Statistical source data for the electrochemical measurements and unprocessed SFG spectra shown in Fig. 6.

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Zhu, Q., Rooney, C.L., Shema, H. et al. The solvation environment of molecularly dispersed cobalt phthalocyanine determines methanol selectivity during electrocatalytic CO2 reduction. Nat Catal (2024). https://doi.org/10.1038/s41929-024-01190-9

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