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Mechanism-guided realization of selective carbon monoxide electroreduction to methanol

Nature Synthesis (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.

Data availability

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

References

  1. Lewis, N. S. Research opportunities to advance solar energy utilization. Science 351, aad1920 (2016).

  2. Chu, S., Cui, Y. & Liu, N. The path towards sustainable energy. Nat. Mater. 16, 16–22 (2017).

    Article  Google Scholar 

  3. Franco, F., Rettenmaier, C., Jeon, H. S. & Roldan Cuenya, B. Transition metal-based catalysts for the electrochemical CO2 reduction: from atoms and molecules to nanostructured materials. Chem. Soc. Rev. 49, 6884–6946 (2020).

    Article  CAS  PubMed  Google Scholar 

  4. Francke, R., Schille, B. & Roemelt, M. Homogeneously catalyzed electroreduction of carbon dioxide-methods, mechanisms, and catalysts. Chem. Rev. 118, 4631–4701 (2018).

    Article  CAS  PubMed  Google Scholar 

  5. Zhang, H., Li, J., Cheng, M.-J. & Lu, Q. CO electroreduction: current development and understanding of Cu-based catalysts. ACS Catal. 9, 49–65 (2018).

    Article  Google Scholar 

  6. Nguyen, T. N. et al. Fundamentals of electrochemical CO2 reduction on single-metal-atom catalysts. ACS Catal. 10, 10068–10095 (2020).

    Article  Google Scholar 

  7. Dinh, C. T. et al. CO2 electroreduction to ethylene via hydroxide-mediated copper catalysis at an abrupt interface. Science 360, 783–787 (2018).

    Article  CAS  PubMed  Google Scholar 

  8. Luo, M. et al. Hydroxide promotes carbon dioxide electroreduction to ethanol on copper via tuning of adsorbed hydrogen. Nat. Commun. 10, 5814 (2019).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  9. Xia, C. et al. Continuous production of pure liquid fuel solutions via electrocatalytic CO2 reduction using solid-electrolyte devices. Nat. Energy 4, 776–785 (2019).

    Article  CAS  Google Scholar 

  10. Monteiro, M. C. O., Philips, M. F., Schouten, K. J. P. & Koper, M. T. M. Efficiency and selectivity of CO2 reduction to CO on gold gas diffusion electrodes in acidic media. Nat. Commun. 12, 4943 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  11. Weng, Z. et al. Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction. Nat. Commun. 9, 415 (2018).

    Article  PubMed  PubMed Central  Google Scholar 

  12. Jia, L. et al. Phase-dependent electrocatalytic CO2 reduction on Pd3Bi nanocrystals. Angew. Chem. Int. Ed. Engl. 60, 21741–21745 (2021).

    Article  CAS  PubMed  Google Scholar 

  13. Guan, A. et al. Boosting CO2 electroreduction to CH4 via tuning neighboring single-copper sites. ACS Energy Lett. 5, 1044–1053 (2020).

    Article  CAS  Google Scholar 

  14. Wang, J., Dou, S. & Wang, X. Structural tuning of heterogeneous molecular catalysts for electrochemical energy conversion. Sci. Adv. 7, eabf3989 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  15. Wu, Y., Liang, Y. & Wang, H. Heterogeneous molecular catalysts of metal phthalocyanines for electrochemical CO(2) reduction reactions. Acc. Chem. Res. 54, 3149–3159 (2021).

    Article  CAS  Google Scholar 

  16. Cao, R. Across the board: Rui Cao on electrocatalytic CO2 reduction. Chem. Sus. Chem. 15, e202201788 (2022).

    Article  CAS  Google Scholar 

  17. Chang, Q. et al. Metal-coordinated phthalocyanines as platform molecules for understanding isolated metal sites in the electrochemical reduction of CO2. J. Am. Chem. Soc. 144, 16131–16138 (2022).

    Article  CAS  PubMed  Google Scholar 

  18. Soucy, T. L. et al. Considering the influence of polymer-catalyst interactions on the chemical microenvironment of electrocatalysts for the CO2 reduction reaction. Acc. Chem. Res. 55, 252–261 (2022).

    Article  CAS  PubMed  Google Scholar 

  19. Zhang, X. et al. Highly selective and active CO2 reduction electrocatalysts based on cobalt phthalocyanine/carbon nanotube hybrid structures. Nat. Commun. 8, 14675 (2017).

    Article  PubMed  PubMed Central  Google Scholar 

  20. Zhang, X. et al. Molecular engineering of dispersed nickel phthalocyanines on carbon nanotubes for selective CO2 reduction. Nat. Energy 5, 684–692 (2020).

    Article  CAS  Google Scholar 

  21. Guo, H. et al. Iron porphyrin with appended guanidyl group for significantly improved electrocatalytic carbon dioxide reduction activity and selectivity in aqueous solutions. Chin. J. Catal. 43, 3089–3094 (2022).

    Article  CAS  Google Scholar 

  22. Ronne, M. H. et al. Ligand-controlled product selectivity in electrochemical carbon dioxide reduction using manganese bipyridine catalysts. J. Am. Chem. Soc. 142, 4265–4275 (2020).

    Article  PubMed  Google Scholar 

  23. Zhang, Z. et al. Reaction mechanisms of well-defined metal-N4 sites in electrocatalytic CO2 reduction. Angew. Chem. Int. Ed. Engl. 57, 16339–16342 (2018).

    Article  CAS  PubMed  Google Scholar 

  24. Soucy, T. L., Liu, Y., Eisenberg, J. B. & McCrory, C. C. L. Enhancing the electrochemical CO2 reduction activity of polymer-encapsulated cobalt phthalocyanine films by modulating the loading of catalysts, polymers, and carbon supports. ACS Appl. Energy Mater. 5, 159–169 (2021).

    Article  Google Scholar 

  25. Wu, Y. et al. Domino electroreduction of CO2 to methanol on a molecular catalyst. Nature 575, 639–642 (2019).

    Article  CAS  PubMed  Google Scholar 

  26. Boutin, E. et al. On the existence and role of formaldehyde during aqueous electrochemical reduction of carbon monoxide to methanol by cobalt phthalocyanine. Chem. Eur. J. 28, e202200697 (2022).

    Article  CAS  PubMed  Google Scholar 

  27. Shi, L. L., Li, M., You, B. & Liao, R. Z. Theoretical study on the electro-reduction of carbon dioxide to methanol catalyzed by cobalt phthalocyanine. Inorg. Chem. 61, 16549–16564 (2022).

    Article  CAS  PubMed  Google Scholar 

  28. Boutin, E. et al. Aqueous electrochemical reduction of carbon dioxide and carbon monoxide into methanol with cobalt phthalocyanine. Angew. Chem. Int. Ed. Engl. 58, 16172–16176 (2019).

    Article  CAS  Google Scholar 

  29. Chen, X., Wei, D. & Ahlquist, M. S. G. Aggregation and significant difference in reactivity therein: blocking the CO2-to-CH3OH reaction. Organometallics 40, 3087–3093 (2021).

    Article  CAS  Google Scholar 

  30. Wu, Y. et al. Heterogeneous nature of electrocatalytic CO/CO2 reduction by cobalt phthalocyanines. Chem. Sus. Chem. 13, 6296–6299 (2020).

    Article  CAS  Google Scholar 

  31. Shang, B. et al. Aqueous photoelectrochemical CO2 reduction to CO and methanol over a silicon photocathode functionalized with a cobalt phthalocyanine molecular catalyst. Angew. Chem. Int. Ed. Engl. 62, e202215213 (2023).

    Article  CAS  PubMed  Google Scholar 

  32. Su, J. et al. Improving molecular catalyst activity using strain-inducing carbon nanotube supports. Preprint at ChemRxiv https://doi.org/10.26434/chemrxiv-2022-r9r22 (2022).

  33. Zeng, J. S., Corbin, N., Williams, K. & Manthiram, K. Kinetic analysis on the role of bicarbonate in carbon dioxide electroreduction at immobilized cobalt phthalocyanine. ACS Catal. 10, 4326–4336 (2020).

    Article  CAS  Google Scholar 

  34. Li, J. et al. Hydroxide is not a promoter of C2+ product formation in the electrochemical reduction of CO on copper. Angew. Chem. Int. Ed. Engl. 59, 4464–4469 (2020).

    Article  CAS  PubMed  Google Scholar 

  35. Resasco, J. et al. Promoter effects of alkali metal cations on the electrochemical reduction of carbon dioxide. J. Am. Chem. Soc. 139, 11277–11287 (2017).

    Article  CAS  PubMed  Google Scholar 

  36. Zhang, G. et al. Selective CO2 electroreduction to methanol via enhanced oxygen bonding. Nat. Commun. 13, 7768 (2022).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  37. Yang, D. et al. Selective electroreduction of carbon dioxide to methanol on copper selenide nanocatalysts. Nat. Commun. 10, 677 (2019).

    Article  PubMed  PubMed Central  Google Scholar 

  38. Guil-Lopez, R. et al. Methanol synthesis from CO2: a review of the latest developments in heterogeneous catalysis. Materials 12, 3902 (2019).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  39. Chang, X. et al. Tuning Cu/Cu2O interfaces for the reduction of carbon dioxide to methanol in aqueous solutions. Angew. Chem. Int. Ed. Engl. 57, 15415–15419 (2018).

    Article  CAS  PubMed  Google Scholar 

  40. Wu, Y. et al. Direct electrosynthesis of methylamine from carbon dioxide and nitrate. Nat. Sustain. 4, 725–730 (2021).

    Article  Google Scholar 

  41. Li, J. et al. Electrokinetic and in situ spectroscopic investigations of CO electrochemical reduction on copper. Nat. Commun. 12, 3264 (2021).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  42. Ji, Y. L. et al. Selective CO-to-acetate electroreduction via intermediate adsorption tuning on ordered Cu-Pd sites. Nat. Catal. 5, 251–258 (2022).

    Article  CAS  Google Scholar 

  43. Overa, S. et al. Enhancing acetate selectivity by coupling anodic oxidation to carbon monoxide electroreduction. Nat. Catal. 5, 738–745 (2022).

    Article  CAS  Google Scholar 

  44. Li, J. et al. Weak CO binding sites induced by Cu-Ag interfaces promote CO electroreduction to multi-carbon liquid products. Nat. Commun. 14, 698 (2023).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  45. Yin, Z. et al. An alkaline polymer electrolyte CO2 electrolyzer operated with pure water. Energy Environ. Sci. 12, 2455–2462 (2019).

    Article  CAS  Google Scholar 

  46. Fan, L. et al. Electrochemical CO2 reduction to high-concentration pure formic acid solutions in an all-solid-state reactor. Nat. Commun. 11, 3633 (2020).

    Article  CAS  PubMed  PubMed Central  Google Scholar 

Download references

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).

Author information

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

Authors
  1. Jing Li
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  2. Bo Shang
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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 (2023). https://doi.org/10.1038/s44160-023-00384-6

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