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Supramolecular tuning of supported metal phthalocyanine catalysts for hydrogen peroxide electrosynthesis

Nature Catalysis volume 6, pages 234–243 (2023)Cite this article

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Abstract

Two-electron oxygen reduction offers a route to H2O2 that is potentially cost-effective and less energy-intensive than the industrial anthraquinone process. However, the catalytic performance of the highest performing prior heterogeneous electrocatalysts to H2O2 has lain well below the >300 mA cm−2 needed for capital efficiency. Herein, guided by computation, we present a supramolecular approach that utilizes oxygen functional groups in a carbon nanotube substrate that—when coupled with a cobalt phthalocyanine catalyst—improve cobalt phthalocyanine adsorption, preventing agglomeration; and that further generate an electron-deficient Co centre whose interaction with the key H2O2 intermediate is tuned towards optimality. The catalysts exhibit an overpotential of 280 mV at 300 mA cm−2 with turnover frequencies over 50 s−1 in a neutral medium, an order of magnitude higher activity compared with the highest performing prior H2O2 electrocatalysts. This performance is sustained for over 100 h of operation.

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Fig. 1: Computational studies of electronically tuned H2O2 molecular electrocatalysts.
Fig. 2: The synthesis and structural characterization of CoPc-CNT(O).
Fig. 3: Electrochemical characterization of CoPc-CNT(O).
Fig. 4: H2O2 production performance in flow cells.

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Data availability

The data supporting the findings of this study are provided with the paper and its Supplementary Information files. Geometries are also available at https://github.com/hitarth64/CoPc-CNT. Further requests about data can be addressed to the corresponding authors. Source data are provided with this paper.

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Acknowledgements

This work was supported by the Natural Gas Innovation Fund, the Natural Sciences and Engineering Research Council of Canada, the Natural Resources Canada Clean Growth Program, and the Ontario Research Fund—Research Excellence programme. All DFT computations were performed on the Niagara supercomputer at the SciNet HPC Consortium. SciNet is funded by the Canada Foundation for Innovation, the Government of Ontario, the Ontario Research Fund Research Excellence Program, and the University of Toronto. This work was also supported by the Research Center Program of the IBS (IBS-R006-A2, Y.-E.S; IBS-R006-D1, T.H) in Korea.

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Author notes

  1. These authors contributed equally: Byoung-Hoon Lee, Heejong Shin, Armin Sedighian Rasouli, Hitarth Choubisa.

Authors and Affiliations

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

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

  2. Center for Nanoparticle Research, Institute for Basic Science, Seoul, Republic of Korea

    Heejong Shin, Hyeon Seok Lee, Taeghwan Hyeon & Yung-Eun Sung

  3. School of Chemical and Biological Engineering, and Institute of Chemical Processes, Seoul National University, Seoul, Republic of Korea

    Heejong Shin, Hyeon Seok Lee, Taeghwan Hyeon & Yung-Eun Sung

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

    Rui Kai Miao & David Sinton

  5. Department of Chemistry, Northwestern University, Evanston, IL, USA

    Edward H. Sargent

  6. Department of Electrical and Computer Engineering, Northwestern University, Evanston, IL, USA

    Edward H. Sargent

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Contributions

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

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Correspondence to Taeghwan Hyeon, Yung-Eun Sung or Edward H. Sargent.

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Nature Catalysis thanks Hailiang Wang and the other, anonymous, reviewers for their contribution to the peer review of this work.

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Lee, BH., Shin, H., Rasouli, A.S. et al. Supramolecular tuning of supported metal phthalocyanine catalysts for hydrogen peroxide electrosynthesis. Nat Catal 6, 234–243 (2023). https://doi.org/10.1038/s41929-023-00924-5

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