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Regulation of the electrocatalytic nitrogen cycle based on sequential proton–electron transfer

Nature Catalysis volume 5, pages 798–806 (2022)Cite this article

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Abstract

The selective transformation of nitrogen compounds is a foundation of the modern chemical industry. Existing thermochemical processes largely rely on fossil fuels and innovating electrocatalytic processes that could use renewable energy remains challenging. Here we report the electrochemical regulation of a nitrite reduction network using a molybdenum sulfide catalyst by modulating the thermodynamic driving force of proton and electron transfer. The strategy behind this approach is based on the theory of sequential proton–electron transfer, in which the driving force of proton and electron transfer can be optimized independently. This makes it possible to target the desired reactions with selectivities of up to 80% for NO, 61% for N2O, 36% for N2 and 100% for NH4+, comparable to the highest values reported to date using a specific catalyst optimized for a single target product. Consistency with numerical simulation highlights that sequential proton–electron transfer can be used to rationally regulate the electrochemical nitrogen network.

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Fig. 1: The nitrogen cycle network in natural and industrial processes.
Fig. 2: Model of proton–electron transfer and its application for selective nitrite reduction.
Fig. 3: Characterization of MoS2.
Fig. 4: NO2− reduction to NO, N2O and NH4+ on MoS2 in a wide pH–E space.
Fig. 5: Simulation of the effects of E and pKa on the selectivity of NO2− reduction.
Fig. 6: Mechanism of N–N coupling and catalytic performance for full denitrification.

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Data availability

The data that support the findings of this study are available from the corresponding authors upon request. The Python program for numerical simulations can be found at GitHub (https://github.com/HideshiOoka/SI_for_Publications).

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Acknowledgements

We thank H. Ofuchi at SPring-8 for his assistance with the XAFS measurements. R.N. was supported by a JSPS Grant-in-Aid for Scientific Research (number 26288092). H.O. was supported by Fusion Oriented Research for Disruptive Science and Technology program of Japan Science and Technology Agency (JST). Y.L. was supported by a JSPS Grant-in-Aid for Scientific Research (number 19K15671). N.Y. and S.T. were supported by a JSPS Kiban-S Grant-in-Aid (number 17H06105). S.H.K. was supported by the Creative Materials Discovery Program (NRF-2017M3D1A1039380). The synchrotron radiation experiments were performed at the BL14B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI) (proposal numbers 2021A1664, 2021B1920, 2022A1045 and 2022A1669).

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Authors and Affiliations

  1. Earth-Life Science Institute (ELSI), Tokyo Institute of Technology, Tokyo, Japan

    Daoping He, Yamei Li, Naohiro Yoshida & Ryuhei Nakamura

  2. Biofunctional Catalyst Research Team, RIKEN Center for Sustainable Resource Science (CSRS), Wako, Japan

    Daoping He, Hideshi Ooka, Akira Yamaguchi & Ryuhei Nakamura

  3. Western Seoul Center, Korea Basic Science Institute, Seoul, Republic of Korea

    Yujeong Kim & Sun Hee Kim

  4. Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Republic of Korea

    Yujeong Kim & Sun Hee Kim

  5. School of Materials and Chemical Technology, Tokyo Institute of Technology, Tokyo, Japan

    Akira Yamaguchi & Ryuhei Nakamura

  6. Materials Characterization Support Team, RIKEN Center for Emergent Matter Science (CEMS), Wako, Japan

    Kiyohiro Adachi & Daisuke Hashizume

  7. School of Materials and Chemical Technology, Tokyo Institute of Technology, Yokohama, Japan

    Naohiro Yoshida & Sakae Toyoda

  8. National Institute of Information and Communications Technology, Tokyo, Japan

    Naohiro Yoshida

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Contributions

D. He and R.N. conceived and designed the experiments. D. He performed the experiments. H.O. performed the theoretical simulations. Y.L., N.Y. and S.T. performed the site-preference isotope measurements. Y.K., A.Y. and S.H.K. performed the EPR measurements. K.A. and D. Hashizume performed the XAFS measurements. D. He, H.O. and R.N. co-wrote the paper. All the authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Daoping He or Ryuhei Nakamura.

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Nature Catalysis thanks Bin Zhang and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–24, Tables 1–10, note 1 and references

Supplementary Data 1

The code for numerical simulation of the Faradaic efficiency.

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He, D., Ooka, H., Li, Y. et al. Regulation of the electrocatalytic nitrogen cycle based on sequential proton–electron transfer. Nat Catal 5, 798–806 (2022). https://doi.org/10.1038/s41929-022-00833-z

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