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Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites

Author

Listed:
  • Eamonn Murphy

    (University of California)

  • Yuanchao Liu

    (University of California)

  • Ivana Matanovic

    (University of New Mexico
    Los Alamos National Laboratory)

  • Martina Rüscher

    (Fritz Haber Institute of the Max Planck Society)

  • Ying Huang

    (University of California)

  • Alvin Ly

    (University of California)

  • Shengyuan Guo

    (University of California)

  • Wenjie Zang

    (University of California)

  • Xingxu Yan

    (University of California)

  • Andrea Martini

    (Fritz Haber Institute of the Max Planck Society)

  • Janis Timoshenko

    (Fritz Haber Institute of the Max Planck Society)

  • Beatriz Roldán Cuenya

    (Fritz Haber Institute of the Max Planck Society)

  • Iryna V. Zenyuk

    (University of California
    University of California)

  • Xiaoqing Pan

    (University of California)

  • Erik D. Spoerke

    (Sandia National Laboratories)

  • Plamen Atanassov

    (University of California
    University of California)

Abstract

Electrocatalytic reduction of waste nitrates (NO3−) enables the synthesis of ammonia (NH3) in a carbon neutral and decentralized manner. Atomically dispersed metal-nitrogen-carbon (M-N-C) catalysts demonstrate a high catalytic activity and uniquely favor mono-nitrogen products. However, the reaction fundamentals remain largely underexplored. Herein, we report a set of 14; 3d-, 4d-, 5d- and f-block M-N-C catalysts. The selectivity and activity of NO3− reduction to NH3 in neutral media, with a specific focus on deciphering the role of the NO2− intermediate in the reaction cascade, reveals strong correlations (R=0.9) between the NO2− reduction activity and NO3− reduction selectivity for NH3. Moreover, theoretical computations reveal the associative/dissociative adsorption pathways for NO2− evolution, over the normal M-N4 sites and their oxo-form (O-M-N4) for oxyphilic metals. This work provides a platform for designing multi-element NO3RR cascades with single-atom sites or their hybridization with extended catalytic surfaces.

Suggested Citation

  • Eamonn Murphy & Yuanchao Liu & Ivana Matanovic & Martina Rüscher & Ying Huang & Alvin Ly & Shengyuan Guo & Wenjie Zang & Xingxu Yan & Andrea Martini & Janis Timoshenko & Beatriz Roldán Cuenya & Iryna , 2023. "Elucidating electrochemical nitrate and nitrite reduction over atomically-dispersed transition metal sites," Nature Communications, Nature, vol. 14(1), pages 1-15, December.
    • Handle: RePEc:nat:natcom:v:14:y:2023:i:1:d:10.1038_s41467-023-40174-4
    DOI: 10.1038/s41467-023-40174-4
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    References listed on IDEAS

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