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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

    as
    1. Mengfan Wang & Sisi Liu & Tao Qian & Jie Liu & Jinqiu Zhou & Haoqing Ji & Jie Xiong & Jun Zhong & Chenglin Yan, 2019. "Over 56.55% Faradaic efficiency of ambient ammonia synthesis enabled by positively shifting the reaction potential," Nature Communications, Nature, vol. 10(1), pages 1-8, December.
    2. Jaecheol Choi & Bryan H. R. Suryanto & Dabin Wang & Hoang-Long Du & Rebecca Y. Hodgetts & Federico M. Ferrero Vallana & Douglas R. MacFarlane & Alexandr N. Simonov, 2020. "Identification and elimination of false positives in electrochemical nitrogen reduction studies," Nature Communications, Nature, vol. 11(1), pages 1-10, December.
    3. Zhe Weng & Yueshen Wu & Maoyu Wang & Jianbing Jiang & Ke Yang & Shengjuan Huo & Xiao-Feng Wang & Qing Ma & Gary W. Brudvig & Victor S. Batista & Yongye Liang & Zhenxing Feng & Hailiang Wang, 2018. "Active sites of copper-complex catalytic materials for electrochemical carbon dioxide reduction," Nature Communications, Nature, vol. 9(1), pages 1-9, December.
    4. Hong Bin Yang & Sung-Fu Hung & Song Liu & Kaidi Yuan & Shu Miao & Liping Zhang & Xiang Huang & Hsin-Yi Wang & Weizheng Cai & Rong Chen & Jiajian Gao & Xiaofeng Yang & Wei Chen & Yanqiang Huang & Hao M, 2018. "Atomically dispersed Ni(i) as the active site for electrochemical CO2 reduction," Nature Energy, Nature, vol. 3(2), pages 140-147, February.
    5. Zhen-Yu Wu & Mohammadreza Karamad & Xue Yong & Qizheng Huang & David A. Cullen & Peng Zhu & Chuan Xia & Qunfeng Xiao & Mohsen Shakouri & Feng-Yang Chen & Jung Yoon (Timothy) Kim & Yang Xia & Kimberly , 2021. "Electrochemical ammonia synthesis via nitrate reduction on Fe single atom catalyst," Nature Communications, Nature, vol. 12(1), pages 1-10, December.
    6. Wenhui He & Jian Zhang & Stefan Dieckhöfer & Swapnil Varhade & Ann Cathrin Brix & Anna Lielpetere & Sabine Seisel & João R. C. Junqueira & Wolfgang Schuhmann, 2022. "Splicing the active phases of copper/cobalt-based catalysts achieves high-rate tandem electroreduction of nitrate to ammonia," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    7. Wen Ju & Alexander Bagger & Guang-Ping Hao & Ana Sofia Varela & Ilya Sinev & Volodymyr Bon & Beatriz Roldan Cuenya & Stefan Kaskel & Jan Rossmeisl & Peter Strasser, 2017. "Understanding activity and selectivity of metal-nitrogen-doped carbon catalysts for electrochemical reduction of CO2," Nature Communications, Nature, vol. 8(1), pages 1-9, December.
    8. Yueshen Wu & Zhan Jiang & Zhichao Lin & Yongye Liang & Hailiang Wang, 2021. "Direct electrosynthesis of methylamine from carbon dioxide and nitrate," Nature Sustainability, Nature, vol. 4(8), pages 725-730, August.
    9. Gao-Feng Chen & Yifei Yuan & Haifeng Jiang & Shi-Yu Ren & Liang-Xin Ding & Lu Ma & Tianpin Wu & Jun Lu & Haihui Wang, 2020. "Electrochemical reduction of nitrate to ammonia via direct eight-electron transfer using a copper–molecular solid catalyst," Nature Energy, Nature, vol. 5(8), pages 605-613, August.
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