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Molecular Self-Assembly in Conductive Covalent Networks for Selective Nitrate Electroreduction to Ammonia
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    Molecular Self-Assembly in Conductive Covalent Networks for Selective Nitrate Electroreduction to Ammonia
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    • Feiqing Sun
      Feiqing Sun
      Department of Chemistry, Zhejiang University, Hangzhou 310058, China
      More by Feiqing Sun
    • Yifan Gao
      Yifan Gao
      Department of Chemistry, Zhejiang University, Hangzhou 310058, China
      More by Yifan Gao
    • Mengjie Li
      Mengjie Li
      Department of Chemistry, Zhejiang University, Hangzhou 310058, China
      More by Mengjie Li
    • Yingke Wen
      Yingke Wen
      Department of Chemistry, Zhejiang University, Hangzhou 310058, China
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    • Yanjie Fang
      Yanjie Fang
      Department of Chemistry, Zhejiang University, Hangzhou 310058, China
      More by Yanjie Fang
    • Thomas J. Meyer
      Thomas J. Meyer
      Department of Chemistry, The University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599, United States
    • Bing Shan*
      Bing Shan
      Department of Chemistry, Zhejiang University, Hangzhou 310058, China
      Key Laboratory of Excited-State Materials of Zhejiang Province, Hangzhou 310058, China
      *Email: [email protected]
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    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 39, 21491–21501
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    https://doi.org/10.1021/jacs.3c07320
    Published September 21, 2023
    Copyright © 2023 American Chemical Society

    Abstract

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    Electrochemical nitrate (NO3) reduction in aqueous media provides a useful approach for ammonia (NH3) synthesis. While efforts are focused on developing catalysts, the local microenvironment surrounding the catalyst centers is of great importance for controlling electrocatalytic performance. Here, we demonstrate that a self-assembled molecular iron catalyst integrated in a free-standing conductive hydrogel is capable of selective production of NH3 from NO3 at efficiencies approaching unity. With the electrocatalytic hydrogel, the NH3 selectivity is consistently high under a range of negative biases, which results from the hydrophobicity increase of the polycarbazole-based electrode substrate. In mildly acidic media, proton reduction is suppressed by electro-dewetting of the hydrogel electrode, enhancing the selectivity of NO3 reduction. The electrocatalytic hydrogel is capable of continuous production of NH3 for at least 100 h with NH3 selectivity of ∼89 to 98% at high current densities. Our results highlight the role of constructing an internal hydrophobic surface for electrocatalysts in controlling selectivity in aqueous media.

    Copyright © 2023 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/jacs.3c07320.

    • Synthetic scheme; FTIR spectra; current responses for HE; calibration plots; 15N-isotope labeling data; XPS spectra; SEM micrographs; Raman spectra; CV of HE–PP2Fe2+; additional electrocatalytic and calculational results; proposed reaction mechanism; surface coverages; NO3-concentration dependent results; isotopic competition experiment results; continuous electrocatalysis data; electrocatalytic performances for HS; pH dependent results; concentration of Fe; molecular catalyst performance for NO3RR; control experiments data; and description of DFT calculations (PDF)

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    Cited By

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    This article is cited by 8 publications.

    1. Feiyang Hong, Xinhao Su, Yanjie Fang, Xinjia He, Bing Shan. Manipulating Photoconduction in Supramolecular Networks for Solar-Driven Nitrate Conversion to Ammonia and Oxygen. Journal of the American Chemical Society 2024, 146 (36) , 25200-25210. https://doi.org/10.1021/jacs.4c09052
    2. Jing Zhou, Jiani Zhao, Dengmeng Song, Jiquan Liu, Wenhua Xu, Jun Li, Ning Wang. Cascade Electrocatalytic Reduction of Nitrate to Ammonia Using a Heterobimetallic Covalent Organic Framework Composed of Cu-Porphyrin and Co-Bipyridine. Inorganic Chemistry 2024, 63 (32) , 15177-15185. https://doi.org/10.1021/acs.inorgchem.4c02553
    3. Siyu Yi, Shicheng Yang, Zhikang Xie, Jie Yun, Xiangcheng Pan. Carbene-Mediated Polymer Modification Using Diazo Compounds under Photo or Thermal Activation Conditions. ACS Macro Letters 2024, 13 (6) , 711-718. https://doi.org/10.1021/acsmacrolett.4c00222
    4. Jinxiu Zhao, Xuejing Liu, Xiang Ren, Chang-Wen Zhang, Qin Wei, Dan Wu. High Active and Selective Electrocatalytic Nitrate-to-Ammonia Conversion in Fluorine-Rich ZnF2 Nanorod: Experimental and Theoretical Insight. ACS Sustainable Chemistry & Engineering 2024, 12 (24) , 8990-8997. https://doi.org/10.1021/acssuschemeng.4c02310
    5. Huijiao Wang, Gening Du, Jinzhi Jia, Junfeng Huang, Mudong Tu, Jinhua Zhang, Yong Peng, Hua Li, Cailing Xu. Ru-Doped NiFe-MIL-53 with Facilitated Reconstruction and Active Hydrogen Supplement for Enhanced Nitrate Reduction. Inorganic Chemistry 2024, 63 (20) , 9212-9220. https://doi.org/10.1021/acs.inorgchem.4c00766
    6. Kaiwen Yang, Shu-He Han, Chuanqi Cheng, Chengying Guo, Tieliang Li, Yifu Yu. Unveiling the Reaction Mechanism of Nitrate Reduction to Ammonia Over Cobalt-Based Electrocatalysts. Journal of the American Chemical Society 2024, 146 (19) , 12976-12983. https://doi.org/10.1021/jacs.3c13517
    7. Yanbiao Liu, Yiqing Zheng, Yifan Ren, Ying Wang, Shijie You, Meng Liu. Selective Nitrate Electroreduction to Ammonia on CNT Electrodes with Controllable Interfacial Wettability. Environmental Science & Technology 2024, 58 (16) , 7228-7236. https://doi.org/10.1021/acs.est.4c01464
    8. Maiko J. Askari, Jeremy D. Kallick, Charles C. L. McCrory. Selective Reduction of Aqueous Nitrate to Ammonium with an Electropolymerized Chromium Molecular Catalyst. Journal of the American Chemical Society 2024, 146 (11) , 7439-7455. https://doi.org/10.1021/jacs.3c12783

    Journal of the American Chemical Society

    Cite this: J. Am. Chem. Soc. 2023, 145, 39, 21491–21501
    Click to copy citationCitation copied!
    https://doi.org/10.1021/jacs.3c07320
    Published September 21, 2023
    Copyright © 2023 American Chemical Society

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