Zhang Wuyong, Zhan Shaoqi, Xiao Jie, Petit Tristan, Schlesiger Christopher, Mellin Maximilian, Hofmann Jan P, Heil Tobias, Müller Riccarda, Leopold Kerstin, Oschatz Martin
Key Laboratory of Advanced Fuel Cells and Electrolyzers Technology of Zhejiang Province, Qianwan Institute of CNITECH, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo, Zhejiang, 315201, P. R. China.
Center for Energy and Environmental Chemistry Jena (CEEC Jena), Institute for Technical Chemistry and Environmental Chemistry, Friedrich-Schiller-University Jena, Philosophenweg 7a, 07743, Jena, Germany.
Adv Sci (Weinh). 2023 Oct;10(28):e2302623. doi: 10.1002/advs.202302623. Epub 2023 Aug 6.
Electrochemical nitrate reduction to ammonia powered by renewable electricity is not only a promising alternative to the established energy-intense and non-ecofriendly Haber-Bosch reaction for ammonia generation but also a future contributor to the ever-more important denitrification schemes. Nevertheless, this reaction is still impeded by the lack of understanding for the underlying reaction mechanism on the molecular scale which is necessary for the rational design of active, selective, and stable electrocatalysts. Herein, a novel single-site bismuth catalyst (Bi-N-C) for nitrate electroreduction is reported to produce ammonia with maximum Faradaic efficiency of 88.7% and at a high rate of 1.38 mg h mg at -0.35 V versus reversible hydrogen electrode (RHE). The active center (described as BiN C ) is uncovered by detailed structural analysis. Coupled density functional theory calculations are applied to analyze the reaction mechanism and potential rate-limiting steps for nitrate reduction based on the BiN C model. The findings highlight the importance of model catalysts to utilize the potential of nitrate reduction as a new-generation nitrogen-management technology based on the construction of efficient active sites.
由可再生电力驱动的电化学硝酸盐还原制氨，不仅是现有能源密集型且不环保的哈伯-博施法制氨的一种有前景的替代方案，也是未来对日益重要的反硝化方案的一大贡献。然而，该反应仍因缺乏对分子尺度下潜在反应机理的理解而受阻，而这种理解对于合理设计活性、选择性和稳定的电催化剂是必要的。在此，报道了一种用于硝酸盐电还原的新型单原子铋催化剂（Bi-N-C），在相对于可逆氢电极（RHE）为-0.35 V时，以88.7%的最大法拉第效率和1.38 mg h mg的高速率产氨。通过详细的结构分析揭示了活性中心（表示为BiN C）。基于BiN C模型，应用耦合密度泛函理论计算来分析硝酸盐还原的反应机理和潜在限速步骤。这些发现凸显了模型催化剂对于基于构建高效活性位点来利用硝酸盐还原作为新一代氮管理技术潜力的重要性。
