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  • Title: Molecular Engineering of Hydrogen-Bonded Organic Framework for Enhanced Nitrate Electroreduction to Ammonia.
    Author: Zhai P, Wang C, Li Y, Jin D, Shang B, Chang Y, Liu W, Gao J, Hou J.
    Journal: Nano Lett; 2024 Jul 17; 24(28):8687-8695. PubMed ID: 38973752.
    Abstract:
    Electrocatalytic nitrate reduction is an efficient way to produce ammonia sustainably. Herein, we rationally designed a copper metalloporphyrin-based hydrogen-bonded organic framework (HOF-Cu) through molecular engineering strategies for electrochemical nitrate reduction. As a result, the state-of-the-art HOF-Cu catalyst exhibits high NH3 Faradaic efficiency of 93.8%, and the NH3 production rate achieves a superior activity of 0.65 mmol h-1 cm-2. The in situ electrochemical spectroscopic combined with density functional theory calculations reveals that the dispersed Cu promotes the adsorption of NO3- and the mechanism is followed by deoxidation of NO3- to *NO and accompanied by deep hydrogenation. The generated *H participates in the deep hydrogenation of intermediate with fast kinetics as revealed by operando electrochemical impedance spectroscopy, and the competing hydrogen evolution reaction is suppressed. This research provides a promising approach to the conversion of nitrate to ammonia, maintaining the nitrogen balance in the atmosphere.
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