Zhai Panlong, Wang Chen, Li Yaning, Jin Dingfeng, Shang Bing, Chang Yuan, Liu Wei, Gao Junfeng, Hou Jungang
State Key Laboratory of Fine Chemical, Frontiers Science Center for Smart Materials Oriented Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, P. R. China.
The Key Laboratory of Materials Modification by Laser, Ion and Electron Beams of Ministry of Education, Dalian University of Technology, Dalian 116024, P. R. China.
Nano Lett. 2024 Jul 17;24(28):8687-8695. doi: 10.1021/acs.nanolett.4c02030. Epub 2024 Jul 8.
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 NH Faradaic efficiency of 93.8%, and the NH production rate achieves a superior activity of 0.65 mmol h cm. The in situ electrochemical spectroscopic combined with density functional theory calculations reveals that the dispersed Cu promotes the adsorption of NO and the mechanism is followed by deoxidation of NO 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.
电催化硝酸盐还原是一种可持续生产氨的有效方法。在此，我们通过分子工程策略合理设计了一种基于铜金属卟啉的氢键有机框架（HOF-Cu）用于电化学硝酸盐还原。结果，最先进的HOF-Cu催化剂表现出93.8%的高NH法拉第效率，NH生成速率达到0.65 mmol h cm的优异活性。原位电化学光谱结合密度泛函理论计算表明，分散的Cu促进了NO的吸附，其机制是NO脱氧为NO并伴随深度氢化。原位电化学阻抗谱表明，生成的H以快速动力学参与中间体的深度氢化，同时抑制了竞争性析氢反应。本研究为硝酸盐转化为氨提供了一种有前景的方法，维持了大气中的氮平衡。
