Yang Chenxia, Tang Ying, Yang Qian, Wang Bo, Liu Xianghao, Li Yuxiang, Yang Weixia, Zhao Kunxuan, Wang Gang, Wang Zongyuan, Yu Feng
Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China.
Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi 832003, China; Carbon Neutralization and Environmental Catalytic Technology Laboratory (CN&ECT Lab), Bingtuan Industrial Technology Research Institute, Shihezi University, Shihezi 832003, China.
J Hazard Mater. 2024 Dec 5;480:136036. doi: 10.1016/j.jhazmat.2024.136036. Epub 2024 Oct 3.
Reducing nitrate (NO) in an aqueous solution to ammonia under ambient conditions can provide a green and sustainable NH-synthesis technology and mitigate global energy and pollution issues. In this work, a CuNi-1,3,5-benzenetricarboxylic acid/nickel foam (CuNi-MOF/NF) catalyst grown in situ was prepared via a one-pot method as an efficient cathode material for electrocatalytic nitrate reduction reaction (NORR). The CuNi-MOF/NF catalyst exhibited excellent electrocatalytic NORR performance at -1.0 V versus a reversible hydrogen electrode, achieving an outstanding faradaic efficiency of 95.88 % and an NH yield of 51.78 mg h cm. The N isotope labeling experiments confirmed that the sole source of N in the electrocatalytic NORR was the NO in the electrolyte. The reaction pathway for the electrocatalytic NORR was derived by in situ Fourier transform infrared spectroscopy and in situ differential electrochemical mass spectrometry. Density functional theory calculations revealed that the Ni element in the CuNi-MOF/NF catalyst had excellent O-H activation ability and strong *H adsorption capacity. These *H species were transferred from the Ni sites to the *NO adsorption intermediates located on the Cu sites, providing a continuous supply of *H to Cu, thereby promoting the formation of *NOH intermediates and enhancing the hydrogenation process of the electrocatalytic NORR.
在环境条件下将水溶液中的硝酸盐（NO）还原为氨可以提供一种绿色可持续的氨合成技术，并缓解全球能源和污染问题。在这项工作中，通过一锅法原位制备了一种生长在泡沫镍上的CuNi-均苯三甲酸（CuNi-MOF/NF）催化剂，作为电催化硝酸盐还原反应（NORR）的高效阴极材料。相对于可逆氢电极，CuNi-MOF/NF催化剂在-1.0 V时表现出优异的电催化NORR性能，实现了95.88%的出色法拉第效率和51.78 mg h cm的氨产率。氮同位素标记实验证实，电催化NORR中氮的唯一来源是电解液中的NO。通过原位傅里叶变换红外光谱和原位差分电化学质谱推导了电催化NORR的反应途径。密度泛函理论计算表明，CuNi-MOF/NF催化剂中的镍元素具有优异的O-H活化能力和较强的H吸附能力。这些H物种从镍位点转移到位于铜位点的NO吸附中间体上，为铜提供了持续的H供应，从而促进了*NOH中间体的形成并增强了电催化NORR的氢化过程。
