Liu Yunliang, Zhuang Zechao, Liu Yixian, Liu Naiyun, Li Yaxi, Cheng Yuanyuan, Yu Jingwen, Yu Ruohan, Wang Dingsheng, Li Haitao
Institute for Energy Research, Jiangsu University, 212013, Zhenjiang, China.
Department of Chemistry, Tsinghua University, 100084, Beijing, China.
Angew Chem Int Ed Engl. 2024 Oct 21;63(43):e202411396. doi: 10.1002/anie.202411396. Epub 2024 Sep 12.
Electrochemical nitrate reduction method (NitRR) is a low-carbon, environmentally friendly, and efficient method for synthesizing ammonia, which has received widespread attention in recent years. Copper-based catalysts have a leading edge in nitrate reduction due to their good adsorption of *NO. However, the formation of active hydrogen (*H) on Cu surfaces is difficult and insufficient, resulting in a large amount of the by-product NO . In this work, Pd single atoms suspended on the interlayer unsaturated bonds of CuO atoms formed due to dislocations (Pd-CuO) were prepared by low temperature treatment, and the Pd single atoms located on the dislocations were subjected to shear stress and the dynamic effect of support formation to promote the conversion of nitrate into ammonia. The catalysis had an ammonia yield of 4.2 mol. g . h, and a Faraday efficiency of 90 % for ammonia production at -0.5 V vs. RHE. Electrochemical in situ characterization and theoretical calculations indicate that the dynamic effects of Pd single atoms and carriers under shear stress obviously promote the production of active hydrogen, reduce the reaction energy barrier of the decision-making step for nitrate conversion to ammonia, further promote ammonia generation.
电化学硝酸盐还原法（NitRR）是一种合成氨的低碳、环保且高效的方法，近年来受到广泛关注。铜基催化剂因其对*NO的良好吸附在硝酸盐还原方面具有优势。然而，在铜表面活性氢（*H）的形成困难且不足，导致大量副产物NO生成。在这项工作中，通过低温处理制备了悬浮在位错形成的CuO原子层间不饱和键上的钯单原子（Pd-CuO），位于位错处的钯单原子受到剪切应力和载体形成的动态效应，促进硝酸盐向氨的转化。该催化反应的氨产率为4.2 mol·g⁻¹·h⁻¹，在相对于可逆氢电极（RHE）为-0.5 V时氨生成的法拉第效率为90%。电化学原位表征和理论计算表明，钯单原子和载体在剪切应力下的动态效应明显促进了活性氢的产生，降低了硝酸盐转化为氨的决速步反应能垒，进一步促进了氨的生成。
