Wu Limin, Feng Jiaqi, Zhang Libing, Jia Shunhan, Song Xinning, Zhu Qinggong, Kang Xinchen, Xing Xueqing, Sun Xiaofu, Han Buxing
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Colloid and Interface and Thermodynamics, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China.
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2023 Oct 23;62(43):e202307952. doi: 10.1002/anie.202307952. Epub 2023 Sep 19.
The renewable-energy-powered electroreduction of nitrate (NO ) to ammonia (NH ) has garnered significant interest as an eco-friendly and promising substitute for the Haber-Bosch process. However, the sluggish kinetics hinders its application at a large scale. Herein, we first calculated the N-containing species (*NO and *NO ) binding energy and the free energy of the hydrogen evolution reaction over Cu with different metal dopants, and it was shown that Zn was a promising candidate. Based on the theoretical study, we designed and synthesized Zn-doped Cu nanosheets, and the as-prepared catalysts demonstrated excellent performance in NO -to-NH . The maximum Faradaic efficiency (FE) of NH could reach 98.4 % with an outstanding yield rate of 5.8 mol g h , which is among the best results up to date. The catalyst also had excellent cycling stability. Meanwhile, it also presented a FE exceeding 90 % across a wide potential range and NO concentration range. Detailed experimental and theoretical studies revealed that the Zn doping could modulate intermediates adsorption strength, enhance NO conversion, change the *NO adsorption configuration to a bridge adsorption, and decrease the energy barrier, leading to the excellent catalytic performance for NO -to-NH .
可再生能源驱动的硝酸盐（NO ）电还原制氨（NH ）作为哈伯-博施法的一种环保且有前景的替代方法，已引起了广泛关注。然而，缓慢的动力学阻碍了其大规模应用。在此，我们首先计算了不同金属掺杂的铜上含氮物种（NO和NO ）的结合能以及析氢反应的自由能，结果表明锌是一个有潜力的候选者。基于理论研究，我们设计并合成了锌掺杂的铜纳米片，所制备的催化剂在NO 电还原制NH 中表现出优异的性能。NH 的最大法拉第效率（FE）可达98.4%，产率高达5.8 mol g h ，这是迄今为止最好的结果之一。该催化剂还具有出色的循环稳定性。同时，在较宽的电位范围和NO 浓度范围内，其FE也超过90%。详细的实验和理论研究表明，锌掺杂可以调节中间体的吸附强度，增强NO 转化，将*NO的吸附构型转变为桥式吸附，并降低能垒，从而导致其在NO 电还原制NH 中具有优异的催化性能。
