Efficient electrochemical reduction of nitrate to ammonia over metal-organic framework single-atom catalysts

期刊论文
出版模式：

开放获取
发表日期：

2024年6月20日

查看全文

Lutong Shan,
Yujie Ma,
Shaojun Xu,
Meng Zhou,
Meng He,
Alena M. Sheveleva,
Rongsheng Cai,
Daniel Lee,
Yongqiang Cheng,
Boya Tang,
Bing Han,
Yinlin Chen,
Lan An,
Tianze Zhou,
Martin Wilding,
Alexander S. Eggeman,
Floriana Tuna,
Eric J. L. McInnes,
Sarah J. Day,
Stephen P. Thompson,
Sarah J. Haigh,
Xinchen Kang,
Buxing Han,
Martin Schröder,
Sihai Yang

摘要

The design and preparation of efficient catalysts for ammonia production under mild conditions is a desirable but highly challenging target. Here, we report a series of single-atom catalysts [M-SACs, M = Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Mo(II)] derived from UiO-66 containing structural defects and their application to electrochemical reduction of nitrate (NO₃^-) to ammonia (NH₃). Cu-SAC and Fe-SAC exhibit remarkable yield rates for NH₃ production of 30.0 and 29.0 mg h⁻¹ cm⁻², respectively, with a high Faradaic efficiency (FE_NH3) of over 96% at −1.0 V versus the reversible hydrogen electrode. Importantly, their catalytic performance can be retained in various simulated wastewaters. Complementary experiments confirmed the nature of single-atom sites within these catalysts and the binding domains of NO₃^- in UiO-66-Cu. In situ spectroscopic techniques, coupled with density functional theory calculations confirm the strong binding of NO₃^- and the formation of reaction intermediates, thus facilitating the catalytic conversion to NH₃.