Zhang Guike, Wang Guohui, Wan Yuying, Liu Xijun, Chu Ke
School of Materials Science and Engineering, Lanzhou Jiaotong University, Lanzhou 730070, China.
State Key Laboratory of Featured Metal Materials and Life-cycle Safety for Composite Structures, School of Resource, Environments and Materials, Guangxi University, Nanning 530004, China.
ACS Nano. 2023 Nov 14;17(21):21328-21336. doi: 10.1021/acsnano.3c05946. Epub 2023 Oct 23.
Electrochemical conversion of NO into NH (NORR) holds an enormous prospect to simultaneously yield valuable NH and alleviate NO pollution. Herein, we report monodispersed Bi-doped FeS (Bi-FeS) as a highly effective NORR catalyst. Atomic coordination characterizations of Bi-FeS disclose that the isolated Bi dopant coordinates with its adjacent Fe atom to create the unconventional p-d hybridized Bi-Fe dinuclear sites. Operando spectroscopic measurements combined with theoretical calculations disclose that Bi-Fe dinuclear sites can synergistically enhance the hydrogenation energetics of NO-to-NH pathway, while suppressing the competitive hydrogen evolution, leading to a high NORR selectivity and activity. Consequently, the specially designed flow cell equipped with Bi-FeS exhibits a high NH yield rate of 83.7 mg h cm with a near-100% NO-to-NH Faradaic efficiency at an ampere-level current density of 1023.2 mA cm, together with an excellent long-term stability for 100 h of electrolysis, ranking almost the highest performance among all reported NORR catalysts.
将一氧化氮电化学转化为氨（NORR）对于同时生产有价值的氨和减轻一氧化氮污染具有巨大的前景。在此，我们报道了单分散的铋掺杂硫化铁（Bi-FeS）作为一种高效的NORR催化剂。Bi-FeS的原子配位表征表明，孤立的铋掺杂剂与其相邻的铁原子配位，形成非常规的p-d杂化铋-铁双核位点。原位光谱测量结合理论计算表明，铋-铁双核位点可以协同增强NO到NH途径的氢化能，同时抑制竞争性析氢，从而导致高NORR选择性和活性。因此，配备Bi-FeS的特殊设计的流动电池在1023.2 mA cm的安培级电流密度下表现出83.7 mg h cm的高氨产率，NO到NH的法拉第效率接近100%，并且在100小时的电解过程中具有出色的长期稳定性，在所有报道的NORR催化剂中几乎排名最高。
