Structural insight into [Fe–S2–Mo] motif in electrochemical reduction of N2 over Fe1-supported molecular MoS2

Zheng, J; Wu, S; Lu, L; Huang, C; Ho, P-L; Kirkland, A; Sudmeier, T; Arrigo, R; Gianolio, D; Edman Tsang, SC

Abstract

The catalytic synthesis of NH3 from the thermodynamically challenging N2 reduction reaction under mild conditions is currently a significant problem for scientists. Accordingly, herein, we report the development of a nitrogenase-inspired inorganic-based chalcogenide system for the efficient electrochemical conversion of N2 to NH3, which is comprised of the basic structure of [Fe–S2–Mo]. This material showed high activity of 8.7 mgNH3 mgFe−1 h−1 (24 μgNH3 cm−2 h−1) with an excellent faradaic efficiency of 27% for the conversion of N2 to NH3 in aqueous medium. It was demonstrated that the Fe1 single atom on [Fe–S2–Mo] under the optimal negative potential favors the reduction of N2 to NH3 over the competitive proton reduction to H2. Operando X-ray absorption and simulations combined with theoretical DFT calculations provided the first and important insights on the particular electron-mediating and catalytic roles of the [Fe–S2–Mo] motifs and Fe1, respectively, on this two-dimensional (2D) molecular layer slab.

Citation

Zheng, J., Wu, S., Lu, L., Huang, C., Ho, P., Kirkland, A., …Edman Tsang, S. (2021). Structural insight into [Fe–S2–Mo] motif in electrochemical reduction of N2 over Fe1-supported molecular MoS2. Chemical Science, 12(2), 688-695. https://doi.org/10.1039/d0sc04575f

• Journal Article Type: Article
• Acceptance Date: Oct 21, 2020
• Online Publication Date: Nov 12, 2020
• Publication Date: Jan 14, 2021
• Deposit Date: Nov 23, 2020
• Publicly Available Date: Nov 23, 2020
• Journal: Chemical Science
• Print ISSN: 2041-6520
• Electronic ISSN: 2041-6539
• Publisher: Royal Society of Chemistry
• Volume: 12
• Issue: 2
• Pages: 688-695
• DOI: https://doi.org/10.1039/d0sc04575f
• Publisher URL: https://doi.org/10.1039/D0SC04575F
• Related Public URLs: https://pubs.rsc.org/en/journals/journal/sc
• Additional Information: Additional Information : ** Article version: VoR ** From Crossref journal articles via Jisc Publications Router ** Licence for VoR version of this article starting on 12-11-2020: http://creativecommons.org/licenses/by-nc/3.0/ **Journal IDs: pissn 2041-6520; eissn 2041-6539 **History: published 2021; Funders : Engineering and Physical Sciences Research Council (EPSRC);Engineering and Physical Sciences Research Council; Projects : DGE 102000; Grant Number: DGE 102000