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

DOI: 10.1039/D0SC04575F

Authors: Jianwei Zheng (University of Oxford) , Simson Wu (University of Oxford) , Lilin Lu (Wuhan University of Science and Technology) , Chen Huang (University of Oxford) , Ping-Luen Ho (University of Oxford) , Angus Kirkland (University of Oxford) , Tim Sudmeier (University of Oxford) , Rosa Arrigo (Diamond Light Source; University of Salford) , Diego Gianolio (Diamond Light Source) , Shik Chi Edman Tsang (University of Oxford)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science , VOL 12 , PAGES 688 - 695

State: Published (Approved)
Published: January 2021
Diamond Proposal Number(s): 20856

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.

Subject Areas: Chemistry


Instruments: B18-Core EXAFS

Added On: 04/02/2021 08:28

Documents:
d0sc04575f.pdf

Discipline Tags:

Physical Chemistry Catalysis Chemistry Inorganic Chemistry

Technical Tags:

Spectroscopy X-ray Absorption Spectroscopy (XAS) Extended X-ray Absorption Fine Structure (EXAFS) X-ray Absorption Near Edge Structure (XANES)