skip to main content

DOE PAGESDOE PAGES

Title: Nitrogenase-mimic iron-containing chalcogels for photochemical reduction of dinitrogen to ammonia

A nitrogenase-inspired biomimetic chalcogel system comprising double-cubane [Mo 2Fe 6S 8(SPh) 3] and single-cubane (Fe 4S 4) biomimetic clusters demonstrates photocatalytic N 2 fixation and conversion to NH 3 in ambient temperature and pressure conditions. Replacing the Fe 4S 4 clusters in this system with other inert ions such as Sb 3+, Sn 4+, Zn 2+ also gave chalcogels that were photocatalytically active. Finally, molybdenum-free chalcogels containing only Fe 4S 4 clusters are also capable of accomplishing the N2 fixation reaction with even higher efficiency than their Mo 2Fe 6S 8(SPh) 3-containing counterparts. In this study, our results suggest that redox-active iron-sulfide–containing materials can activate the N 2 molecule upon visible light excitation, which can be reduced all of the way to NH 3 using protons and sacrificial electrons in aqueous solution. Evidently, whereas the Mo 2Fe 6S 8(SPh) 3 is capable of N 2 fixation, Mo itself is not necessary to carry out this process. The initial binding of N 2 with chalcogels under illumination was observed with in situ diffuse-reflectance Fourier transform infrared spectroscopy (DRIFTS). 15N 2 isotope experiments confirm that the generated NH 3 derives from N 2. Density functional theory (DFT) electronic structure calculations suggest thatmore » the N 2 binding is thermodynamically favorable only with the highly reduced active clusters. Finally, the results reported herein contribute to ongoing efforts of mimicking nitrogenase in fixing nitrogen and point to a promising path in developing catalysts for the reduction of N 2 under ambient conditions.« less
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Univ. of Ioannina, Ioannina (Greece)
Publication Date:
Grant/Contract Number:
SC0001059
Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 113; Journal Issue: 20; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
Northwestern Univ., Evanston, IL (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; nitrogenase mimics; chalcogel; N2 fixation; ammonia synthesis; photocatalytic
OSTI Identifier:
1250547
Alternate Identifier(s):
OSTI ID: 1347972