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Title: Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane

Iron-containing zeolites exhibit unprecedented reactivity in the low-temperature hydroxylation of methane to form methanol. Reactivity occurs at a mononuclear ferrous active site, α-Fe(II), that is activated by N 2O to form the reactive intermediate α-O. This has been defined as an Fe(IV)=O species. Using nuclear resonance vibrational spectroscopy coupled to X-ray absorption spectroscopy, we probe the bonding interaction between the iron center, its zeolite lattice-derived ligands, and the reactive oxygen. α-O is found to contain an unusually strong Fe(IV)=O bond resulting from a constrained coordination geometry enforced by the zeolite lattice. As a result, density functional theory calculations clarify how the experimentally determined geometric structure of the active site leads to an electronic structure that is highly activated to perform H-atom abstraction.
Authors:
 [1] ;  [1] ;  [2] ;  [1] ;  [1] ;  [1] ; ORCiD logo [3] ;  [3] ;  [3] ;  [4] ;  [5] ;  [2] ;  [2] ;  [5]
  1. Stanford Univ., Stanford, CA (United States)
  2. KU Leuven, Leuven (Belgium)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Grant/Contract Number:
CHE-1660611; G0A2216N; P41GM103393; AC02-06CH11357; DGE-11474; AC02-76SF00515
Type:
Accepted Manuscript
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 115; Journal Issue: 18; Journal ID: ISSN 0027-8424
Publisher:
National Academy of Sciences, Washington, DC (United States)
Research Org:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND TECHNOLOGY; 36 MATERIALS SCIENCE; nuclear resonance vibrational spectroscopy; X-ray absorption spectroscopy; density functional theory; zeolites; methane partial oxidation
OSTI Identifier:
1457409
Alternate Identifier(s):
OSTI ID: 1430783