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

Abstract

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:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1457409
Alternate Identifier(s):
OSTI ID: 1430783
Grant/Contract Number:
CHE-1660611; G0A2216N; P41GM103393; AC02-06CH11357; DGE-11474; AC02-76SF00515
Resource Type:
Journal Article: 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)
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

Citation Formats

Snyder, Benjamin E. R., Bottger, Lars H., Bols, Max L., Yan, James J., Rhoda, Hannah M., Jacobs, Ariel B., Hu, Michael Y., Zhao, Jiyong, Alp, E. Ercan, Hedman, Britt, Hodgson, Keith O., Schoonheydt, Robert A., Sels, Bert F., and Solomon, Edward I. Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane. United States: N. p., 2018. Web. doi:10.1073/pnas.1721717115.
Snyder, Benjamin E. R., Bottger, Lars H., Bols, Max L., Yan, James J., Rhoda, Hannah M., Jacobs, Ariel B., Hu, Michael Y., Zhao, Jiyong, Alp, E. Ercan, Hedman, Britt, Hodgson, Keith O., Schoonheydt, Robert A., Sels, Bert F., & Solomon, Edward I. Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane. United States. doi:10.1073/pnas.1721717115.
Snyder, Benjamin E. R., Bottger, Lars H., Bols, Max L., Yan, James J., Rhoda, Hannah M., Jacobs, Ariel B., Hu, Michael Y., Zhao, Jiyong, Alp, E. Ercan, Hedman, Britt, Hodgson, Keith O., Schoonheydt, Robert A., Sels, Bert F., and Solomon, Edward I. Mon . "Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane". United States. doi:10.1073/pnas.1721717115.
@article{osti_1457409,
title = {Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane},
author = {Snyder, Benjamin E. R. and Bottger, Lars H. and Bols, Max L. and Yan, James J. and Rhoda, Hannah M. and Jacobs, Ariel B. and Hu, Michael Y. and Zhao, Jiyong and Alp, E. Ercan and Hedman, Britt and Hodgson, Keith O. and Schoonheydt, Robert A. and Sels, Bert F. and Solomon, Edward I.},
abstractNote = {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 N2O 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.},
doi = {10.1073/pnas.1721717115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 18,
volume = 115,
place = {United States},
year = {Mon Apr 02 00:00:00 EDT 2018},
month = {Mon Apr 02 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on April 2, 2019
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