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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 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.

Authors:
 [1];  [1];  [2];  [1];  [1];  [1]; ORCiD logo [3];  [3];  [3];  [4];  [5];  [2];  [2];  [5]
+ Show Author Affiliations
  1. Department of Chemistry, Stanford University, Stanford, CA 94305,
  2. Department of Microbial and Molecular Systems, Centre for Surface Chemistry and Catalysis, KU Leuven, B-3001 Leuven, Belgium,
  3. Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439,
  4. Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA 94025
  5. Department of Chemistry, Stanford University, Stanford, CA 94305,, Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, Menlo Park, CA 94025
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE; National Science Foundation (NSF)
OSTI Identifier:
1430783
Alternate Identifier(s):
OSTI ID: 1457409; OSTI ID: 1466306
Grant/Contract Number:  
AC02-06CH11357; CHE-1660611; G0A2216N; P41GM103393; DGE-11474; AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 18; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
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., Böttger, 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.
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Snyder, Benjamin E. R., Böttger, 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. https://doi.org/10.1073/pnas.1721717115
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Snyder, Benjamin E. R., Böttger, 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. https://doi.org/10.1073/pnas.1721717115.
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@article{osti_1430783,
title = {Structural characterization of a non-heme iron active site in zeolites that hydroxylates methane},
author = {Snyder, Benjamin E. R. and Böttger, 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}
}
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https://doi.org/10.1073/pnas.1721717115
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