@article{65df958c0e69476387493641a6c047b4,
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. 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.",
keywords = "Density functional theory, Methane partial oxidation, Nuclear resonance vibrational spectroscopy, X-ray absorption spectroscopy, Zeolites",
author = "Snyder, {Benjamin E.R.} and B{\"o}ttger, {Lars H.} and Bols, {Max L.} and Yan, {James J.} and Rhoda, {Hannah M.} and Jacobs, {Ariel B.} and Hu, {Michael Y.} and Jiyong Zhao and {Ercan Alp}, E. and Britt Hedman and Hodgson, {Keith O.} and Schoonheydt, {Robert A.} and Sels, {Bert F.} and Solomon, {Edward I.}",
note = "Funding Information: ACKNOWLEDGMENTS. B.E.R.S. acknowledges support from National Science Foundation Graduate Research Fellowship Program Grant DGE-11474 and from the Munger, Pollock, Reynolds, Robinson, Smith & Yoedicke Stanford Graduate Fellowship. Funding for this work was provided by National Science Foundation Grant CHE-1660611 (to E.I.S.) and Research Foundation– Flanders Grant G0A2216N (to B.F.S.). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under Contract DE-AC02-76SF00515. The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research and by National Institutes of Health, National Institute of General Medical Sciences Grant P41GM103393 (to K.O.H. and B.H.). This research used resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. Funding Information: B.E.R.S. acknowledges support from National Science Foundation Graduate Research Fellowship Program Grant DGE-11474 and from the Munger, Pollock, Reynolds, Robinson, Smith & Yoedicke Stanford Graduate Fellowship. Funding for this work was provided by National Science Foundation Grant CHE-1660611 (to E.I.S.) and Research Foundation–Flanders Grant G0A2216N (to B.F.S.). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences under Contract DE-AC02-76SF00515. The SSRL Structural Molecular Biology Program is supported by the DOE Office of Biological and Environmental Research and by National Institutes of Health, National Institute of General Medical Sciences Grant P41GM103393 (to K.O.H. and B.H.). This research used resources of the Advanced Photon Source, a US DOE Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract DE-AC02-06CH11357. Publisher Copyright: {\textcopyright} 2018 National Academy of Sciences. All rights reserved.",
year = "2018",
month = may,
day = "1",
doi = "10.1073/pnas.1721717115",
language = "English (US)",
volume = "115",
pages = "4565--4570",
journal = "Proceedings of the National Academy of Sciences of the United States of America",
issn = "0027-8424",
publisher = "National Academy of Sciences",
number = "18",
}