Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal–Organic Framework
Abstract
Metal organic frameworks (MOFs), with their crystalline, porous structures, can be synthesized to incorporate a wide range of catalytically active metals in tailored surroundings. These materials have potential as catalysts for conversion of light alkanes, feedstocks available in large quantities from shale gas that are changing the economics of manufacturing commodity chemicals. Mononuclear high-spin (S = 2) Fe(II) sites situated in the nodes of the MOF MIL-100(Fe) convert propane via dehydrogenation, hydroxylation, and overoxidation pathways in reactions with the atomic oxidant N2O. Pair distribution function analysis, N2 adsorption isotherms, X-ray diffraction patterns, and infrared and Raman spectra confirm the single-phase crystallinity and stability of MIL-100(Fe) under reaction conditions (523 K in vacuo, 378–408 K C3H8 + N2O). Density functional theory (DFT) calculations illustrate a reaction mechanism for the formation of 2-propanol, propylene, and 1-propanol involving the oxidation of Fe(II) to Fe(III) via a high-spin Fe(IV)$$=$$O intermediate. The speciation of Fe(II) and Fe(III) in the nodes and their dynamic interchange was characterized by in situ X-ray absorption spectroscopy and ex situ Mössbauer spectroscopy. Furthermore, the catalytic relevance of Fe(II) sites and the number of such sites were determined using in situ chemical titrations with NO. N2 and C3H6 production rates were found to be first-order in N2O partial pressure and zero-order in C3H8 partial pressure, consistent with DFT calculations that predict the reaction of Fe(II) with N2O to be rate determining. DFT calculations using a broken symmetry method show that Fe-trimer nodes affecting reaction contain antiferromagnetically coupled iron species, and highlight the importance of stabilizing high-spin (S = 2) Fe(II) species for effecting alkane oxidation at low temperatures (<408 K).
- Authors:
-
[1];
[2];
[3];
[2];
[5];
[4];
[3];
[6];
[2];
[1]
- Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455 (United States)
- Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455 (United States)
- Department of Chemical Engineering, University of California, Davis, California 95616 (United States)
- SSRL, SLAC National Accelerator Laboratory, Menlo Park, California 94025 (United States)
- Department of Chemistry, Stony Brook University, 100 Nicolls Road, Stony Brook, New York 11794 (United States)
- Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, (United States)
- Publication Date:
- Research Org.:
- SLAC National Accelerator Lab., Menlo Park, CA (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
- Sponsoring Org.:
- National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
- OSTI Identifier:
- 1597907
- Grant/Contract Number:
- AC02-76SF00515; SC0012702; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 45; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Iron; Metal organic frameworks; Catalysts; Extended X-ray absorption fine structure; Alkyls
Citation Formats
Simons, Matthew C., Vitillo, Jenny G., Babucci, Melike, Hoffman, Adam S., Boubnov, Alexey, Beauvais, Michelle L., Chen, Zhihengyu, Cramer, Christopher J., Chapman, Karena W., Bare, Simon R., Gates, Bruce C., Lu, Connie C., Gagliardi, Laura, and Bhan, Aditya. Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal–Organic Framework. United States: N. p., 2019.
Web. doi:10.1021/jacs.9b08686.
Simons, Matthew C., Vitillo, Jenny G., Babucci, Melike, Hoffman, Adam S., Boubnov, Alexey, Beauvais, Michelle L., Chen, Zhihengyu, Cramer, Christopher J., Chapman, Karena W., Bare, Simon R., Gates, Bruce C., Lu, Connie C., Gagliardi, Laura, & Bhan, Aditya. Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal–Organic Framework. United States. https://doi.org/10.1021/jacs.9b08686
Simons, Matthew C., Vitillo, Jenny G., Babucci, Melike, Hoffman, Adam S., Boubnov, Alexey, Beauvais, Michelle L., Chen, Zhihengyu, Cramer, Christopher J., Chapman, Karena W., Bare, Simon R., Gates, Bruce C., Lu, Connie C., Gagliardi, Laura, and Bhan, Aditya. Thu .
"Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal–Organic Framework". United States. https://doi.org/10.1021/jacs.9b08686. https://www.osti.gov/servlets/purl/1597907.
@article{osti_1597907,
title = {Structure, Dynamics, and Reactivity for Light Alkane Oxidation of Fe(II) Sites Situated in the Nodes of a Metal–Organic Framework},
author = {Simons, Matthew C. and Vitillo, Jenny G. and Babucci, Melike and Hoffman, Adam S. and Boubnov, Alexey and Beauvais, Michelle L. and Chen, Zhihengyu and Cramer, Christopher J. and Chapman, Karena W. and Bare, Simon R. and Gates, Bruce C. and Lu, Connie C. and Gagliardi, Laura and Bhan, Aditya},
abstractNote = {Metal organic frameworks (MOFs), with their crystalline, porous structures, can be synthesized to incorporate a wide range of catalytically active metals in tailored surroundings. These materials have potential as catalysts for conversion of light alkanes, feedstocks available in large quantities from shale gas that are changing the economics of manufacturing commodity chemicals. Mononuclear high-spin (S = 2) Fe(II) sites situated in the nodes of the MOF MIL-100(Fe) convert propane via dehydrogenation, hydroxylation, and overoxidation pathways in reactions with the atomic oxidant N2O. Pair distribution function analysis, N2 adsorption isotherms, X-ray diffraction patterns, and infrared and Raman spectra confirm the single-phase crystallinity and stability of MIL-100(Fe) under reaction conditions (523 K in vacuo, 378–408 K C3H8 + N2O). Density functional theory (DFT) calculations illustrate a reaction mechanism for the formation of 2-propanol, propylene, and 1-propanol involving the oxidation of Fe(II) to Fe(III) via a high-spin Fe(IV)$=$O intermediate. The speciation of Fe(II) and Fe(III) in the nodes and their dynamic interchange was characterized by in situ X-ray absorption spectroscopy and ex situ Mössbauer spectroscopy. Furthermore, the catalytic relevance of Fe(II) sites and the number of such sites were determined using in situ chemical titrations with NO. N2 and C3H6 production rates were found to be first-order in N2O partial pressure and zero-order in C3H8 partial pressure, consistent with DFT calculations that predict the reaction of Fe(II) with N2O to be rate determining. DFT calculations using a broken symmetry method show that Fe-trimer nodes affecting reaction contain antiferromagnetically coupled iron species, and highlight the importance of stabilizing high-spin (S = 2) Fe(II) species for effecting alkane oxidation at low temperatures (<408 K).},
doi = {10.1021/jacs.9b08686},
journal = {Journal of the American Chemical Society},
number = 45,
volume = 141,
place = {United States},
year = {Thu Oct 31 00:00:00 EDT 2019},
month = {Thu Oct 31 00:00:00 EDT 2019}
}
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