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Beyond Radical Rebo...
Beyond Radical Rebound : Methane Oxidation to Methanol Catalyzed by Iron Species in Metal–Organic Framework Nodes
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- Simons, Matthew C. (författare)
- Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, United States
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- Prinslow, Steven D. (författare)
- Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
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- Babucci, Melike (författare)
- Department of Chemical Engineering, University of California, Davis, Davis, California 95616, United States
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- Hoffman, Adam S. (författare)
- SSRL, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
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- Hong, Jiyun (författare)
- SSRL, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
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- Vitillo, Jenny G. (författare)
- Department of Science and High Technology and INSTM, University of Insubria, 22100 Como, Italy
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- Bare, Simon R. (författare)
- SSRL, SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
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- Gates, Bruce C. (författare)
- Department of Chemical Engineering, University of California, Davis, Davis, California 95616, United States
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- Lu, Connie C. (författare)
- Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
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- Gagliardi, Laura (författare)
- Department of Chemistry, Pritzker School of Molecular Engineering, The James Franck Institute and Chicago Center for Theoretical Chemistry, The University of Chicago, Chicago, Illinois 60637, United States
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- Bhan, Aditya (författare)
- Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, United States
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(creator_code:org_t)
- 2021-07-27
- 2021
- Engelska.
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 143:31, s. 12165-12174
- Relaterad länk:
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https://urn.kb.se/re...
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https://doi.org/10.1...
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Abstract
Ämnesord
Stäng
- Recent work has exploited the ability of metalorganic frameworks (MOFs) to isolate Fe sites that mimic the structures of sites in enzymes that catalyze selective oxidations at low temperatures, opening new pathways for the valorization of underutilized feedstocks such as methane. Questions remain as to whether the radical-rebound mechanism commonly invoked in enzymatic and homogeneous systems also applies in these rigid-framework materials, in which resisting the overoxidation of desired products is a major challenge. We demonstrate that MOFs bearing Fe(II) sites within Fe-3-mu(3)-oxo nodes active for conversion of CH4 + N2O mixtures (368-408 K) require steps beyond the radical-rebound mechanism to protect the desired CH3OH product. Infrared spectra and density functional theory show that CH3OH(g) is stabilized as Fe(III)-OCH3 groups on the MOF via hydrogen atom transfer with Fe(III)-OH groups, eliminating water. Consequently, upon addition of a protonic zeolite in inter- and intrapellet mixtures with the MOF, we observed increases in (CHOH)-O-3 selectivity with increasing ratio and proximity of zeolitic H+ to MOF-based Fe(II) sites, as methanol is protected within the zeolite. We infer from the data that (CHOH)-O-3( g) is formed via the radical-rebound mechanism on Fe(II) sites but that subsequent transport and dehydration steps are required to protect (CHOH)-O-3( g) from overoxidation. The results demonstrate that the radical-rebound mechanism commonly invoked in this chemistry is insufficient to explain the reactivity of these systems, that the selectivity-controlling steps involve both chemical and physical rate phenomena, as well as offering a strategy to mitigate overoxidation in these and similar systems.
Nyckelord
- Colloid and Surface Chemistry
- Biochemistry
- General Chemistry
- Catalysis
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- Av författaren/redakt...
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Simons, Matthew ...
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Prinslow, Steven ...
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Babucci, Melike
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Hoffman, Adam S.
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Hong, Jiyun
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Vitillo, Jenny G ...
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visa fler...
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Bare, Simon R.
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Gates, Bruce C.
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Lu, Connie C.
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Gagliardi, Laura
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Bhan, Aditya
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visa färre...
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