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Title: Influence of First and Second Coordination Environment on Structural Fe(II) Sites in MIL-101 for C–H Bond Activation in Methane

Abstract

Divalent iron sites in tri-iron oxo-centered metal nodes in metal–organic frameworks (MOFs) catalyze light alkane oxidation. The first two steps of the reaction sequence, which are also the most energetically demanding ones, are the formation of the active species, Fe(IV)=O, by N2O decomposition and subsequent C–H bond cleavage. We have employed Kohn–Sham density functional methods to explore how modification of the microenvironment around the Fe(II) center can modulate its catalytic activity, akin to what noted in metalloenzymes. We have varied the substituents on the organic linker of the MIL-101(Fe) MOF, as a way to modulate the energy barriers associated with the first two steps of the methane to methanol reaction. The calculations show that varying substituents has a minimal electronic effect on the iron center and its first coordination shell. However, their proximity to the active site can modify the barriers by 20%. Hydrogen bond donors can lower both barriers, such that the resulting Fe(IV)=O species are simultaneously more stable and more reactive than those of the parent MOF. The screening of a large set of systems allowed us to establish rules for the selection of second coordination shell elements to improve the reactivity of oxoferryl-based catalysts: (i) functionality withmore » a low pKa or large positive electrostatic potential, (ii) a distance around 1.5 Å between the oxoferryl and any atom of the ring substituent, and (iii) low conformational flexibility of the added substituent.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431, United States, Department of Science and High Technology and INSTM, Università degli Studi dell’Insubria, Via Valleggio 9, I-22100 Como, Italy
  2. Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street Southeast, Minneapolis, Minnesota 55455-0431, United States
  3. Department of Chemical Engineering and Materials Science, University of Minnesota, 421 Washington Avenue Southeast, Minneapolis, Minnesota 55455, United States
  4. Department of Chemistry, Pritzker School of Molecular Engineering, James Franck Institute, University of Chicago, Chicago, Illinois 60637, United States
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1765944
Alternate Identifier(s):
OSTI ID: 1771299
Grant/Contract Number:  
SC0012702
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Name: ACS Catalysis Journal Volume: 11 Journal Issue: 2; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; C−H bond activation; MOFs; catalysis; nonheme iron; density functional theory; MIL-101; second shell interactions; iron; hydrocarbons; peptides and proteins; metal organic frameworks; cluster chemistry

Citation Formats

Vitillo, Jenny G., Lu, Connie C., Cramer, Christopher J., Bhan, Aditya, and Gagliardi, Laura. Influence of First and Second Coordination Environment on Structural Fe(II) Sites in MIL-101 for C–H Bond Activation in Methane. United States: N. p., 2020. Web. doi:10.1021/acscatal.0c03906.
Vitillo, Jenny G., Lu, Connie C., Cramer, Christopher J., Bhan, Aditya, & Gagliardi, Laura. Influence of First and Second Coordination Environment on Structural Fe(II) Sites in MIL-101 for C–H Bond Activation in Methane. United States. https://doi.org/10.1021/acscatal.0c03906
Vitillo, Jenny G., Lu, Connie C., Cramer, Christopher J., Bhan, Aditya, and Gagliardi, Laura. 2020. "Influence of First and Second Coordination Environment on Structural Fe(II) Sites in MIL-101 for C–H Bond Activation in Methane". United States. https://doi.org/10.1021/acscatal.0c03906.
@article{osti_1765944,
title = {Influence of First and Second Coordination Environment on Structural Fe(II) Sites in MIL-101 for C–H Bond Activation in Methane},
author = {Vitillo, Jenny G. and Lu, Connie C. and Cramer, Christopher J. and Bhan, Aditya and Gagliardi, Laura},
abstractNote = {Divalent iron sites in tri-iron oxo-centered metal nodes in metal–organic frameworks (MOFs) catalyze light alkane oxidation. The first two steps of the reaction sequence, which are also the most energetically demanding ones, are the formation of the active species, Fe(IV)=O, by N2O decomposition and subsequent C–H bond cleavage. We have employed Kohn–Sham density functional methods to explore how modification of the microenvironment around the Fe(II) center can modulate its catalytic activity, akin to what noted in metalloenzymes. We have varied the substituents on the organic linker of the MIL-101(Fe) MOF, as a way to modulate the energy barriers associated with the first two steps of the methane to methanol reaction. The calculations show that varying substituents has a minimal electronic effect on the iron center and its first coordination shell. However, their proximity to the active site can modify the barriers by 20%. Hydrogen bond donors can lower both barriers, such that the resulting Fe(IV)=O species are simultaneously more stable and more reactive than those of the parent MOF. The screening of a large set of systems allowed us to establish rules for the selection of second coordination shell elements to improve the reactivity of oxoferryl-based catalysts: (i) functionality with a low pKa or large positive electrostatic potential, (ii) a distance around 1.5 Å between the oxoferryl and any atom of the ring substituent, and (iii) low conformational flexibility of the added substituent.},
doi = {10.1021/acscatal.0c03906},
url = {https://www.osti.gov/biblio/1765944}, journal = {ACS Catalysis},
issn = {2155-5435},
number = 2,
volume = 11,
place = {United States},
year = {2020},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1021/acscatal.0c03906

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