Quantum Chemical Characterization of Structural Single Fe(II) Sites in MIL-Type Metal-Organic Frameworks for the Oxidation of Methane to Methanol and Ethane to Ethanol

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Abstract

Single non-heme Fe(II) ions present as structural moieties in several metal-organic frameworks (e.g., MIL-100, MIL-101, and MIL-808, where MIL indicates Materials of Institute Lavoisier) are identified by Kohn-Sham density functional calculations as promising catalysts for C-H bond activation, with energetic barriers as low as 40 kJ mol-1 for ethane and 60 kJ mol-1 for methane following the oxidative activation of iron. The rate-determining step is the activation of N2O and has a barrier of 140 kJ mol-1. Through consideration of the full reaction profile leading to the corresponding alcohols, ethanol and methanol, we have identified key changes in the chemical composition of the node that would modulate catalytic activity. The thermal and chemical stabilities of these materials, together with the scalability of their syntheses, make them attractive catalysts for the selective low-temperature conversion of light alkanes to higher-value oxygenates.

Original languageEnglish (US)
Pages (from-to)2870-2879
Number of pages10
JournalACS Catalysis
Volume9
Issue number4
DOIs
StatePublished - Apr 5 2019

Fingerprint

Ethane
Methane
Methanol
Ethanol
Metals
Chemical activation
Oxidation
Catalysts
Alkanes
Chemical stability
Paraffins
Density functional theory
Scalability
Catalyst activity
Alcohols
Thermodynamic stability
Iron
Ions
Chemical analysis
N(1)-methyl-2-lysergic acid diethylamide

Keywords

  • C-H bond activation
  • MIL-100
  • MOFs
  • catalysis
  • density functional theory
  • multi-reference methods
  • non-heme iron

Cite this

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title = "Quantum Chemical Characterization of Structural Single Fe(II) Sites in MIL-Type Metal-Organic Frameworks for the Oxidation of Methane to Methanol and Ethane to Ethanol",
abstract = "Single non-heme Fe(II) ions present as structural moieties in several metal-organic frameworks (e.g., MIL-100, MIL-101, and MIL-808, where MIL indicates Materials of Institute Lavoisier) are identified by Kohn-Sham density functional calculations as promising catalysts for C-H bond activation, with energetic barriers as low as 40 kJ mol-1 for ethane and 60 kJ mol-1 for methane following the oxidative activation of iron. The rate-determining step is the activation of N2O and has a barrier of 140 kJ mol-1. Through consideration of the full reaction profile leading to the corresponding alcohols, ethanol and methanol, we have identified key changes in the chemical composition of the node that would modulate catalytic activity. The thermal and chemical stabilities of these materials, together with the scalability of their syntheses, make them attractive catalysts for the selective low-temperature conversion of light alkanes to higher-value oxygenates.",
keywords = "C-H bond activation, MIL-100, MOFs, catalysis, density functional theory, multi-reference methods, non-heme iron",
author = "Vitillo, {Jenny G.} and Aditya Bhan and Cramer, {Christopher J.} and Lu, {Connie C} and Laura Gagliardi",
year = "2019",
month = "4",
day = "5",
doi = "10.1021/acscatal.8b04813",
language = "English (US)",
volume = "9",
pages = "2870--2879",
journal = "ACS Catalysis",
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publisher = "American Chemical Society",
number = "4",

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TY - JOUR

T1 - Quantum Chemical Characterization of Structural Single Fe(II) Sites in MIL-Type Metal-Organic Frameworks for the Oxidation of Methane to Methanol and Ethane to Ethanol

AU - Vitillo, Jenny G.

AU - Bhan, Aditya

AU - Cramer, Christopher J.

AU - Lu, Connie C

AU - Gagliardi, Laura

PY - 2019/4/5

Y1 - 2019/4/5

N2 - Single non-heme Fe(II) ions present as structural moieties in several metal-organic frameworks (e.g., MIL-100, MIL-101, and MIL-808, where MIL indicates Materials of Institute Lavoisier) are identified by Kohn-Sham density functional calculations as promising catalysts for C-H bond activation, with energetic barriers as low as 40 kJ mol-1 for ethane and 60 kJ mol-1 for methane following the oxidative activation of iron. The rate-determining step is the activation of N2O and has a barrier of 140 kJ mol-1. Through consideration of the full reaction profile leading to the corresponding alcohols, ethanol and methanol, we have identified key changes in the chemical composition of the node that would modulate catalytic activity. The thermal and chemical stabilities of these materials, together with the scalability of their syntheses, make them attractive catalysts for the selective low-temperature conversion of light alkanes to higher-value oxygenates.

AB - Single non-heme Fe(II) ions present as structural moieties in several metal-organic frameworks (e.g., MIL-100, MIL-101, and MIL-808, where MIL indicates Materials of Institute Lavoisier) are identified by Kohn-Sham density functional calculations as promising catalysts for C-H bond activation, with energetic barriers as low as 40 kJ mol-1 for ethane and 60 kJ mol-1 for methane following the oxidative activation of iron. The rate-determining step is the activation of N2O and has a barrier of 140 kJ mol-1. Through consideration of the full reaction profile leading to the corresponding alcohols, ethanol and methanol, we have identified key changes in the chemical composition of the node that would modulate catalytic activity. The thermal and chemical stabilities of these materials, together with the scalability of their syntheses, make them attractive catalysts for the selective low-temperature conversion of light alkanes to higher-value oxygenates.

KW - C-H bond activation

KW - MIL-100

KW - MOFs

KW - catalysis

KW - density functional theory

KW - multi-reference methods

KW - non-heme iron

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