Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox-Active Fe(II/III) Sites in a Metal−Organic Framework

Ah Reum Kim; Sol Ahn; Tae Ung Yoon; Justin M. Notestein; Omar K. Farha; Youn Sang Bae

doi:10.1002/cctc.201901050

Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox-Active Fe(II/III) Sites in a Metal−Organic Framework

Ah Reum Kim, Sol Ahn, Tae Ung Yoon, Justin M. Notestein^*, Omar K. Farha, Youn Sang Bae

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

6 Scopus citations

Abstract

MIL-100(Fe), a metal−organic framework containing coordinatively unsaturated iron sites, was prepared by a solvothermal method and utilized in cyclohexane oxidation. Interestingly, the composition and fraction of redox-active Fe(II/III) sites in MIL-100(Fe) could be tuned by using different pretreatment temperatures. The obtained materials were characterized by means of field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (PXRD), N₂ adsorption-desorption isotherms, and X-ray photoelectron spectroscopy (XPS). Due to the presence of redox-active coordinatively unsaturated sites (CUS) at the iron atoms, MIL-100(Fe) exhibited good performance for cyclohexane oxidation under mild reaction conditions. Oxidation rates were significantly enhanced when reduced Fe^II sites were generated by high-temperature pretreatments. In either high-temperature or low-temperature pretreatment, the isolated Fe(II/III) sites in MIL-100 were far more reactive in cyclohexane oxidation than were bulk iron oxide materials. Finally, possible reaction pathways were proposed based on radical, Haber-Weiss routes.

Original language	English (US)
Pages (from-to)	5650-5656
Number of pages	7
Journal	ChemCatChem
Volume	11
Issue number	22
DOIs	https://doi.org/10.1002/cctc.201901050
State	Published - Nov 21 2019

Keywords

Cyclohexane
Metal−organic frameworks (MOFs)
Oxidation
Redox-active sites

ASJC Scopus subject areas

Catalysis
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{e118724972d844428c57d163a52e58ee,

title = "Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox-Active Fe(II/III) Sites in a Metal−Organic Framework",

abstract = "MIL-100(Fe), a metal−organic framework containing coordinatively unsaturated iron sites, was prepared by a solvothermal method and utilized in cyclohexane oxidation. Interestingly, the composition and fraction of redox-active Fe(II/III) sites in MIL-100(Fe) could be tuned by using different pretreatment temperatures. The obtained materials were characterized by means of field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (PXRD), N2 adsorption-desorption isotherms, and X-ray photoelectron spectroscopy (XPS). Due to the presence of redox-active coordinatively unsaturated sites (CUS) at the iron atoms, MIL-100(Fe) exhibited good performance for cyclohexane oxidation under mild reaction conditions. Oxidation rates were significantly enhanced when reduced FeII sites were generated by high-temperature pretreatments. In either high-temperature or low-temperature pretreatment, the isolated Fe(II/III) sites in MIL-100 were far more reactive in cyclohexane oxidation than were bulk iron oxide materials. Finally, possible reaction pathways were proposed based on radical, Haber-Weiss routes.",

keywords = "Cyclohexane, Metal−organic frameworks (MOFs), Oxidation, Redox-active sites",

author = "Kim, {Ah Reum} and Sol Ahn and Yoon, {Tae Ung} and Notestein, {Justin M.} and Farha, {Omar K.} and Bae, {Youn Sang}",

year = "2019",

month = nov,

day = "21",

doi = "10.1002/cctc.201901050",

language = "English (US)",

volume = "11",

pages = "5650--5656",

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number = "22",

}

Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox-Active Fe(II/III) Sites in a Metal−Organic Framework. / Kim, Ah Reum; Ahn, Sol; Yoon, Tae Ung; Notestein, Justin M.; Farha, Omar K.; Bae, Youn Sang.

In: ChemCatChem, Vol. 11, No. 22, 21.11.2019, p. 5650-5656.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Fast Cyclohexane Oxidation Under Mild Reaction Conditions Through a Controlled Creation of Redox-Active Fe(II/III) Sites in a Metal−Organic Framework

AU - Kim, Ah Reum

AU - Ahn, Sol

AU - Yoon, Tae Ung

AU - Notestein, Justin M.

AU - Farha, Omar K.

AU - Bae, Youn Sang

PY - 2019/11/21

Y1 - 2019/11/21

N2 - MIL-100(Fe), a metal−organic framework containing coordinatively unsaturated iron sites, was prepared by a solvothermal method and utilized in cyclohexane oxidation. Interestingly, the composition and fraction of redox-active Fe(II/III) sites in MIL-100(Fe) could be tuned by using different pretreatment temperatures. The obtained materials were characterized by means of field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (PXRD), N2 adsorption-desorption isotherms, and X-ray photoelectron spectroscopy (XPS). Due to the presence of redox-active coordinatively unsaturated sites (CUS) at the iron atoms, MIL-100(Fe) exhibited good performance for cyclohexane oxidation under mild reaction conditions. Oxidation rates were significantly enhanced when reduced FeII sites were generated by high-temperature pretreatments. In either high-temperature or low-temperature pretreatment, the isolated Fe(II/III) sites in MIL-100 were far more reactive in cyclohexane oxidation than were bulk iron oxide materials. Finally, possible reaction pathways were proposed based on radical, Haber-Weiss routes.

AB - MIL-100(Fe), a metal−organic framework containing coordinatively unsaturated iron sites, was prepared by a solvothermal method and utilized in cyclohexane oxidation. Interestingly, the composition and fraction of redox-active Fe(II/III) sites in MIL-100(Fe) could be tuned by using different pretreatment temperatures. The obtained materials were characterized by means of field-emission scanning electron microscopy (FE-SEM), powder X-ray diffraction (PXRD), N2 adsorption-desorption isotherms, and X-ray photoelectron spectroscopy (XPS). Due to the presence of redox-active coordinatively unsaturated sites (CUS) at the iron atoms, MIL-100(Fe) exhibited good performance for cyclohexane oxidation under mild reaction conditions. Oxidation rates were significantly enhanced when reduced FeII sites were generated by high-temperature pretreatments. In either high-temperature or low-temperature pretreatment, the isolated Fe(II/III) sites in MIL-100 were far more reactive in cyclohexane oxidation than were bulk iron oxide materials. Finally, possible reaction pathways were proposed based on radical, Haber-Weiss routes.

KW - Cyclohexane

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