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

Department of Chemical and Biomolecular Engineering

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

20 Citations (Scopus)

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

Bibliographical note

Funding Information:
This work was supported by the National Research Foundation of Korea under Grant (NRF-2019R1A2C2002313). Also, the authors gratefully acknowledge the financial support from the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DESC0012702). This research was supported by Human Resources Program in Energy Technology of the Korea Institute of Energy Technology Evaluation and Planning (KETEP), granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No.20174010201640).

Publisher Copyright:
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

All Science Journal Classification (ASJC) codes

Catalysis
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1002/cctc.201901050

Cite this

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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.",

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

note = "Funding Information: This work was supported by the National Research Foundation of Korea under Grant (NRF-2019R1A2C2002313). Also, the authors gratefully acknowledge the financial support from the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DESC0012702). This research was supported by Human Resources Program in Energy Technology of the Korea Institute of Energy Technology Evaluation and Planning (KETEP), granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No.20174010201640). Publisher Copyright: {\textcopyright} 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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AU - Ahn, Sol

AU - Yoon, Tae Ung

AU - Notestein, Justin M.

AU - Farha, Omar K.

AU - Bae, Youn Sang

N1 - Funding Information: This work was supported by the National Research Foundation of Korea under Grant (NRF-2019R1A2C2002313). Also, the authors gratefully acknowledge the financial support from the Inorganometallic Catalyst Design Center, an EFRC funded by the DOE, Office of Basic Energy Sciences (DESC0012702). This research was supported by Human Resources Program in Energy Technology of the Korea Institute of Energy Technology Evaluation and Planning (KETEP), granted financial resource from the Ministry of Trade, Industry & Energy, Republic of Korea (No.20174010201640). Publisher Copyright: © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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.

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

Abstract

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