Methane partial oxidation by monomeric Cu active center confined on ZIF-7

Hyesung Lee; Choah Kwon; Changjoon Keum; Hee Eun Kim; Hyunjoo Lee; Byungchan Han; Sang Yup Lee

doi:10.1016/j.cej.2022.138472

Methane partial oxidation by monomeric Cu active center confined on ZIF-7

Hyesung Lee, Choah Kwon, Changjoon Keum, Hee Eun Kim, Hyunjoo Lee, Byungchan Han, Sang Yup Lee

Department of Chemical and Biomolecular Engineering

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

4 Citations (Scopus)

Abstract

The monomeric cupric ion (Cu²⁺) species coordinated to four nitrogen ligands (CuN₄) is recognized as a possible active site for particulate methane monooxygenase (pMMO) of the methanotrophic bacteria that convert methane to methanol. Herein, inspired by the active site of pMMO, a copper-doped zeolitic imidazolate framework-7 (Cu/ZIF-7) was prepared, the mononuclear CuN₄ centers of which displayed catalytic partial oxidative activity and converted methane to methanol, methyl hydroperoxide, and hydroxymethyl hydroperoxide without producing the overoxidized product of formic acid. Spectroscopy studies established the mononuclear Cu²⁺ center coordinates with four benzimidazole nitrogens. The catalytic activity of Cu/ZIF-7 was scrutinized considering the potential reaction mechanism at the CuN₄ center, which substantially reduced the strong acidity of ZIF-7 to afford the partial oxidation of methane without forming formic acid.

Original language	English
Article number	138472
Journal	Chemical Engineering Journal
Volume	450
DOIs	https://doi.org/10.1016/j.cej.2022.138472
Publication status	Published - 2022 Dec 15

Bibliographical note

Funding Information:
This research used resources of the Pohang Accelerator Laboratory (PAL). Experiments at PLS-II were supported in part by MSIT and POSTECH. We are grateful to K. Kim and Prof. J. Cho (Ulsan National Institute of Science and Technology) for the reaction mechanism study.

Funding Information:
This study was supported by a grant from the Korean Research Foundation funded by the Korean Government (2021M3D3A1A01079478) and by the Global Frontier Program through the Global Frontier Hybrid Interface Materials (GFHIM) (2013M3A6B1078882) funded by the Ministry of Science and ICT.

Publisher Copyright:
© 2022 Elsevier B.V.

All Science Journal Classification (ASJC) codes

Chemistry(all)
Environmental Chemistry
Chemical Engineering(all)
Industrial and Manufacturing Engineering

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10.1016/j.cej.2022.138472

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title = "Methane partial oxidation by monomeric Cu active center confined on ZIF-7",

abstract = "The monomeric cupric ion (Cu2+) species coordinated to four nitrogen ligands (CuN4) is recognized as a possible active site for particulate methane monooxygenase (pMMO) of the methanotrophic bacteria that convert methane to methanol. Herein, inspired by the active site of pMMO, a copper-doped zeolitic imidazolate framework-7 (Cu/ZIF-7) was prepared, the mononuclear CuN4 centers of which displayed catalytic partial oxidative activity and converted methane to methanol, methyl hydroperoxide, and hydroxymethyl hydroperoxide without producing the overoxidized product of formic acid. Spectroscopy studies established the mononuclear Cu2+ center coordinates with four benzimidazole nitrogens. The catalytic activity of Cu/ZIF-7 was scrutinized considering the potential reaction mechanism at the CuN4 center, which substantially reduced the strong acidity of ZIF-7 to afford the partial oxidation of methane without forming formic acid.",

author = "Hyesung Lee and Choah Kwon and Changjoon Keum and Kim, {Hee Eun} and Hyunjoo Lee and Byungchan Han and Lee, {Sang Yup}",

note = "Funding Information: This research used resources of the Pohang Accelerator Laboratory (PAL). Experiments at PLS-II were supported in part by MSIT and POSTECH. We are grateful to K. Kim and Prof. J. Cho (Ulsan National Institute of Science and Technology) for the reaction mechanism study. Funding Information: This study was supported by a grant from the Korean Research Foundation funded by the Korean Government (2021M3D3A1A01079478) and by the Global Frontier Program through the Global Frontier Hybrid Interface Materials (GFHIM) (2013M3A6B1078882) funded by the Ministry of Science and ICT. Publisher Copyright: {\textcopyright} 2022 Elsevier B.V.",

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AU - Kwon, Choah

AU - Keum, Changjoon

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AU - Lee, Hyunjoo

AU - Han, Byungchan

AU - Lee, Sang Yup

N1 - Funding Information: This research used resources of the Pohang Accelerator Laboratory (PAL). Experiments at PLS-II were supported in part by MSIT and POSTECH. We are grateful to K. Kim and Prof. J. Cho (Ulsan National Institute of Science and Technology) for the reaction mechanism study. Funding Information: This study was supported by a grant from the Korean Research Foundation funded by the Korean Government (2021M3D3A1A01079478) and by the Global Frontier Program through the Global Frontier Hybrid Interface Materials (GFHIM) (2013M3A6B1078882) funded by the Ministry of Science and ICT. Publisher Copyright: © 2022 Elsevier B.V.

PY - 2022/12/15

Y1 - 2022/12/15

N2 - The monomeric cupric ion (Cu2+) species coordinated to four nitrogen ligands (CuN4) is recognized as a possible active site for particulate methane monooxygenase (pMMO) of the methanotrophic bacteria that convert methane to methanol. Herein, inspired by the active site of pMMO, a copper-doped zeolitic imidazolate framework-7 (Cu/ZIF-7) was prepared, the mononuclear CuN4 centers of which displayed catalytic partial oxidative activity and converted methane to methanol, methyl hydroperoxide, and hydroxymethyl hydroperoxide without producing the overoxidized product of formic acid. Spectroscopy studies established the mononuclear Cu2+ center coordinates with four benzimidazole nitrogens. The catalytic activity of Cu/ZIF-7 was scrutinized considering the potential reaction mechanism at the CuN4 center, which substantially reduced the strong acidity of ZIF-7 to afford the partial oxidation of methane without forming formic acid.

AB - The monomeric cupric ion (Cu2+) species coordinated to four nitrogen ligands (CuN4) is recognized as a possible active site for particulate methane monooxygenase (pMMO) of the methanotrophic bacteria that convert methane to methanol. Herein, inspired by the active site of pMMO, a copper-doped zeolitic imidazolate framework-7 (Cu/ZIF-7) was prepared, the mononuclear CuN4 centers of which displayed catalytic partial oxidative activity and converted methane to methanol, methyl hydroperoxide, and hydroxymethyl hydroperoxide without producing the overoxidized product of formic acid. Spectroscopy studies established the mononuclear Cu2+ center coordinates with four benzimidazole nitrogens. The catalytic activity of Cu/ZIF-7 was scrutinized considering the potential reaction mechanism at the CuN4 center, which substantially reduced the strong acidity of ZIF-7 to afford the partial oxidation of methane without forming formic acid.

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Methane partial oxidation by monomeric Cu active center confined on ZIF-7

Abstract

Bibliographical note

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