Catalytic Performance of Zr‐Based Metal‐Organic Frameworks Zr‐abtc and MIP‐200 in Selective Oxidations with H2O2 Full article
| Journal |
Chemistry - A European Journal
ISSN: 0947-6539 , E-ISSN: 1521-3765 |
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| Output data | Year: 2021, Volume: 27, Number: 23, Pages: 6985-6992 Pages count : 8 DOI: 10.1002/chem.202005152 | ||||||||
| Tags | Metal-organic frameworks, Hydrogen peroxide, Epoxidation, Zr, α,β-Unsaturated Ketones | ||||||||
| Authors |
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| Affiliations |
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Funding (2)
| 1 | Russian Foundation for Basic Research | 18-29-04022 |
| 2 | Ministry of Science and Higher Education of the Russian Federation | 0239-2021-0009 |
Abstract:
Catalytic performance of Zr-abtc and MIP-200 metal-organic frameworks consisted of 8-connected Zr6-clusters and tetratopic linkers was investigated in H2O2-based selective oxidations and compared with that of 12-coordinated UiO-66 and UiO-67. Zr-abtc demonstrated advantages in both substrate conversion and product selectivity for epoxidation of electron-deficient C=C bonds in α,β-unsaturated ketones. A significant predomination of 1,2-epoxide in carvone epoxidation, coupled to high sulfone selectivity in thioether oxidation, points to a nucleophilic oxidation mechanism over Zr-abtc. The superior catalytic performance in the epoxidation of unsaturated ketones correlates with a larger amount of weak basic sites in Zr-abtc. Electrophilic activation of H2O2 can also be realized, as evidenced by high activity of Zr-abtc in epoxidation of electron-rich C=C bond in caryophyllene. XRD and FTIR studies confirmed the retention of the Zr-abtc structure after the catalysis. Low activity of MIP-200 in H2O2-based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H2O2.
Cite:
Maksimchuk N.V.
, Ivanchikova I.D.
, Cho K.H.
, Zalomaeva O.V.
, Evtushok V.Y.
, Larionov K.P.
, Glazneva T.S.
, Chang J-S.
, Kholdeeva O.A.
Catalytic Performance of Zr‐Based Metal‐Organic Frameworks Zr‐abtc and MIP‐200 in Selective Oxidations with H2O2
Chemistry - A European Journal. 2021. V.27. N23. P.6985-6992. DOI: 10.1002/chem.202005152 WOS Scopus РИНЦ AN PMID OpenAlex
Catalytic Performance of Zr‐Based Metal‐Organic Frameworks Zr‐abtc and MIP‐200 in Selective Oxidations with H2O2
Chemistry - A European Journal. 2021. V.27. N23. P.6985-6992. DOI: 10.1002/chem.202005152 WOS Scopus РИНЦ AN PMID OpenAlex
Dates:
| Submitted: | Dec 1, 2020 |
| Accepted: | Feb 8, 2021 |
| Published online: | Feb 8, 2021 |
| Published print: | Apr 22, 2021 |
Identifiers:
| Web of science: | WOS:000628882000001 |
| Scopus: | 2-s2.0-85100933240 |
| Elibrary: | 46748133 |
| Chemical Abstracts: | 2021:645633 |
| PMID: | 33559238 |
| OpenAlex: | W3126712626 |