Catalytic Performance of Zr-Based Metal-Organic Frameworks Zr-abtc and MIP-200 in Selective Oxidations with H 2 O 2 .

Autor: Maksimchuk NV; Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk, 630090, Russia., Ivanchikova ID; Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk, 630090, Russia., Cho KH; Research Center for Nanocatalysts, Korea Research Institute of Chemical Technology, P.O. Box 107, Yuseong, Daejeon, 305-600, Korea., Zalomaeva OV; Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk, 630090, Russia., Evtushok VY; Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk, 630090, Russia.; Department of Natural Sciences, Novosibirsk State University, Pirgova str. 2, Novosibirsk, 630090, Russia., Larionov KP; Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk, 630090, Russia.; Department of Natural Sciences, Novosibirsk State University, Pirgova str. 2, Novosibirsk, 630090, Russia., Glazneva TS; Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk, 630090, Russia., Chang JS; Research Center for Nanocatalysts, Korea Research Institute of Chemical Technology, P.O. Box 107, Yuseong, Daejeon, 305-600, Korea.; Department of Chemistry, Sungkyunkwan University, Suwon, 440-475, Korea., Kholdeeva OA; Boreskov Institute of Catalysis, pr. Lavrentieva 5, Novosibirsk, 630090, Russia.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2021 Apr 21; Vol. 27 (23), pp. 6985-6992. Date of Electronic Publication: 2021 Mar 15.
DOI: 10.1002/chem.202005152
Abstrakt: The catalytic performance of Zr-abtc and MIP-200 metal-organic frameworks consisting of 8-connected Zr 6 clusters and tetratopic linkers was investigated in H 2 O 2 -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. The significant predominance of 1,2-epoxide in carvone epoxidation, coupled with 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 H 2 O 2 can also be realized, as evidenced by the high activity of Zr-abtc in epoxidation of the electron-rich C=C bond in caryophyllene. XRD and FTIR studies confirmed the retention of the Zr-abtc structure after the catalysis. The low activity of MIP-200 in H 2 O 2 -based oxidations is most likely related to its specific hydrophilicity, which disfavors adsorption of organic substrates and H 2 O 2 .
(© 2021 Wiley-VCH GmbH.)
Databáze: MEDLINE
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