Catalytic Performance of Zr‐Based Metal‐Organic Frameworks Zr‐abtc and MIP‐200 in Selective Oxidations with H2O2

Catalytic Performance of Zr‐Based Metal‐Organic Frameworks Zr‐abtc and MIP‐200 in Selective Oxidations with H2O2 Научная публикация

Журнал

Chemistry - A European Journal
ISSN: 1521-3765 , E-ISSN: 0947-6539

Вых. Данные

Год: 2021, Том: 27, Номер: 23, Страницы: 6985-6992 Страниц : 8 DOI: 10.1002/chem.202005152

Авторы

Maksimchuk Nataliya V. ¹ , Ivanchikova Irina D. ¹ , Cho Kyung Ho ² , Zalomaeva Olga V. ¹ , Evtushok Vasiliy Yu. ^1,3 , Larionov Kirill P. ^1,3 , Glazneva Tatiana S. ¹ , Chang Jong-San ^2,4 , Kholdeeva Oxana A. ¹

Организации

1	Boreskov Institute of Catalysis
2	Research Center for Nanocatalysts, Korea Research Institute of Chemical Technology
3	Department of Natural Sciences, Novosibirsk State University
4	Department of Chemistry, Sungkyunkwan University

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.

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 CAPlus PMID OpenAlex Sciact

Поступила в редакцию:	1 дек. 2020 г.
Принята к публикации:	8 февр. 2021 г.
Опубликована online:	8 февр. 2021 г.
Опубликована в печати:	22 апр. 2021 г.

Web of science:	WOS:000628882000001
Scopus:	2-s2.0-85100933240
РИНЦ:	46748133
Chemical Abstracts:	2021:645633
PMID (PubMed):	33559238
OpenAlex:	W3126712626
Sciact:	39770