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Alkene Epoxidation and Thioether Oxidation with Hydrogen Peroxide Catalyzed by Mesoporous Zirconium-Silicates Full article

Journal Catalysts
ISSN: 2073-4344
Output data Year: 2022, Volume: 12, Number: 7, Article number : 742, Pages count : 22 DOI: 10.3390/catal12070742
Tags alkene; epoxidation; evaporation–induced self–assembly; heterogeneous catalysis; hydrogen peroxide; mesoporous zirconium–silicate
Authors Ivanchikova Irina D. 1 , Zalomaeva Olga V. 1 , Maksimchuk Nataliya V. 1 , Stonkus Olga A. 1 , Glazneva Tatiana S. 1 , Chesalov Yurii A. 1 , Shmakov Alexander N. 1 , Guidotti Matteo 2 , Kholdeeva Oxana A. 1
Affiliations
1 Boreskov Institute of Catalysis, Lavrentieva Ave. 5, Novosibirsk 630090, Russia
2 CNR-SCITEC, Via C. Golgi 19, 20133 Milano, Italy

Funding (2)

1 Ministry of Science and Higher Education of the Russian Federation 0239-2021-0009
2 Russian Foundation for Basic Research 21-53-15010

Abstract: Mesoporous zirconium-silicates have been prepared using two different methodologies, evaporation-induced self-assembly and solventless organometallic precursor dry impregnation of commercial SiO2. The samples were characterized by elemental analysis, XRD, N2 adsorption, TEM, DRS UV–vis and Raman spectroscopic techniques. The catalytic performance of the Zr-Si catalysts was assessed in the epoxidation of three representative alkenes, cyclohexene, cyclooctene and caryophyllene, as well as in the oxidation of methyl phenyl sulfide using aqueous hydrogen peroxide as a green oxidant, with special attention drawn to the structure/activity relationship and catalyst stability issues. The key factors which affect substrate conversion and epoxide selectivity have been defined. The catalysts with larger contents of oligomeric ZrO2 species revealed higher activity. The nature of alkene and, in particular, its molecular hindrance is crucial, since the adsorption of the epoxide product is the main factor leading to fast catalyst deactivation. In fact, bulky epoxides do not show this effect. After optimization, the oxidation of caryophyllene gave endocyclic monoepoxide with 77% selectivity at 87% alkene conversion. Methyl phenyl sulfoxide afforded 37% of sulfoxide and 63% of sulfone at 57% sulfide conversion. The nature of catalysis was truly heterogeneous and no Zr leaching was observed.
Cite: Ivanchikova I.D. , Zalomaeva O.V. , Maksimchuk N.V. , Stonkus O.A. , Glazneva T.S. , Chesalov Y.A. , Shmakov A.N. , Guidotti M. , Kholdeeva O.A.
Alkene Epoxidation and Thioether Oxidation with Hydrogen Peroxide Catalyzed by Mesoporous Zirconium-Silicates
Catalysts. 2022. V.12. N7. 742 :1-22. DOI: 10.3390/catal12070742 WOS Scopus РИНЦ AN OpenAlex
Dates:
Submitted: Jun 14, 2022
Accepted: Jul 3, 2022
Published print: Jul 5, 2022
Published online: Jul 5, 2022
Identifiers:
Web of science: WOS:000834374300001
Scopus: 2-s2.0-85133310402
Elibrary: 49151092
Chemical Abstracts: 2022:1992049
OpenAlex: W4284702639
Citing:
DB Citing
Scopus 13
Web of science 12
Elibrary 10
OpenAlex 14
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