Hydrogen peroxide activation and liquid‐phase selective oxidations over Ti,Zr‐based metal–organic framework PCN‐415

A mixed Ti,Zr‐based metal–organic framework, PCN‐415 (Porous Coordination Network), and the corresponding Ti,Zr‐oxocluster [Ti8Zr2O12(CH3COO)16] have been synthesized and comprehensively characterized by powder X‐Ray diffraction (PXRD), low‐temperature nitrogen adsorption, scanning electron microsco...

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Bibliographic Details
Published in:	Applied organometallic chemistry Vol. 38; no. 7
Main Authors:	Evtushok, Vasilii Yu, Zalomaeva, Olga V., Larionov, Kirill P., Ivanchikova, Irina D., Maksimchuk, Nataliya V., Kozulin, Fedor S., Chesalov, Yurii A., Kholdeeva, Oxana A.
Format:	Journal Article
Language:	English
Published:	Chichester Wiley Subscription Services, Inc 01-07-2024
Subjects:	Butyl hydroperoxide Catalysis Catalytic activity Fourier transforms heterogeneous catalysis Hydrogen peroxide Infrared analysis Infrared spectroscopy Leaching Metal-organic frameworks metal–organic framework Oxidation Oxidizing agents Raman spectroscopy selective oxidation Spectrum analysis Thermogravimetric analysis titanium Zirconium
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Summary:	A mixed Ti,Zr‐based metal–organic framework, PCN‐415 (Porous Coordination Network), and the corresponding Ti,Zr‐oxocluster [Ti8Zr2O12(CH3COO)16] have been synthesized and comprehensively characterized by powder X‐Ray diffraction (PXRD), low‐temperature nitrogen adsorption, scanning electron microscopy, thermogravimetric analysis, Fourier‐transform infrared spectroscopy, and Raman spectroscopy. The catalytic performance of both PCN‐415 and the Ti,Zr‐oxocluster was evaluated in the selective oxidation of representative thioethers, alkenes, and alkylphenols using aqueous hydrogen peroxide and tert‐butyl hydroperoxide as oxidants. The nature of the oxidation products formed indicates that, most likely, both Ti and Zr sites contribute to the catalytic activity of PCN‐415, although the contribution of Ti seems to be more significant. Examination of PCN‐415 after treatment with H2O2 using diffuse reflectance UV–vis spectroscopy indicates the formation of Ti peroxo complexes while Raman spectroscopy shows evidence for the formation of both Ti and Zr peroxo species. The potential formation of missing linker‐type defects and their role in facilitating catalytic activity were addressed. The stability of the PCN‐415 structure under the catalytic conditions was confirmed by PXRD. The absence of metal leaching and the heterogeneous nature of the catalysis were verified. The catalyst could be easily recovered from the reaction mixture and reused several times without loss of the catalytic properties. The metal–organic framework PCN‐415 and the corresponding Ti,Zr‐oxocluster can activate H2O2 at both Ti and Zr sites to form active peroxo species and catalyze the selective oxidation of 2,3,5‐trimethylphenol and methylphenyl sulfide.
ISSN:	0268-2605 1099-0739
DOI:	10.1002/aoc.7549