TY - JOUR

T1 - Hydrogen peroxide activation and liquid-phase selective oxidations over Ti,Zr-based metal–organic framework PCN-415

AU - Evtushok, Vasilii Yu

AU - Zalomaeva, Olga V.

AU - Larionov, Kirill P.

AU - Ivanchikova, Irina D.

AU - Maksimchuk, Nataliya V.

AU - Kozulin, Fedor S.

AU - Chesalov, Yurii A.

AU - Kholdeeva, Oxana A.

N1 - The authors thank Dr. A. A. Leonova for N adsorption, Dr. A. N. Serkova for SEM imaging, Dr. I. E. Soshnikov for NMR measurements, and Dr. I. G. Danilova for DRS UV\u2013vis measurements. The authors are grateful to Dr. Z. Huang for providing the crystallographic structural data of PCN\u2010415. This work was funded by the Ministry of Science and Higher Education of the Russian Federation within the governmental order for the Boreskov Institute of Catalysis (project FWUR\u20102024\u20100032). The studies were carried out using facilities of the shared research center \u201CNational center of investigation of catalysts\u201D at the Boreskov Institute of Catalysis. Raman spectra were measured using the equipment of the Center for Collective Use \u201CVTAN\u201D of the Analytical and Technological Research Center of the Department of Physics of Novosibirsk State University.

PY - 2024/7

Y1 - 2024/7

N2 - 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.

AB - 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.

KW - heterogeneous catalysis

KW - hydrogen peroxide

KW - metal–organic framework

KW - selective oxidation

KW - titanium

KW - zirconium

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-85193980369&origin=inward&txGid=d5df0ca4629fa8dd9b44fdb80618dbe2

UR - https://www.mendeley.com/catalogue/ace3dd4b-eafb-3600-9fa9-031d0968ef32/

U2 - 10.1002/aoc.7549

DO - 10.1002/aoc.7549

M3 - Article

VL - 38

JO - Applied Organometallic Chemistry

JF - Applied Organometallic Chemistry

SN - 0268-2605

IS - 7

M1 - e7549

ER -