Van Speybroeck, Veronique

Vandichel, Matthias

Waroquier, Michel

English

Ghent University Academic Bibliography

Important notes:Do NOT write outside the grey boxes. Any text or images outside the boxes will be deleted.Do NOT alter the structure of this form. Simply enter your information into the boxes. The form will be automatically processed – if you alter its structure your submission will not be processed correctly.Do not include keywords – you can add them when you submit the abstract online.Title:Modelling the effect of linker substituents on reactions in MOFsAuthors & affiliations:Matthias Vandichel, Michel Waroquier, Veronique Van SpeybroeckAbstract:  (Your abstract must use Normal style and must fit in this box.  Your abstract should be no longer than 300 words. The box will ‘expand’ over 2 pages as you add text/diagrams into it.)Nowadays, Metal-organic frameworks (MOFs) attract increasing interest in catalysis. In this talk, we will discuss the construction of accurate catalyst models to describe various reaction classes within those heterogeneous nanoporous materials and compare them with equivalent homogeneous catalysts for their activity (1-5). In the first part, two MOFs containing Lewis acid sites (UiO-66 and Cu3BTC2) will be compared with the industrially used homogeneous catalysts (ZrBr2 and ATPH) for the citronellal cyclization (1-2). In the second part, we will focus on the epoxidation of cyclohexene with tert-butylhydroperoxide (TBHP) and compare the heterogeneous catalyst MIL-47 with the homogeneous VO(acac)2 (3-5).Experimentally, linear free energy relationships have been found when the reactions were performed on linker substituted variants of the V- and Zr-MOFs, showing that the electronic effects of  linker substitution (-X) can be used as a tool to modulate the activity of the material. The relative conversion (kX/kH) in function of a substituent constant σ does then obey a Hammett equation. If the actual nature of the active site within the MOF is identified, a substituted cluster model can easily be constructed to reproduce these trends with first-principles chemical kinetics (2,5).References (1) Vermoortele, F., Vandichel, M.,  Van de Voorde, B., Ameloot, R., Waroquier, M., Van Speybroeck, V., De Vos, D. E., Angew. Chem. Int. Ed. 2012, 51, 4887.(2)  Vandichel,  M.,  Vermoortele,  F.,  Cottenie,  S.,  Devos,  D.E.,  Waroquier,  M.,  Van Speybroeck, V., submitted(3) Leus, K.; Vandichel, M.; Liu, Y. Y.; Muylaert, I.; Musschoot, J.; Pyl, S.; Vrielinck, H.; Callens, F.; Marin, G. B.; Detavernier, C.; Wiper, P. V.; Khimyak, Y. Z.; Waroquier, M.; Van Speybroeck, V.; Van der Voort, P. J Catal 2012, 285, 196.(4) Vandichel, M.; Leus, K.; Van Der Voort, P.; Waroquier, M.; Van Speybroeck, V. J Catal  2012, 294, 1(5)  Vandichel,  M.;  Biswas,  S.;  Leus,  K.;  Paier,  J.;  Sauer,  J.;  Van  Der  Voort,  P.; Waroquier, M.; Van Speybroeck, V. submitted

Modelling the effect of linker substituents on reactions in MOFs

https://biblio.ugent.be/publication/4171459/file/4171463.pdf

Modelling the effect of linker substituents on reactions in MOFs

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