A. Vimont

Metal-organic and covalent organic frameworks as single-site catalysts

S.M.J. Rogge, A. Bavykina, J. Hajek, H. Garcia, A.I. Olivos-Suarez, A. Sepúlveda-Escribano, A. Vimont, G. Clet, P. Bazin, F. Kapteijn, M. Daturi, E.V. Ramos-Fernandez, F.X. Llabres i Xamena, V. Van Speybroeck, J. Gascon
Chemical Society Reviews
46 (11), 3134-3184


Heterogeneous single-site catalysts consist of isolated, well-defined, active sites that are spatially separated in a given solid and, ideally, structurally identical. In this review, the potential of metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) as platforms for the development of heterogeneous single-site catalysts is reviewed thoroughly. In the first part of this article, synthetic strategies and progress in the implementation of such sites in these two classes of materials are discussed. Because these solids are excellent playgrounds to allow a better understanding of catalytic functions, we highlight the most important recent advances in the modelling and spectroscopic characterization of single-site catalysts based on these materials. Finally, we discuss the potential of MOFs as materials in which several single-site catalytic functions can be combined within one framework along with their potential as powerful enzyme-mimicking materials. The review is wrapped up with our personal vision on future research directions.

Open Access version available at UGent repository
Gold Open Access

Synthesis modulation as a tool to increase the catalytic activity of MOFs: the unique case of UiO-66(Zr)

F. Vermoortele, B. Bueken, G. Le Bars, B. Van de Voorde, M. Vandichel, K. Houthoofd, A. Vimont, M. Daturi, M. Waroquier, V. Van Speybroeck, C. Kirschhock, D. De Vos
JACS (Journal of the American Chemical Society)
135 (31), 11465–11468


The catalytic activity of the zirconium terephthalate UiO-66(Zr) can be drastically increased by using a modulation approach. The combined use of trifluoroacetic acid and HCl during the synthesis results in a highly crystalline material, with partial substitution of terephthalates by trifluoroacetate. Thermal activation of the material leads not only to dehydroxylation of the hexanuclear Zr cluster but also to post-synthetic removal of the trifluoroacetate groups, resulting in a more open framework with a large number of open sites. Consequently, the material is a highly active catalyst for several Lewis acid catalyzed reactions.

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