ABSTRACT
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.
ABSTRACT
The gate-opening phenomenon in ZIFs is of paramount importance to understand their behavior in industrial molecular separations. Here we show for the first time using in situ inelastic neutron scattering (INS) the swinging of the -CH3 groups and the imidazolate linkers in the prototypical ZIF-8 and ZIF-8@AC hybrid materials upon exposure to mild N2 pressure.
ABSTRACT
One of the main concerns in the technological application of several metal-organic frameworks (MOFs) relates to their structural instability under pressure (after a conforming step). Here we report for the first time that mechanical instability can be highly improved via nucleation and growth of MOF nanocrystals in the confined nanospace of activated carbons.
