Desilication: On the controlled generation of mesoporosity in MFI zeolites

Recent studies have shown that desilication by treatment in alkaline medium is, with respect to other methods, a very suitable and reproducible methodology to obtain mesoporous ZSM-5 zeolites with preserved structural integrity. This feature article analyzes mechanistic and kinetic aspects associated with this post-synthesis treatment. Framework aluminium controls the process of framework silicon extraction and makes desilication selective towards intracrystalline mesopore formation. An optimal molar Si/Al ratio in the range of 25-50 has been identified. At higher Si/Al ratios non-selective and excessive extraction of framework silicon occurs, while minor extraction and limited mesopore formation occurs at lower ratios. The presence of non-framework aluminium species, for example obtained by steam treatment, inhibits mesopore formation by alkaline treatment due to reinsertion of these species into the zeolite framework. Additional kinetic optimization of the physicochemical properties of the hierarchical porous zeolite structures is achieved by variation of time and temperature of the alkaline treatment. A successive combination of post-treatments, in which desilication is followed by dealumination, enables a decoupled modification of the mesoporous and acidic properties, being interesting in catalyst design and optimization. Preliminary work on other zeolite framework types has shown a promising outlook of the alkaline treatment. Development of mesoporous zeolites via desilication should induce a more efficient usage of the zeolite crystal due to an improved accessibility and a facilitated transport to and from the active sites.