Novel insights into the surfactant-templating process leading to the formation of tailored intracrystalline mesoporosity in USY zeolite are presented in the light of the changes in the textural, morphological, and chemical properties of this zeolite produced during its treatment in a basic solution of cetyltrimethylammonium bromide (CTAB). The inability of analogous surfactants with bulkier heads to produce mesoporosity suggests that individual CTAB molecules can actually enter the zeolite through its microporosity. Once inside, the surfactant molecules self-assemble to produce the micelles responsible for the formation of mesoporosity causing the expansion of the zeolite crystals, as evidenced by He pycnometry measurements. The analysis of ultramicrotomed samples by transmission electron microscopy evidenced the formation of uniform intracrystalline mesoporosity throughout the entire crystals. In order to investigate an alternative method, namely, the dissolution and reassembly of zeolites, this was performed in USY leading to the formation of composite materials, which are distinctly different from the zeolite with intracrystalline mesoporosity obtained by surfactant-templating. Finally, it was proved that the presence of mesoporosity in the initial zeolite is not needed for the surfactant-templating to occur. This was verified by surfactant-templating of a NaY zeolite, which does not present the large mesopores found in USY.

Highly productive: Grafted monolith silica skeleton microreactors process bulky molecules more efficiently than a batch mode reactor. This efficiency is due to a higher contact area, shorter diffusion path, and lower inhibition by products in the thin monolith skeleton. These materials provide a new approach in the field of heterogeneous catalysis for the synthesis of fine chemicals.

The development of intracrystalline mesoporosity within zeolites has been a long-standing goal in catalysis as it greatly contributes to alleviating the diffusion limitations of these widely used microporous materials. The combination of in situ synchrotron X-ray diffraction and liquid-cell transmission electron microscopy enabled the first in situ observation of the development of intracrystalline mesoporosity in zeolites and provided structural and kinetic information on the changes produced in zeolites to accommodate the mesoporosity. The interpretation of the time-resolved diffractograms together with computational simulations evidenced the formation of short-range hexagonally ordered mesoporosity within the zeolite framework, and the in situ electron microscopy studies allowed the direct observation of structural changes in the zeolite during the process. The evidence for the templating and protective role of the surfactant and the rearrangement of the zeolite crystal to accommodate intracrystalline mesoporosity opens new and exciting opportunities for the production of tailored hierarchical zeolites.