Mild treatment of zeolite UTL results in degradation of its structure with preservation of the initially present dense layers connected by D4R "bridges". The lamellar product obtained through this 3D to 2D zeolite conversion has been structurally modified similar to methodologies applied to layered zeolite precursors, which show the opposite 2D to 3D zeolite transformation.

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Swelling of layered zeolite precursors such as MCM-22P with cationic surfactants at high pH is the key step in their subsequent conversion into expanded lamellar materials by pillaring and delamination. Increasing Al content in the precursors can yield more active catalysts but affects their swelling efficiency especially at lower temperature, which was reported as favorable for layer structure preservation with more siliceous MCM-22P. The latter, a (multi)­layered precursor, was investigated in this work and showed inadequate swelling of its high-Al representatives with organic hydroxide/surfactant mixtures and especially when NaOH is the source of high pH. In contrast, the unilamellar MCM-56 was found to swell readily at room temperature with various hydroxide sources, and notably with NaOH, in combination with the surfactant. The observed differences between MCM-56 and MCM-22P, especially with regard to swelling with NaOH, are attributed to the fundamentally different nature of their layer surface and interlayer linking. The former has surface terminated with AlOH–Na+ moieties, producing weak connections, instead of the pyramidal SiOHs populating the MCM-22P surface and forming interlayer H-bonding. The methods used for validating the swelling and product characterization included XRD, nitrogen sorption, IR spectroscopy and TEM imaging. The microscopy confirmed, by direct visualization, the extensive but not complete swelling of MCM-56, which can be enhanced by treatment at higher temperature.

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The unilamellar form of zeolite MWW, MCM-56, which is obtained by direct hydrothermal synthesis has been studied with regard to acidity and porosity in its original and post-synthesis modified pillared and delaminated forms. The acidity measured by FTIR was found to be only slightly lower than the highly active 3-D MWW forms, MCM-22 and MCM-49. Pivalonitrile adsorption, which is a measure of spatial openness, showed 50% accessibility vs. <30% for MCM-22/49. It highlights the potential of MCM-56 as a layered material with increased access to acid sites because it does not entail laborious post-synthesis modification. Swelling, pillaring and delamination of MCM-56 are facile but result in a reduction in the number of Brønsted acid sites (BAS) while increasing accessibility to pivalonitrile. The delamination procedure involving sonication and acidification of the highly basic mother liquor produces the most visible increase in surface area and access to all BAS. The accompanying doubling of the solid yield and the decrease in absolute number of BAS suggest significant precipitation of dissolved silica generated during swelling and sonication in high pH medium. The viability of separating surfactant covered layers upon sonication with the consequence of exposing hydrophobic hydrocarbon tails to aqueous environment is addressed.

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Hydrolysis of germanosilicate zeolites with the IWW structure shows two different outcomes depending on the composition of the starting materials. Ge-rich IWW (Si/Ge=3.1) is disassembled into a layered material (IPC-5P), which can be reassembled into an almost pure silica IWW on treatment with diethoxydimethylsilane. Ge-poor IWW (Si/Ge=6.4) is not completely disassembled on hydrolysis, but retains some 3D connectivity. This structure can be reassembled into IWW by incorporation of Al to fill the defects left when the Ge is removed.