Novel layered zeolitic organic-inorganic materials have been synthesized using a two-dimensional zeolite precursor IPC-1P prepared by a top-down approach from zeolite UTL. The formation of porous materials containing organic linkers or polyhedral oligomeric siloxane covalently bonded to zeolite layers in the interlayer space was confirmed by a variety of characterization techniques (N2/Ar sorption analysis, XRD, (29)Si and (13)C NMR, TEM). The organic-inorganic porous hybrids obtained by intercalation with silsesquioxane posessed layered morphology and contained large crystalline domains. The hybrids exhibited mesoporous or hierarchical micro-/mesoporous systems, stable up to 350 °C. Textural properties of the formed zeolitic organic-inorganic materials can be controlled by varying the linker or synthetic conditions over a broad range. Surface areas and pore volumes of synthesized hybrids significantly exceed those for parent zeolite UTL and corresponding swollen material; the amount of micropores increased with increasing rigidity and size of the organic linker in the order biphenyl > phenylene > ethanediyl.

Organic–inorganic aluminosilicate hybrids are an attractive new class of materials that add organic functionalities to conventional properties of solid inorganic catalysts. ECS-17, a novel crystalline hybrid, was synthesized using 1,4-bis-(triethoxysilyl)-benzene as the sole silicon source. Its structure was solved by direct methods starting from high-resolution synchrotron X-ray diffraction data and is composed of inorganic layers, characterized by 10 rings, held together by phenylene rings. ECS-17 is the first aluminosilicate built from only the three-ring secondary building unit. This new material shows intriguing reversible collapsibility upon dehydration/rehydration. Mild thermal treatment under vacuum causes its crystalline structure to collapse due to facile elimination of the water molecules around the cations. Successive exposure to ambient atmospheric moisture gives back the hydrated crystalline form. ECS-17 shows remarkably high thermal stability for a hybrid, being stable up to 450 °C under vacuum and breaking down at 350 °C in air. Structural, thermal, and optical properties were examined by X-ray powder diffraction, thermogravimetric analysis, nuclear magnetic resonance, and ultraviolet–visible-near-infrared reflectance and fluorescence spectroscopies

The influence of H3BO3 on the crystallization of hybrid organic-inorganic aluminosilicates denoted as Eni Carbon Silicates (ECS's) was investigated. Syntheses were carried out at 100 °C under different experimental conditions, using bridged silsesquioxanes of general formula (EtO)3Si-R-Si(OEt)3 (R = -C6H4- (BTEB), -C10H6- (BTEN) and -C6H4-C6H4- (BTEBP)), in the presence of equimolar concentrations of NaAlO2 and H3BO3. The study, involving the synthesis of three different but structurally related phases (ECS-14 from BTEB, ECS-13 here described for the first time from BTEN, and ECS-5 from BTEBP), confirmed a catalytic role for H3BO3 which in general increased the crystallization rate and improved the product quality in terms of amount of crystallized phase (crystallinity), size of the crystallites and phase purity, while it was weakly incorporated in trace amounts in the framework of ECS's.

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