Topotactic condensation of layer silicates with ferrierite-type layers forming porous tectosilicates

Abstract

Five different hydrous layer silicates (HLSs) containing fer layers (ferrierite-type layers) were obtained by hydrothermal syntheses from mixtures of silicic acid, water and tetraalkylammonium/tetraalkylphosphonium hydroxides. The organic cations had been added as structure directing agents (SDA). A characteristic feature of the structures is the presence of strong to medium strong hydrogen bonds between the terminal silanol/siloxy groups of neighbouring layers. The five-layered silicates differ chemically only with respect to the organic cations. Structurally, they differ with respect to the arrangement of the fer layers relative to each other, which is distinct for every SDA-fer-layer system. RUB-20 (containing tetramethylammonium) and RUB-40 (tetramethylphosphonium) are monoclinic with stacking sequence AAA and shift vectors between successive layers 1a₀ + 0b₀ + 0.19c₀ and 1a₀ + 0b₀ + 0.24c₀, respectively. RUB-36 (diethyldimethylammonium), RUB-38 (methyltriethylammonium) and RUB-48 (trimethylisopropylammonium) are orthorhombic with stacking sequence ABAB and shift vectors 0.5a₀ + 0b₀ ± 0.36c₀, 0.5a₀ + 0b₀ + 0.5c₀ and 0.5a₀ + 0b₀ ± 0.39c₀, respectively. Unprecedented among the HLSs, two monoclinic materials are made up of fer layers which possess a significant amount of ordered defects within the layer. The ordered defects involve one particular Si–O–Si bridge which is, to a fraction of ca. 50%, hydrolyzed to form nests of two Si–OH groups. When heated to 500–600 °C in air, the HLSs condense to form framework silicates. Although all layered precursors were moderately to well ordered, the resulting framework structures were of quite different crystallinity. The orthorhombic materials RUB-36, -38 and -48, general formula SDA₄Si₃₆O₇₂(OH)₄, which possess very strong hydrogen bonds (d[O⋯O] ≈ 2.4 Å), transform into a fairly or well ordered CDO-type silica zeolite RUB-37. The monoclinic materials RUB-20 and -40, general formula SDA₂Si₁₈O₃₆(OH)₂OH, possessing medium strong hydrogen bonds (d[O⋯O] ≈ 2.65 Å) are transformed into poorly ordered framework silicates. Some rules of thumb can be established concerning the successful zeolite synthesis via a topotactic condensation of layered precursors. Favourably, the precursor (i) possesses already a well ordered structure without defects, (ii) contains strong inter-layer hydrogen bonds and does not contain strong intra-layer hydrogen bonds and (iii) contains a suitable cation. The nature of the organic cation (size, geometry, flexibility, thermal stability) plays a key role in the formation of a microporous tectosilicate with well ordered structure. RUB-36 which meets these criteria yields a well ordered condensation product (RUB-37).