The substitution of germanium for silicon in AST-type zeolite

Abstract

The substitution of silicon by germanium in the AST zeolite framework type, [Si n Ge 40− n O 80] ∗4(SDA +F −) expressed as unit cell content in its cubic F-centered symmetry, has been studied. Three different kinds of templates, dimethyldiethylammonium, dimethyldiisopropylammonium and isopropyltrimethylammonium cations, were used in the hydrothermal synthesis process in fluoride medium. The products were identified with XRD, MAS NMR, SEM and thermal analysis. The analysis of the X-ray powder diagrams shows that AST crystallizes in different space group symmetries depending on the nature of the SDA and the degree of Ge-substitution. The resonance signals of 19F in MAS NMR experiments for the pure Si- and Ge-end members are at −38.2 and ∼−15 ppm, respectively, indicating that the F −-anion is located as co-template in the double-four-ring (D4R) of the tetrahedral framework. This is confirmed by Rietveld analysis of powder diffraction data of the pure Ge-end member. The peak splitting of the 19F NMR signal in pure GeO 2AST-type material is related to the displacement of F − location inside the D4R. Two more distinct signals at ∼−8 and ∼−19 ppm, respectively, are observed for X-ray pure AST-samples of intermediate compositions and assigned to fluoride in D4R built of 4[GeO 4]- and 4[SiO 4]-tetrahedra (4Ge, 4Si) and to (2Ge, 6Si)-D4R, respectively. An ordered distribution of Ge in the AST-framework is proposed for cubic AST with compositions around Si/Ge=1.5–1 by correlating the intensities of 19F NMR signals and the results from chemical analysis. This model is further confirmed by the quantitative analyses of the corresponding 29Si MAS NMR spectra.