Elucidating the Germanium Distribution in ITQ‐13 Zeolites by Density Functional Theory

ITQ‐13 is a medium‐pore zeolite that can be prepared in all‐silica form and as silicogermanate with Si/Ge ratios as low as 3. Usually synthesised in the presence of fluoride, ITQ‐13 is among the very few systems containing fluoride anions in two distinct cage types, cube‐like d4r units and [4 ⋅ 5(6)] cages. Here, dispersion‐corrected density functional theory (DFT) calculations are used to investigate the energetically most favourable Ge distributions for Si/Ge ratios between 55 and 6. The calculations show Ge atoms are incorporated at both the corners of d4r cages and at the basal plane of the [4 ⋅ 5(6)] cages, in accordance with (19)F NMR spectroscopy. Two Ge atoms at adjacent corners of [4 ⋅ 5(6)] cages are stable at the highest Ge content considered (Si/Ge=6). Such a local environment has not yet been considered in the experimental literature. A calculation of the corresponding (19)F NMR resonance points to overlap with other resonances, which might preclude its clear identification. Additional calculations investigate the variation of the dynamic behaviour of the fluoride anions as a function of the local environment as well as the selective defluorination of the [4 ⋅ 5(6)] cages.