Fluoride Anions in All-Silica Zeolites: Studying Preferred Fluoride Sites and Dynamic Disorder with Density Functional Theory Calculations

In all-silica zeolites synthesised via the “fluoride route”, the fluoride anions are typically incorporated in small cages, forming [SiO₄F]^- trigonal bipyramids. While diffraction and NMR experiments can elucidate the fluoride location(s) and the occurrence/absence of dynamic disorder, they provide limited insights into the factors that determine equilibrium position and dynamic behaviour. To develop a more thorough understanding, electronic structure calculations in the framework of dispersion-corrected density functional theory (DFT) were performed for five all-silica zeolites (NON, STF, IFR, STT, CHA frameworks). DFT-based predictions of the energetically preferred fluoride location within a given cage were mostly in excellent agreement with experiment. Apart from the known tendency of fluoride anions to locate close to small rings, there are no easily generalisable crystal-chemical rules to predict the most probable fluoride sites.

DFT-based molecular dynamics calculations were employed to predict and explain the dynamic behaviour of the fluoride anions, which differs markedly among the different frameworks. On the basis of the simulations, it could be determined that local interactions of fluoride anions with framework Si atoms have larger impact on the (non-)occurrence of dynamic disorder than longer-range interactions with the organic structure-directing agents. In addition to providing detailed understanding of the behaviour of fluoride anions in as-synthesised all-silica zeolites, the findings of the present work could contribute to a further elucidation of the structure-directing role of fluoride during zeolite synthesis.