RESUMO
Sn-doped zeolites are potent Lewis acid catalysts for important reactions in the context of green and sustainable chemistry; however, their synthesis can have long reaction times and harsh chemical requirements, presenting an obstacle to scale-up and industrial application. To incorporate Sn into the ß zeolite framework, solid-state incorporation (SSI) has recently been demonstrated as a fast and solvent-free synthetic method, with no impairment to the high activity and selectivity associated with Sn-ß for its catalytic applications. Here, we report an ab initio computational study that combines periodic density functional theory with high-level embedded-cluster quantum/molecular mechanical (QM/MM) to elucidate the mechanistic steps in the synthetic process. Initially, once the Sn(II) acetate precursor coordinates to the ß framework, acetic acid forms via a facile hydrogen transfer from the ß framework onto the monodentate acetate ligand, with low kinetic barriers for subsequent dissociation of the ligand from the framework-bound Sn. Ketonization of the dissociated acetic acid can occur over the Lewis acidic Sn(II) site to produce CO2 and acetone with a low kinetic barrier (1.03 eV) compared to a gas-phase process (3.84 eV), helping to explain product distributions in good accordance with experimental analysis. Furthermore, we consider the oxidation of the Sn(II) species to form the Sn(IV) active site in the material by O2- and H2O-mediated mechanisms. The kinetic barrier for oxidation via H2 release is 3.26 eV, while the H2O-mediated dehydrogenation process has a minimum barrier of 1.38 eV, which indicates the possible role of residual H2O in the experimental observations of SSI synthesis. However, we find that dehydrogenation is facilitated more significantly by the presence of dioxygen (O2), introduced in the compressed air gas feed, via a two-step process oxidation process that forms H2O2 as an intermediate and has greatly reduced kinetic barriers of 0.25 and 0.26 eV. The results provide insight into how Sn insertion into ß occurs during SSI and demonstrate the possible mechanism of top-down synthetic procedures for metal insertion into zeolites.
RESUMO
The characterization of zeolitic materials is often facilitated by spectroscopic analysis of vibrations, which informs about the bonding character of the substrate and any adsorbents. Computational simulations aid the interpretation of the spectra but often ignore anharmonic effects that can affect the spectral characteristics significantly. Here, the impact of anharmonicity is demonstrated with a combination of dynamical and static simulations applied to the structures formed during the synthesis of Sn-BEA via solid-state incorporation (SSI): the initial siliceous BEA (Si-ß), aluminosilicate BEA (H-ß), dealuminated BEA (deAl-ß), and Sn-BEA (Sn-ß). Heteroatom and defect-containing BEA are shown to have strong anharmonic vibrational contributions, with atomic and elemental resolution highlighting particularly the prevalence for H atoms (H-ß, deAl-ß) as well as localization to heteroatoms at defect sites. We simulate the vibrational spectra of BEA accounting for anharmonic contributions and observe an improved agreement with experimental data compared to harmonic methods, particularly at wavenumbers below 1500 cm-1. The results demonstrate the importance of incorporating anharmonic effects in simulations of vibrational spectra, with consequences toward future characterization and application of zeolitic materials.