Computational Study of the Solid-State Incorporation of Sn(II) Acetate into Zeolite β

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 β 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-β 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 β framework, acetic acid forms via a facile hydrogen transfer from the β 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 β occurs during SSI and demonstrate the possible mechanism of top-down synthetic procedures for metal insertion into zeolites.