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 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.

Evaluating the Role of Anharmonic Vibrations in Zeolite β Materials.

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 solid-state incorporation (SSI): the initial siliceous BEA (Si-β), aluminosilicate BEA (H-β), dealuminated BEA (deAl-β), and Sn-BEA (Sn-β).

The application of QM/MM simulations in heterogeneous catalysis.

The QM/MM simulation method is provenly efficient for the simulation of biological systems, where an interplay of extensive environment and delicate local interactions drives a process of interest through a funnel on a complex energy landscape. Recent advances in quantum chemistry and force-field methods present opportunities for the adoption of QM/MM to simulate heterogeneous catalytic processes, and their related systems, where similar intricacies exist on the energy landscape. Herein, the fundamental theoretical considerations for performing QM/MM simulations, and the practical considerations for setting up QM/MM simulations of catalytic systems, are introduced; then, areas of heterogeneous catalysis are explored where QM/MM methods have been most fruitfully applied.