Prediction of C6–C12 Interconversion Rates Using DFT and Zeolite-specific kinetic Monte Carlo Simulation Methods

This study introduces a novel kinetic Monte Carlo (KMC) simulation package which models H-ZSM-5 crystals across experimentally relevant time and length scales to understand the role of transport during arene interconversion reactions (~100 reactions). This small subset of the methanol-to-hydrocarbon (MTH) network was previously modeled using periodic, dispersion-corrected density functional theory (DFT) to determine activation barriers and reaction energies for these KMC methods. Transport of arene molecules through the straight and sinusoidal channels of MFI was modeled as site-hopping and the DFT-calculated barriers are incorporated into the KMC model to account for mass-transport limitations. Barriers of different arene molecules trend well with their effective radii, and species with a smaller effective radii diffusive more readily. A previously published maximum rate analysis of arene interconversion pathways—previously validated by experimental data—is compared to a diffusion-free KMC model to confirm the accuracy of this KMC package. The temperature and pressure dependencies of rates obtained from KMC agree well with those of maximum rate analysis on the diffusion-free model, demonstrating that KMC effectively predicts rates as well as maximum rate analysis methods commonly used in kinetic applications of DFT. Arene interconversion pathways were also analyzed on KMC models incorporating diffusion to and from interior crystal sites. These simulations suggest that large species, such as hexamethylbenzene, become trapped at 10–20% of sites, thus causing site deactivation by limiting diffusion through MFI channels and lowering overall rates of product formation. Benzene diffusion barriers are artificially varied from 20–200 kJ mol⁻¹ and rates of benzene methylation decrease by 4-fold with diffusion barriers greater than 80 kJ mol⁻¹; this suggests that species with diffusion barriers greater than 80 kJ mol⁻¹ (such as penta- and hexamethylbenzene) will likely become trapped at interior sites and ultimately cause catalyst deactivation. This study serves as a proof-of-concept for a novel KMC package that expedites kinetic analysis of complex reaction pathways and introduces mass-transport limitations which are not commonly accounted for in kinetic DFT studies. This KMC package can predict the behavior of diffusion-limited species, such as penta- and hexamethylbenzene, and the mechanisms by which they are formed and eventually lead to catalyst deactivation.