(215c) Molecular and Mechanistic Modeling of Heterogeneous Catalysis in Supercritical Fluids

While heterogeneous catalysis in supercritical fluids has been studied quite extensively experimentally, there have been few computational studies devoted to these systems. In this talk, I will review a series of density functional theory (DFT), molecular simulation (molecular dynamics and Monte Carlo), and micro-kinetic modeling studies targeted at two heterogeneous catalytic systems: 1. Fischer-Tropsch synthesis in supercritical hexane (SCF-FT) and 2. thermochemical biomass conversion in supercritical water (SCW). These results include DFT computations of the potential energy and Gibbs free energy landscapes during SCF-FT. Further, these DFT results, when coupled with transition state theory, produced a micro-kinetic model which allowed an analysis of the effects of SCF hexane on the surface kinetics and pathways relative to the ideal gas (vacuum) limit. In addition, molecular dynamics simulations were used to compute the potential of mean force of carbon monoxide adsorption on Cobalt during SCF-FT and to highlight the SCF solvent effect. Finally, grand canonical Monte Carlo simulations were conducted to explore the adsorbed layer composition and thermodynamics during both SCF-FT and biomass conversion in SCW.

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4. Benjamin, K. M., Asiaee, A., Veer, C., Losinski, C., Gunderson, S., and Larson, T., J. Phys. Chem. C, 2016, 120, 21336.