Kinetic analysis and modelling in heterogeneous catalysis

A combination of Temporal Analysis of Products, Temperature Programmed Reduction, and Density Functional theory techniques have been used to perform kinetic analysis on data from heterogeneous catalysis experiments. A new method of data filtering has been developed for Temporal Analysis of Products, and has been applied to a system of 4 Pt−Mo2C, and the current methodology has been expanded upon to calculate rate coefficients for the oxidation of CO to CO2 via the Boudard reaction. From the kinetic constants it appears that a phase change occurs in the material at approximately 200C. The current theory for analysing Temperature Programmed Reduction has been applied in a new methodology which is able to perform the deconvolution of thermograms with high accuracy, while also calculating the kinetic parameters related to the reduction processes. This new methodology has been applied to a system of CeO2 calcined at 400, 500 and 600C and the strengths and limitations of the methodology are explored. From the deconvolution procedure it was found that there are three distinct reduction processes occurring on the CeO2 and that a phase change occurs between 400 and 500C. Finally Density Functional Theory combined with classical dynamics has been used to explore the mechanism of the hydrogenation of Levulinic Acid to gamma-Valerolactone over a CuZrO2 catalyst. It was found that the Levulinic Acid is more likely to hydrogenate then cyclise, and from using molecular dynamics simulations it was shown that the solvent H2O plays a very important role in the cyclisation of the hydrogenated intermediate