Kinetic Modeling of Pt Catalyzed and Computation-Driven Catalyst Discovery for Ethylene Glycol Decomposition

Abstract

Knowledge of the underlying mechanisms controlling oxygenate catalytic decomposition to synthesis gas can lead to the design of better catalysts and reactors, enabling the utilization of biomass feedstock for fuels and chemicals. This work studies the decomposition of ethylene glycol, as a simple surrogate to biomass-derived polyols, through the analysis of two catalytic kinetic models. First, a density functional theory (DFT) and statistical mechanical parametrized model of 81 reversible, elementary-like reactions is used to predict and understand ethylene glycol decomposition on Pt. Reaction path analysis indicates that while the majority of decomposition occurs through initial O–H bond breaking, initial C–H bond breaking is active at temperatures around 500 K. Further, sensitivity analysis shows that early dehydrogenation reactions (specifically HOCH2CH2O* → HOCH2CHO* + H*) are kinetically important reactions, rather than C–C bond breaking. We show that steady state reactor conditions open up new react...