Rational Catalyst Design for Oxygenate Reforming

Understanding and controlling bond breaking sequences of oxygenates on transition metal catalysts can greatly impact the utilization of biomass feedstocks for fuels and chemicals.  Specifically, the reforming of biomass and biomass derivatives to synthesis gas can act as a first step towards this transformation to value added products.  In this study, the decomposition of ethylene glycol, as the simplest representative of biomass-derived polyols, was studied via density functional theory (DFT) calculations to identify the differences in reaction pathways between Pt and the more active Ni/Pt bimetallic catalyst. Temperature programmed desorption (TPD) experiments were conducted with deuterated ethylene glycols for comparison with DFT results.  Insights from these fundamental studies were used to parameterize a semi-empirical based microkinetic model to probe for active and selective catalysts for ethylene glycol decomposition to synthesis gas.  Finally, this model was extended to other C1 and C2 oxygenates and optimal catalysts were tested experimentally.