Stability of intermediates in the glycerol hydrogenolysis on transition metal catalysts from first principles

The hydrogenolysis reaction catalyzed by a transition metal solid catalyst is a potential way to transform glycerol to 1,2-propylene glycol or 1,3-propylene glycol, two important chemicals. We explore the thermodynamic profile of this reaction from first principle simulation, comparing Ni, Rh and Pd catalysts modeled by (111) surfaces. The stability of adsorbed reactants, dehydrated intermediates, and hydrogenated propylene glycol is compared, with a special focus on the factors controlling the selectivity of the reaction. From a global thermodynamic view point, the formation of 1,2-propylene glycol is favored, and in addition the most stable intermediates in the gas phase (acetol and 1,2-aldol) lead to the formation of this product. The metal catalyst has three roles. First it stabilizes the dehydrated intermediates and renders the dehydration more exothermic. Second, the adsorption on the surface modifies the relative stability of the dehydrated intermediates, with implications on the reaction selectivity. Third it catalyses the hydrogenation step, leading to propylene glycol.