Computational Investigation of the Catalytic Hydrodeoxygenation of Propanoic Acid over a Cu(111) Surface
Cu-based alloy catalysts have recently been investigated experimentally for the hydrodeoxygenation (HDO) of biomass-derived organic acids. Here, the HDO of propanoic acid (PAc) has been studied over Cu(111) by mean-field microkinetic modeling based on parameters obtained from first-principles calculations. Models were developed for the gas- and liquid-phase HDO in condensed water and 1,4-dioxane. In agreement with experimental observations, the gas-phase PAc conversion rate is low at 573 K and increases in liquid water by 1 order of magnitude. In all reaction environments, the decarboxylation mechanism is dominant at low hydrogen partial pressures less than 0.1 bar, and the C–COO bond dissociation is the rate-controlling elementary step. This observation contrasts with the rate-controlling step identified over most group VIII metal surfaces, which is the C–OH bond dissociation in the decarbonylation mechanism. At high hydrogen (H 2 ) partial pressures greater than 10 bar, the HDO of PAc produces propionaldehyde that can readsorb and further react through decarbonylation to produce C 2 alkane products, which is conceptually different from the low H 2 partial pressure scenario. At high H 2 partial pressures, the initial hydrogenation at the carbonyl carbon of PAc becomes the rate-controlling elementary step.