C–O cleavage of aromatic oxygenates over ruthenium catalysts. A computational study of reactions at step sites

Abstract

We studied the C–O cleavage of phenolate and catecholate at step sites of a Ru catalyst using periodic DFT methods at the GGA level. Both C–O scission steps are associated with activation barriers of about 75 kJ mol⁻¹, hence are significantly more facile than the analogous reactions on Ru terraces. With these computational results, we offer an interpretation of recent experiments on the hydrodeoxygenation of guaiacol (2-methoxyphenol) over Ru/C. We hypothesize that the experimentally observed dependency of the product selectivity on the H₂ pressure is related to the availability of step sites on a Ru catalyst.