RESUMO
Controlled C-O bond scission is an important step for upgrading glycerol, a major byproduct from the continuously increasing biodiesel production. Transition metal nitride catalysts have been identified as promising hydrodeoxygenation (HDO) catalysts, but fundamental understanding regarding the active sites of the catalysts and reaction mechanism remains unclear. This work demonstrates a fundamental surface science study of Mo2N and Cu/Mo2N for the selective HDO reaction of glycerol, using a combination of model surface experiments and first-principles calculations. Temperature-programmed desorption (TPD) experiments showed that clean Mo2N cleaved two or three C-O bonds of glycerol to produce allyl alcohol, propanal, and propylene. The addition of Cu to Mo2N changed the reaction pathway to one C-O bond scission to produce acetol. High-resolution electron energy loss spectroscopy (HREELS) results identified the surface intermediates, showing a facile C-H bond activation on Mo2N. Density functional theory (DFT) calculations revealed that the surface N on Mo2N interacted with the H atoms in glycerol and blocked some Mo sites to enable selective C-O bond scission. This work shows that Mo2N and Cu/Mo2N are active and selective for the controlled C-O bond scission of glycerol and in turn provides insights into the rational catalyst design for selective oxygen removal of relevant biomass-derived oxygenates.
RESUMO
Direct propylene epoxidation by O2 is a challenging reaction because of the strong tendency for complete combustion. Results from the current study demonstrate that by generating highly dispersed and stabilized Cu(+) active sites in a TiCuOx mixed oxide the epoxidation selectivity can be tuned. The TiCuOx surface anchors the key surface intermediate, an oxametallacycle, leading to higher selectivity for epoxidation of propylene.
