Unraveling Unique Surface Chemistry of Transition Metal Nitrides in Controlling Selective C-O Bond Scission Pathways of Glycerol.

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 MoN and Cu/MoN 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 MoN cleaved two or three C-O bonds of glycerol to produce allyl alcohol, propanal, and propylene. The addition of Cu to MoN 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 MoN. Density functional theory (DFT) calculations revealed that the surface N on MoN interacted with the H atoms in glycerol and blocked some Mo sites to enable selective C-O bond scission. This work shows that MoN and Cu/MoN 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.