The effect of Mo2C support on the activity of Cu has been investigated for the hydrodeoxygenation of glycerol using density functional theory and microkinetic modeling. A Cu/Mo2C surface model with a monolayer of Cu supported on a Mo2C(1 0 0) surface and a Cu(1 1 1) surface were studied under ambient pressure and vacuum pressure conditions where experimental data have previously been collected. Our microkinetic analysis predicted a one order of magnitude higher turnover frequency for the Cu/Mo2C surface relative to Cu(1 1 1). In addition, the Cu/Mo2C surface was found to be active for a single C-O bond dissociation of glycerol, i.e., it produced acetol, while the Cu(1 1 1) surface was only able to produce dehydrogenation products. The enhanced activity of the Cu/Mo2C surface for the glycerol activation was attributed to electronic modification of Cu atoms by the Mo2C support, which enhanced the adsorption strength of intermediates and reduced the activation barrier for C/O cleavage reactions. (C) 2020 Elsevier Inc. All rights reserved.