title: Comparison of bond scission sequence of methanol on tungsten monocarbide and Pt-modified tungsten monocarbide.
abstract: The ability to control the bond scission sequence of O-H, C-H, and C-O bonds is of critical importance in the effective utilization of oxygenate molecules, such as in reforming reactions and in alcohol fuel cells. In the current study, we use methanol as a probe molecule to demonstrate the possibility to control the decomposition pathways by supporting monolayer coverage of Pt on a tungsten monocarbide (WC) surface. Density functional theory (DFT) results reveal that on the WC and Pt/WC surfaces CH3OH decomposes via O-H bond scission to form the methoxy (*CH3 O) intermediate. The subsequent decomposition of methoxy on the WC surface occurs through the C-O bond scission to form *CH3, which reacts with surface *H to produce CH4. In contrast, the decomposition of methoxy on the Pt/WC surface favors the C-H bond scission to produce *CH2 O,which prevents the formation of the *CH3 species and leads to the formation of a *CO intermediate through subsequent deprotonation steps. The DFT predictions are validated using temperature programmed desorption to quantify the gas-phase product yields and high resolution electron energy loss spectroscopy to determine the surface intermediates from methanol decomposition on Pt, WC,and Pt/WC surfaces.
authors.affiliation: Department of Chemical Engineering, Center for Catalytic Science and Technology, University of Delaware, Newark, Delaware 19716, USA.
authors.forename: Alan Lee
authors.initials: AL
authors.lastname: Stottlemyer
authors.forename: Ping
authors.initials: P
authors.lastname: Liu
authors.forename: Jingguang G
authors.initials: JG
authors.lastname: Chen
mesh_terms: D000432:Methanol / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D010984:Platinum / Q000737:chemistry*; D013499:Surface Properties; D013696:Temperature; D017973:Tungsten Compounds / Q000737:chemistry*
chemical_list: D017973:Tungsten Compounds; C002802:tungsten carbide; D010984:Platinum; D000432:Methanol