| AVS 58th Annual International Symposium and Exhibition | |
| Surface Science Division | Monday Sessions |
| Session SS1-MoA |
| Session: | Selectivity and Reactivity of Chemisorbed Species |
| Presenter: | Zhenjun Li, Pacific Northwest National Laboratory |
| Authors: | Z.J. Li, Pacific Northwest National Laboratory Y.K. Kim, Pacific Northwest National Laboratory R.J. Rousseau, Pacific Northwest National Laboratory B.D. Kay, Pacific Northwest National Laboratory Z. Dohnálek, Pacific Northwest National Laboratory |
| Correspondent: | Click to Email |
The reactions of C1-C4 aliphatic alcohols over cyclic (WO3)3 and (MoO )n (n ranges from 3 to 6) clusters were studied experimentally and theoretically using temperature-programmed desorption, infrared reflection-absorption spectroscopy, and density functional theory. Three reaction channels, dehydration, dehydrogenation, and condensation, have been identified on (WO3)3 clusters while only dehydration and dehydrogenation have been observed on (MoO3)n. The desorption temperature of reaction products decreases with increasing alkyl chain length. The lack of a condensation channel on (MoO3)n is attributed to the lower reactivity of alcohols with (MoO3)n as compared to (WO3)3 and consequently a negligible concentration of the Mo(VI) centers coordinated with two alkoxy species required for this reaction are formed. DFT calculations provide a detailed explanation for the reactivity and relative selectivity among the reaction channels and W(VI) and Mo(VI) metal centers.
This work was supported by the U.S. Department of Energy Office of Basic Energy Sciences, Division of Chemical Sciences, Biosciences and Geosciences, and was performed at EMSL, a national scientific user facility sponsored by the Department of Energy’s Office of Biological and Environmental Research located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the U.S. DOE by Battelle Memorial Institute under contract no. DE-AC06-76RLO 1830. Computational resources were provided at EMSL and the National Energy Research Scientific Computing Center at Lawrence Berkeley National Laboratory.