Date: 2009. 11. 5, 5:00 PM Place: Mogam Hall, Bldg 500 - Abstract - Understanding the mechanistic details of heterogeneous catalytic reactions will provide a way to tune the selectivity between various competing reaction channels. In this regard, catalytic decomposition of alcohols over the rutile TiO2(110) surface as a model oxide catalyst has been studied to understand the reaction mechanism. In this study, we deliberately employed the temperature-programmed desorption (TPD) technique. The TiO2(110) model catalyst is found to be active toward alcohol dehydration. We find that the active sites are bridge-bonded oxygen vacancies where RO-H heterolytically dissociates and binds to the vacancy to produce alkoxy (RO-) and hydroxyl (HO-). Two protons adsorbed onto the bridge-bonded oxygen atoms (-OH) readily react with each other to form a water molecule at ~500 K and desorb from the surface. The alkoxy (RO-) undergoes decomposition at higher temperatures into the corresponding alkene. Here, the overall desorption kinetics is limited by a first-order decomposition of intermediate alkoxy (RO-) species bound to the vacancy. We show that detailed analysis on the yield and the desorption temperatures as a function of the alkyl substituents provides valuable insights into the reaction mechanism.