Computational Study of Dehydration and Dehydrogenation of Ethanol on (TiO) ( = 2-4) Nanoclusters.

Dehydration and dehydrogenation of an ethanol molecule on (TiO), = 2-4, nanoclusters were studied at the correlated molecular orbital theory CCSD(T)/aug-cc-pVDZ(-PP(Ti)) level using density functional theory B3LYP/DZVP2-optimized geometries. Physisorption and chemisorption of ethanol at the bridge Ti site on the trimer and tetramer are thermodynamically preferred over these reactions at the Ti site with a terminal Ti═O. Two possible lowest energy reaction coordinates of dehydration were predicted for the dimer and trimer where the β hydrogen on ethanol transfers to the adjacent terminal oxygen, or to the adjacent bidentate oxygen. Only the latter reaction coordinate was predicted to be the lowest energy one for the tetramer. Removal of ethylene from the (TiO)OH-CH complex for = 2-4 at 0 K requires 2-7 kcal/mol. For dehydrogenation, transfer of the α hydrogen to the adjacent Ti atom results in the lowest energy reaction coordinate following a proton-coupled electron-transfer (PCET) process. Removal of the acetaldehyde molecule requires 14-26 kcal/mol from the (TiO)H-CHO complex. Loss of H from the (TiO)H complex requires 5-8 kcal/mol. Dehydration and dehydrogenation of one ethanol molecule occur below the reactant asymptote for (TiO), = 2-4, whereas for (WO) and (MoO), two ethanol molecules are required for this process to be below the reactant asymptote. Dehydration of ethanol is thermodynamically preferred over dehydrogenation on (TiO), = 2-4. There is an approximate linear correlation of metal Lewis acidity with physisorption of ethanol. A quadratic correlation is predicted between the chemisorption barrier of ethanol and the corresponding proton affinity of oxygen to which the proton is being transferred. There are linear correlations between the basicity of the oxygen site and the acidity of the OH group versus the energy to remove CH from that site. The results for the nanoclusters for = 3 and 4 are consistent with the experimental results for the reactivity of ethanol on Ti rutile TiO (110) surface sites.