Titanium Oxide/Platinum Catalysis: Charge Transfer from a Titanium Oxide Support Controls Activity and Selectivity in Methanol Oxidation on Platinum

Platinum films of 1 nm thickness were deposited by electron beam evaporation onto 100 nm thick titanium oxide films (TiO x ) with variable oxygen vacancy concentrations and fluorine (F) doping. Methanol oxidation on the platinum films produced formaldehyde, methyl formate, and carbon dioxide. F-doped samples demonstrated significantly higher activity for methanol oxidation when the TiO x was stoichiometric (TiO 2 ), but lower activity when it was nonstoichiometric (TiO 1.7 and TiO 1.9 ). These results correlate with the chemical behavior of the same types of catalysts in CO oxidation. Fluorine doping of stoichiometric TiO 2 also increased selectivity toward partial oxidation of methanol to formaldehyde and methyl formate, but had an opposite effect in the case of nonstoichiometric TiO x . Introduction of oxygen vacancies and fluorine doping both increased the conductivity of the TiO x film. For oxygen vacancies, this occurred by the formation of a conduction channel in the band gap, whereas in the case of fluorine doping, F acted as an n-type donor, forming a conduction channel at the bottom of the conduction band, about 0.5–1.0 eV higher in energy. The higher energy electrons in F-doped stoichiometric TiO x led to higher turnover rates and increased selectivity toward partial oxidation of methanol. This correlation between electronic structure and turnover rate and selectivity indicates that the ability of the support to transfer charges to surface species controls in part the activity and selectivity of the reaction.