Site-specific imaging of elemental steps in dehydration of diols on TiO(2)(110).

Scanning tunneling microscopy is employed to follow elemental steps in conversion of ethylene glycol and 1,3-propylene glycol on partially reduced TiO2(110) as a function of temperature. Mechanistic details about the observed processes are corroborated by density functional theory calculations. The use of these two diol reactants allows us to compare and contrast the chemistries of two functionally similar molecules with different steric constraints, thereby allowing us to understand how molecular geometry may influence the observed chemical reactivity. We find that both glycols initially adsorb on Ti sites, where a dynamic equilibrium between molecularly bound and deprotonated species is observed. As the diols start to diffuse along the Ti rows above 230 K, they irreversibly dissociate upon encountering bridging oxygen vacancies. Surprisingly, two dissociation pathways, one via O-H and the other via C-O bond scission, are observed. Theoretical calculations suggest that the differences in the C-O/O-H bond breaking processes are the result of steric factors enforced upon the diols by the second Ti-bound OH group. Above ∼400 K, a new stable intermediate centered on the bridging oxygen (Ob) row is observed. Combined experimental and theoretical evidence shows that this intermediate is most likely a new dioxo species. Further annealing leads to sequential C-Ob bond cleavage and alkene desorption above ∼500 K. Simulations demonstrate that the sequential C-Ob bond breaking process follows a homolytic diradical pathway, with the first C-Ob bond breaking event accompanied with a nonadiabatic electron transfer within the TiO2(110) substrate.