Kinetics and Mechanism of Methanol Conversion over Anatase Titania Nanoshapes

The kinetics and mechanism of methanol dehydration, redox, and oxidative coupling were investigated at 300 °C under dilute oxygen concentration over anatase TiO2 nanoplates and truncated-bipyramidal nanocrystals in order to understand the surface structure effect of TiO2. The two TiO2 nanoshapes displayed both (001) and (101) facets, with a higher fraction of the (001) facet exposed on the nanoplates, while truncated-bipyramidal nanocrystals were dominated by the (101) facet. A kinetic study using in situ titration with ammonia shows that the active sites for methanol dehydration are acidic and nonequivalent in comparison to redox and oxidative coupling. In situ FTIR spectroscopy reveals that adsorbed methoxy is the dominant surface species for all reactions, while the observed methanol dimer is found to be a spectator species through isotopic methanol exchange, supporting the dissociative mechanism for methanol dehydration via surface methoxy over TiO2 surfaces. Density functional theory calculations show that the formation of dimethyl ether involves the C–H bond dissociation of an adsorbed methoxy, followed by coupling with another surface methoxy on the 5-fold-coordinated Ti cations on the (101) surface, similar to the mechanism reported on the (001) surface. Kinetic isotope effects are observed for dimethyl ether, formaldehyde, and methyl formate in the presence of deuterated methanol (CD3OH and CD3OD), confirming that the cleavage of the C–H bond is the rate-limiting step for the formation of these products. A comparison between estimated kinetic parameters for methanol dehydration over various TiO2 nanocrystals suggests that (001) has a higher dehydration reactivity in comparison to (101), but the surface density of active sites could be limited by the presence of residual fluorine atoms originating from the synthesis. The (001) surface of TiO2 is also more active than the (101) surface in redox and oxidative coupling of methanol, which is due to the reactive surface oxygen on (001) in comparison to the (101) surface.