Methanol Conversion into Dimethyl Ether on the Anatase TiO2(001) Surface

Exploring reactions of methanol on TiO2 surfaces is of great importance in both C1 chemistry and photocatalysis. Reported herein is a combined experimental and theoretical calculation study of methanol adsorption and reaction on a mineral anatase TiO2(001)-(1×4) surface. The methanol-to-dimethyl ether (DME) reaction was unambiguously identified to occur by the dehydration coupling of methoxy species at the fourfold-coordinated Ti(4+) sites (Ti(4c)), and for the first time confirms the predicted higher reactivity of this facet compared to other reported TiO2 facets. Surface chemistry of methanol on the anatase TiO2(001)-(1×4) surface is seldom affected by co-chemisorbed water. These results not only greatly deepen the fundamental understanding of elementary surface reactions of methanol on TiO2 surfaces but also show that TiO2 with a high density of Ti(4c) sites is a potentially active and selective catalyst for the important methanol-to-DME reaction.