Methanol Conversion into Dimethyl Ether on the Anatase TiO 2 (001) Surface

Exploring reactions of methanol on TiO 2 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 TiO 2 (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 TiO 2 facets. Surface chemistry of methanol on the anatase TiO 2 (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 TiO 2 surfaces but also show that TiO 2 with a high density of Ti 4c sites is a potentially active and selective catalyst for the important methanol‐to‐DME reaction.