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

• Published in: Angewandte Chemie International Edition Vol. 55; no. 2; pp. 623 - 628
• Main Authors: Xiong, Feng, Yu, Yan-Yan, Wu, Zongfang, Sun, Guanghui, Ding, Liangbing, Jin, Yuekang, Gong, Xue-Qing, Huang, Weixin
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 11.01.2016; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Adsorption; Anatase; Catalysts; Dehydration; density functional calculations; Dimethyl ether; ethers; heterogeneous catalysis; Methanol; Surface chemistry; Surface reactions; titanium; Titanium dioxide; density functional calculations; ethers; surface chemistry; heterogeneous catalysis; titanium
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201509021

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 Ti4+ sites (Ti4c), 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 Ti4c sites is a potentially active and selective catalyst for the important methanol‐to‐DME reaction. Let's face't: The methanol‐to‐dimethyl ether (DME) reaction was unambiguously identified to occur by the dehydration coupling of methoxy species at the fourfold‐coordinated Ti4+ sites (Ti4c) on a mineral anatase TiO2(001)‐(1×4) surface. The results show, for the first time, the predicted higher reactivity of this facet relative to other reported TiO2 facets.