A site-holding effect of TiO2 surface hydroxyl in the photocatalytic direct synthesis of 1, 1-diethoxyethane from ethanol. Issue 9 (16th January 2017)

• Record Type: Journal Article
• Authors: Zhang, Hongxia; Zhang, Wenqin; Zhao, Min; Yang, Pengju; Zhu, Zhenping
• Is Part Of: Chemical communications. Volume 53:Issue 9(2017)
• Page Start: 1518
• Page End: 1521
• Publication Date: 2017-01-16
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1039/c6cc09050h
• Languages: English
• ISSNs: 1359-7345

Abstract

Abstract : Two different effects of TiO2 surface hydroxyl: an indirect site-holding effect on the C–O coupling process of neat ethanol and direct part of the reaction in the C–C coupling process of ethanol–H2 O. Abstract : To understand the mechanism of the photocatalytic direct synthesis of 1, 1-diethoxyethane (DEE) from ethanol is vital for enhancing the reaction efficiency. Based on photocatalytic data of different phase TiO2 and F–TiO2 catalysts, radical trapping data, and GC-MS data, we proposed a photocatalytic mechanism for the preparation of both DEE in neat ethanol and 2, 3-butanediol (2, 3-BD) in ethanol–H2 O using photocatalytic methods. In neat ethanol, hydroxyl isn't involved in the catalytic cyclic process but hydroxyl has an indirect site-holding effect, thus leading to more hydroxyl groups with higher activity. In ethanol–H2 O, although the strong oxidant ˙OH radical is involved, fewer OH groups lead to higher selectivity of 2, 3-BD. The interaction of the reactant/solvent with the surface group of the catalyst is important in the activity and selectivity of photocatalytic reactions. This finding gives fundamental insight into the role of TiO2 surface hydroxyl in the photocatalytic dehydrogenation process of alcohols and opens a promising path to obtaining both high selectivity and high conversion in TiO2 -based photocatalytic activity.