PIO study on 1,3-butanediol dehydration over CeO2 (1 1 1) surface

✍ Scribed by Naoki Ichikawa; Satoshi Sato; Ryoji Takahashi; Toshiaki Sodesawa

• Publisher: Elsevier Science
• Year: 2005
• Tongue: English
• Weight: 480 KB
• Volume: 231
• Category: Article
• ISSN: 1381-1169
• DOI: 10.1016/j.molcata.2005.01.017

✦ Synopsis

CeO 2 has specific catalytic activity for the selective dehydration of 1,3-diols to unsaturated alcohols. In order to clarify the catalytic mechanism, quantum calculation based on the paired interacting orbital (PIO) theory was adopted to 1,3-butanediol-Ce 9 O 18 cluster systems. Strong attractive interaction was observed between 1,3-butanediol and oxygen-defected CeO 2 (1 1 1), where three in-phase interactions were confirmed between H atom at 2-position in 1,3-butanediol and Ce cation and between two OH groups and other Ce cations. In addition, out-of-phase interaction between H and C atom at 2-position was induced by the in-phase interaction between H atom and Ce cation at appropriate coordinate of 1,3-butanediol. The PIO results suggest that the dehydration of 1,3-diols initiates from the abstraction of H atom at 2-position in 1,3-butanediol adsorbed on an oxygen defect site on CeO 2 (1 1 1) with tridentate coordination.