Experimental and theoretical assessment of the mechanism and site requirements for ketonization of carboxylic acids on oxides

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• 作者：Shuai Wang ; Enrique Iglesia ; ^{iglesia@berkeley.edu}
• 关键词：TiO2 ; ZrO2 ; Ketonization ; Carboxylic acids ; Acid-base pairs ; Density functional theory ; Infrared spectroscopy
• 刊名：Journal of Catalysis
• 出版年：2017
• 出版时间：January 2017
• 年：2017
• 卷：345
• 期：Complete
• 页码：183-206
• 全文大小：5689 K
• 卷排序：345

文摘

Ketonization turnovers occur on TiO or ZrO pairs saturated with monodentate carboxylates. Turnover rates benefit from intermediate strength of acid and base sites and distances that enforce orbital overlap. Inactive bidentate carboxylates form slowly and cause site blocking. Ketonization is limited by CC coupling of 1-hydroxy enolates with monodentate carboxylates. The CC coupling transition state is preferentially stabilized by H-bonds at high coverages.