The Competitive O鈥揌 versus C鈥揌 Bond Activation of Ethanol and Methanol by VO2+ in Gas Phase: A DFT Study

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• 作者：Lianming Zhao ; Min Tan ; Juan Chen ; Qiuyue Ding ; Xiaoqing Lu ; Yuhua Chi ; Guangwu Yang ; Wenyue Guo ; Qingtao Fu
• 刊名：The Journal of Physical Chemistry A
• 出版年：2013
• 出版时间：June 20, 2013
• 年：2013
• 卷：117
• 期：24
• 页码：5161-5170
• 全文大小：501K
• 年卷期：v.117,no.24(June 20, 2013)
• ISSN：1520-5215

文摘

The activation of ethanol and methanol by VO₂⁺ in gas phase has been theoretically investigated by using density functional theory (DFT). For the VO₂⁺/ethanol system, the activation energy (螖E) is found to follow the order of 螖E(C^尾鈥揌) < 螖E(C^伪鈥揌) 鈮?螖E(O鈥揌). Loss of methyl and glycol occurs respectively via O鈥揌 and C^尾鈥揌 activation, while acetaldehyde elimination proceeds through two comparable O鈥揌 and C^伪鈥揌 activations yielding both VO(H₂O)⁺ and V(OH)₂⁺. Loss of water not only gives rise to VO(CH₃CHO)⁺ via both O鈥揌 and C^伪鈥揌 activation but also forms VO₂(C₂H₄)⁺ via C^尾鈥揌 activation. The major product of ethylene is formed via both O鈥揌 and C^尾鈥揌 activation for yielding VO(OH)₂⁺ and VO₂(H₂O)⁺. In the methanol reaction, both initial O鈥揌 and C^伪鈥揌 activation accounts for formaldehyde and water elimination, but the former pathway is preferred.