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.