Theoretical study of partial oxidation of ethylene by vanadium trioxide cluster cation  

作　　者：WANG ZheChen DING XunLei MA YanPing CAO Hai WU XiaoNan ZHAO YanXia HE ShengGui 

机构地区：[1]Beijing National Laboratory for Molecular Sciences (BNLMS), and State Key Laboratory for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China [2]Graduate University of Chinese Academy of Sciences, Beijing 100039, China

出　　处：《Chinese Science Bulletin》2009年第16期2814-2821,共8页

基　　金：Supported by the Hundred Talents Fund;Chinese Academy of Sciences and National Natural Science Foundation of China (Grant No. 20703048)

摘　　要：Density functional theory (DFT) study of reaction between vanadium trioxide cluster cation (VO3+) and ethylene (C2H4) to yield VO2+ + CH3CHO (acetaldehyde) and VO2CH2+ + HCHO (formaldehyde) is carried out. Structures of all reactants, products, intermediates, and transition state in the reaction have been optimized and characterized. The results show unexpected barriers in the reaction due to the existence of a η2-O2 moiety in the ground state structure of VO3+. The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO3+ + C2H4 with VO3 + C2H4 and VO2+ + C2H4 in the previous studies is made in detail. The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.Density functional theory （DFT） study of reaction between vanadium trioxide cluster cation （VO3^＋） and ethylene （C2H4） to yield VO2^＋ ＋ CH3CHO （acetaldehyde） and VO2CH2^＋ ＋ HCHO （formaldehyde） is carried out. Structures of all reactants, products, intermediates, and transition state in the reaction have been optimized and characterized. The results show unexpected barriers in the reaction due to the existence of a η^2-O2 moiety in the ground state structure of VO3^＋. The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO3^＋ ＋ C2H4 with VO3 ＋ C2H4 and VO2^＋ ＋ C2H4 in the previous studies is made in detail. The results of this work may shed light on the understanding of C=C bond cleavage in related heterogeneous catalysis.

关 键 词：氧化乙烯 氧化钒 离子簇 氧化反应 密度泛函理论 基团结构 反应步骤 速率限制 

分 类 号：O614.511[理学—无机化学] TQ326.5[理学—化学]