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

Density functional theory (DFT) study of reaction between vanadium trioxide cluster cation (VO (3) (+) ) and ethylene (C2H4) to yield VO (2) (+) + CH3CHO (acetaldehyde) and VO2CH (2) (+) + 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 eta(2)-O-2 moiety in the ground state structure of VO (3) (+) . The initial reaction steps combining ethylene adsorption, C=C activation and O-O cleavage are proposed as rate limiting processes. Comparison of reactions of VO (3) (+) + C2H4 with VO3 + C2H4 and VO (2) (+) + 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.