Catalytic oxidation of CH3OH to HCOOCH3 on V2O5: A theoretical study

In a previous work, the CH3OH adsorption-oxidation process on V2O5 was studied by mass spectrometry analysis of the reaction atmosphere. The following partial oxidation products were reported: H2CO, CO, CO2, (CH3O)(2)CH2 (methylal), CH3OCH2OH (hemimethylal) and HCOOCH3. The data so obtained allowed a reaction pathway to be proposed. In the present work, we used models of the plane (010) of V2O5 and of CH3OH, to test whether the pathway proposed in this work as well as alternative ones presented by other authors were energetically favorable or not. With this purpose, the variation of the total system energy was computed in each step by extended Huckel-type calculations (ASED, atom superposition and electron delocalization). The results showed, on the one hand, that the pathway proposed in this work is better than alternatives pathways, and on the other hand, the possible existence of other equally-favorable adsorption sites in which bridge oxygen may take part.