Abstract
The mechanism of methylal formation by methanol oxidation on unsupported V 2O 5 catalyst has been investigated in transient isotopic experiments, performing an exchange between CH 3OH and CD 3OD. Adsorbed methoxy groups and hemimethylal (CH 3OCH 2OH) have been identified as intermediate species, the hemimethylal being formed by reaction between an activated methanol species ( CH 2OH) and the surface methoxy groups. The methylal is then obtained by a dehydration reaction between hemimethylal and a methanol molecule or a surface methoxy group. We can also propose that the methyl formate formation (HCOOCH 3) could occur by hemimethylal oxidative dehydrogenation, the hemimethylal (CH 3OCH 2OH) appearing then as the key intermediate in the methanol oxidation to methylal and methyl formate.
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