Degradation of polyvinyl alcohol (PVA) by homogeneous and heterogeneous photocatalysis applied to the photochemically enhanced Fenton reaction

The reaction mechanism of the oxidative degradation of polyvinyl alcohol (P VA) by the photochemically enhanced Fenton reaction was studied using a hom ogeneous (Fe-aq(2+) + H2O2) and a heterogeneous reaction system (iron (III) -exchanged zeolite Y+ H2O2). In the homogeneous Fenton system, efficient de gradation was observed in a batch reactor, equipped with a medium pressure mercury arc in a Pyrex envelope and employing 80% of the stoichiometric amo unt of H2O2 required for the total oxidation of PVA and a concentration rat io as low as 1 mole of iron(II) sulfate per 20 moles of PVA sub-units (C2H4 O). Model PVA polymers of three different molecular weights (15,000, 49,000 and 100,000 g mol(-1)) were found to follow identical degradation patterns . Strong experimental evidence supports the formation of super-macromolecul es (MW: 1 - 5 x 10(6) g/mol) consisting of oxidized PVA and trapped iron(II I) at an early reaction stage. Low molecular weight intermediates, such as oxalic acid, formic acid or formaldehyde were not found during PVA degradat ion in the homogeneous Fenton system, and we may deduce that the manifold o f degradation reactions is mainly taking place within the super-macromolecu les from which CO2 is directly released. However, in the heterogeneous Fent on system, the reaction behavior was found to be distinctly different: a de crease of the molecular weights of all three tested monodisperse PVA sample s was observed by the broadening of the GPC-traces during irradiation, and oxalic acid was formed. The results lead to the mechanistic hypothesis that during the heterogeneous Fenton process, the cleavage of the PVA-chains ma y occur at random positions, the reactive centres being located inside the iron(III)-doped zeolite Y photocatalysts.