Elucidating Dual Pathways for Light‐Driven Degradation Using Intrinsic Azo Dye Photochemistry
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The widespread use of azo dyes in the textile industry and the difficulty in mineralizingthem under environmental conditions makes azo dyes a persistent pollution problem. This work reports the photodegradation of acid violet 3 in which the intrinsic azo dye photochemistry is harnessed to promote degradation. Two photodegradation pathways are proposed: an energy transfer and an electron transfer pathway.
In this work, the photochemical properties of Acid violet 3 (AV3), along with a sacrificial oxidant, MV2+, are used to promote its own degradation in aqueous solutions. Irradiation of light at 375 nm produces excited-state AV3 (*AV3) that is able to be oxidized by MV2+, as monitored through UV–visible spectroscopy. MV2+ is added in various concentrations, showing an increased degradation rate with increasing MV2+ concentrations. Degradation of AV3 is still observed in control experiments in which AV3 is illuminated without the presence of MV2+. Photodegradation experiments are also performed in deuterated water, showing a five times increased rate of degradation, providing evidence of an inverse kinetic isotope effect. Based on these results, two different degradation pathways are proposed: an energy transfer pathway and an electron transfer pathway. In the electron transfer pathway, *AV3 is oxidized by MV2+, which produces MV•+. MV•+ interacts with dissolved oxygen to produce reactive oxygen species, likely superoxide radicals (O2 •−), that are highly reactive and further attack AV3 until it is degraded. In the energy transfer pathway, *AV3 populates a triplet state that is energetically able to sensitize triplet oxygen (3O2) to singlet oxygen (1O2), which can break down AV3.




