Quantitative structure-activity relationship in the photodegradation of azo dyes

The photolysis characteristics of azo dyes are critically important in environmental pollution control, dye-sensitized solar cells, and dyeing-related industries. However, there is still lack of quantitative relationship between the structures of azo dyes and their photolysis characteristics. To address this issue, the photolysis of 22 azo dyes were conducted side by side at three pH (4.0, 6.0, 9.0). The obtained pseudo-first order photodegradation rate constants (k₁) were processed with meta-analysis. Statistically, the hydrazone tautomer had a smaller excitation energy and was easier to undergo photolysis than the azo tautomer. The ortho-substituted sulfonate groups had an obvious protective effect on the photostability of azo dyes. The softness (s), the most positive and negative partial charge on a carbon atom (qC⁺, qC^-) were found to be crucial descriptors in the establishment of QSAR models for the photostability of azo dyes. The QSAR model at pH 9.0 was robust for predicting the photostability of azo dyes under UV irradiation. N₂-purging experiments and quantum chemical computation verified that the cleavage of azo bond was not a result of direct photolysis but was caused by the attack of photoinduced reactive oxygen species. The results here are helpful for the design of more stable azo dyes or the selection of suitable approaches for the treatment of dye-contaminated water bodies.