Role of perovskite non-stoichiometry on catalytic oxygen dark activation for the removal of azo dyes from wastewater

Effluents of the dying and printing industries are a significant contributor to water pollution. Since synthetic dyes are primarily resistant to natural degradation, they remain in water bodies for an exceptionally long time if discharged untreated. Oxygen dark activation is a promising candidate for the degradation of azo dyes as it does not require the use of additional reagents or even the presence of light. It is an advanced catalytic oxidation process that converts oxygen dissolved in wastewater into reactive oxygen species, which subsequently break down dye molecules. The role of the catalyst is to accelerate the process by acting as a bridge for the electron transfer between the dye molecules and adsorbed oxygen. It has been reported that the textural and structural properties of the catalyst play a key role in generating reactive oxygen species. In this work, we synthesized, characterized, and evaluated a series of strontium-based perovskite oxides for the catalytic degradation of azo dyes under dark conditions. The degradation of different dyes was studied in a batch reactor under various conditions, and the reaction progress was monitored by UV-vis absorption spectroscopy. The results showed that the degradation of azo dye was faster when the azo bond was weakened by either electron-withdrawing groups or due to the formation of a stable hydrazone structure. To evaluate the effect of structural defects on the oxygen dark activation process, cation non-stoichiometry was separately introduced in the parent perovskite SrFeO₃ at both A and B sites. Under identical reaction conditions, the degradation efficiency of A-site deficient perovskite Sr_0.90FeO₃ (94 %) and B-site deficient SrFe_0.80O₃ (95 %) was higher than the stoichiometric perovskite SrFeO₃ (46 %). These results demonstrate that cation deficiency in the SrFeO₃ structure strongly favors the catalytic degradation of azo dyes <i>via</i> oxygen dark activation.