Mechanism and Principles of Acid Red GR Degradation in the Cu2+/HCO3−/H2O2 Advanced Oxidation System
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Abstract
To address the refractory degradation of wastewater containing the azo dye Acid Red GR, this study employed a Cu2+-activated HCO3−/H2O2 (BAP) advanced oxidation system for its degradation treatment, and investigated the reaction mechanism of the system as well as the effects of various influencing factors on the degradation efficiency. The results showed that under the conditions of an initial concentration of Acid Red GR at 25 mg·L−1, a concentration of HCO3− at 10 mmol·L−1, a concentration of H2O2 at 4 mmol·L−1, and a concentration of Cu2+ at 15 μmol·L−1, the removal rate of Acid Red GR could reach over 92.7% after 20 minutes of reaction. Due to the pH being in the medium to alkaline range (6.54 ~ 10.85), bicarbonate existed predominantly in the form of HCO3−, which facilitated the generation of carbonate radicals (CO3•−); conversely, under acidic conditions (3.07 ~ 4.98), the limited availability of HCO3− markedly suppressed the reaction rate. Common inorganic anions (H2PO4−, SO42−, Cl−, NO3−) all had inhibitory effects to varying degrees, among which H2PO4− had the greatest impact and NO3− had the least. Radical quenching experiments confirmed the presence of multiple reactive oxygen species in the system, among which CO3•−and singlet oxygen (1O2) played dominant roles, while hydroxyl radicals (•OH) and superoxide radicals (O2•−) participated in the reaction but made limited contributions. Electron paramagnetic resonance (EPR) spectroscopy directly confirmed the presence of •OH, CO3•−, and 1O2.Combined with the analysis of ultraviolet-visible spectra and mass spectra, it was preliminarily inferred that the degradation of Acid Red GR mainly occured through the cleavage of the azo bond, the opening of the benzene ring, and the oxidation of the naphthalene ring. Through total organic carbon (TOC) analysis, the mineralization degree of Acid Red GR reached 49% within 30 minutes.This system achieves efficient degradation of Acid Red GR under neutral to alkaline conditions, with a wide applicable pH range and mild reaction conditions. These findings help reduce operating costs and enhancing the feasibility of practical treatment of dyeing and printing wastewater.
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