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In advanced oxidation technology based on sulfate radicals, thermal activation is one of the most effective methods for persulfate (PS) activation, with broad application potential for the use of solar energy to activate PS to degrade pollutants. In this study, the efficiency and mechanism of degradation of rhodamine B by solar thermally activated PS were investigated using a solar collector reactor. The effects of solar irradiation intensity, PS concentration, substrate concentration, initial pH of the solution, and background water qual