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Various methods for shifting the optical response of TiO2 into the visible (Vis) range have been reported.Herein,we reported the application of a TiO2/H2O2/Vis process and the effects of TiO2 crystalline structure on the degradation of terbuthylazine.The results indicated that TiO2 crystalline structure and H2O2 addition had significant effects on terbuthylazine degradation:its degradation rate could be increased from 7％ to 70％ with H2O2 addition after 180 min of reaction,the synergistic degradation of terbuthylazine by TiO2-Fe3+ was substantially accelerated,with the degradation rate reaching up to 100％ after 20 min of reaction,and ruttle TiO2 showed better photocatalytic activity and a more obvious synergistic effect than anatase TiO2.The addition of free-radical scavengers (tert-butyl alcohol or methanol) inhibited the degradation efficiency of rutile TiO2,but had a relatively minor effect on anatase TiO2.Fluorescence spectrophotometry analysis indicated that hydroxyl free radicals could be continuously produced when using rutile TiO2 as the photocatalyst.Degradation of terbuthylazine catalyzed by rutile TiO2 occurred mainly in solution,but occurred on the particle surface of the photocatalyst when catalyzed by anatase TiO2.This study provides new insight into the role of TiO2 crystalline structure on the degradation of terbuthylazine and its photocatalytic degradation mechanism.