Herein, the pivotal mechanism of defect engineering-mediated triazine-based conjugated polymers (TCPs) is comprehensively elucidated for photosensitized activation of peroxydisulfate (PDS) under nanoconfinement by encapsulating the defective polymer framework into the nanochannel of SBA-15 (d-TCPs@SBA-15). The incorporated hydroxyl defects (-OH defects) substantially accelerate the accumulation of electrons at -OH defects, forming the Lewis basic sites. Due to the facilitated elongation of the S─O bond and reduced energy barrier of SO* generation, the captured PDS undergo prehydrolysis process, oxidized into O and O by surrounding h, thereby setting apart from the conventional reductive activation of SO /•OH generation occurred in pristine TCPs (p-TCPs).
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