In-situ self-assembly of robust Fe (III)-carboxyl functionalized polyacrylonitrile polymeric bead catalyst for efficient photo-Fenton oxidation of p-nitrophenol.

From the view of channel confinement and functional site capture, we develop an in-situ self-assembly strategy to fabricate the carboxyl functionalized Fe-HPAN bead catalyst with highly stable and uniformly dispersed metallic sites for efficient photo-Fenton oxidation of p-nitrophenol (p-NP). BET and FTIR analysis reveal that numerous carboxyl groups and mesopores exist in Fe-HPAN beads, which acts to capture and immobilize iron ions. Catalytic results show that the degradation rate and TOC removal for p-NP were up to 99.78 and 91.68% under the optimal condition. Even at near neutral pH, the degradation rate almost keep the same and the TOC removal can still reach 73.05%. Due to the autocatalytic cycle of FeIII/FeII, the apparent rate constant of Fe-HPAN (0.2247 min-1) was 5.4 times as high as unmodified Fe-PAN (0.0415 min-1) in the presence of H2O2 and visible light irradiation, which was 2-3 orders of magnitude larger than that of other reaction systems. More importantly, Fe-HPAN bead catalyst exhibited little loss of activity even after 20 cycles of re-utilization. The possible degradation pathway of p-NP was also proposed based on GC/MS analysis. The present work may provide a new perspective for the use of synthetic polymer to prepare low-cost, efficient and robust photo-Fenton oxidation catalysts.