Preparation of double-yolk egg-like nanoreactor: Enhanced catalytic activity in Fenton-like reaction and insight on confinement effect

Peroxymonosulfate (PMS)-based Fenton-like reaction is an effective technique for the pollutant degradation, and the Co-based metal organic frameworks displayed the excellent activity for the PMS activation. Nevertheless, how to further improve the catalytic activity, suppress the leaching of toxic cobalt ions, and realize the rapid separation were still challenges for practical application. In this work, a novel solution was proposed: encapsulating Fe₃O₄ and Prussian blue analogue (PBA) into the polypyrrole (PPy) shell and constructing a “double-yolk egg-like” Fe₃O₄/PBA@PPy as a nanoreactor. In Fe₃O₄/PBA@PPy-10, the catalytic performance was remarkably enhanced with the help of confinement effect, and the degradation rate (0.38 L·min·mol⁻¹) was 5.1 times than that of reference Fe₃O₄/PBA-10 (0.074 L·min·mol⁻¹). In addition, the concentration of leached cobalt ions was reduced to only 0.174 mg/L by the protective function from the PPy shell. Moreover, the nanoreactor could be magnetically separated from the reaction solution due to the encapsulation of Fe₃O₄ nanospheres, and 84.5% of activity still preserved after the 4th cycle. The main active species involved in Fe₃O₄/PBA@PPy-10 system was ¹O₂, while that in reference Fe₃O₄/PBA-10 system was OH. Electron spin resonance analysis and radical trapping experiment revealed that the different catalytic mechanisms were attributed to the confinement effect inside the hollow cavity. This work not only presents a feasible way to prepare rarely-reported double-yolk egg-like nanoreactor, but also provides a new insight to solve the bottlenecks in Fenton-like reaction.