Mesocrystalline Zn-Doped Fe₃O₄ Hollow Submicrospheres: Formation Mechanism and Enhanced Photo-Fenton Catalytic Performance

Uniform and magnetic recyclable mesocrystalline Zn-doped Fe₃O₄ hollow submicrospheres (HSMSs) were successfully synthesized via a simple one-pot solvothermal route and were used for efficient heterogeneous photo-Fenton catalyst. XRD, XPS, Raman spectroscopy, Mössbauer spectroscopy, SEM, HRTEM, and EDX analyses revealed that the shell of HSMSs is highly porous and assembled by oriented attachment of magnetite nanocrystal building blocks with Zn-rich surfaces. Furthermore, a possible formation mechanism of mesocrystalline hollow materials was proposed. First, Fe₃O₄ mesocrystals were assembled by oriented nanocrystals, and a Zn-rich amorphous shell grew on the surfaces. Then, Zn gradually diffused into Fe₃O₄ crystals to form Zn-doped Fe₃O₄ due to the Kirkendall effect with increasing the reaction time. Meanwhile, the inner nanocrystals would be dissolved, and outer particles would grow larger owing to the Ostwald ripening process, leading to the formation of a hollow structure with porous shell. The Zn-doped Fe₃O₄ HSMSs exhibited high and stable photo-Fenton activity for degradation of rhodamine B (RhB) and cephalexin under visible-light irradiation in the presence of H₂O₂, which results from their hollow mesocrystal structure and Zn doping. It could be easily separated and reused by an external magnetic field. The results suggested that the as-obtained magnetite hollow mesocrystals could be a promising catalyst in the photo-Fenton process.