ZnFe₂O₄@WO_3- /Polypyrrole: An Efficient Ternary Photocatalytic System for Energy and Environmental Application

Environmental protection and the necessity of green energy have become fundamental concerns for humankind. However, rapid recombination of photoexcitons in semiconductors often gets in the path of photocatalytic reactions and annoyingly suppresses the photocatalytic activity. In this study, a polypyrrole (PPY)-supported step-scheme (S-scheme) ZnFe₂O₄@WO_3- (PZFW15) ternary composite was fabricated by a multistep process: hydrothermal and calcination processes, followed by polymerization. During the formation of the heterojunction, the oxygen vacancy (OV) on WO_3- promotes effective separation and increases the redox power of the photogenerated excitons via the built-in internal electric field of S-scheme pathways between ZnF and WO_3- The successful construction of the S-scheme heterojunction was substantiated through X-ray photoelectron spectroscopy, experimental calculations, radical trapping experiment, and liquid electron spin resonance (ESR) characterization, whereas the existence of OVs was well confirmed by EPR and Raman analyses. Meanwhile, the PPY served as a supporter, and the polaron and bipolaron species of PPY acted as electron and hole acceptors, respectively, which further enhances the charge-carrier transmission and separation in the ternary PZFW15 photocatalyst. The designed ternary nanohybrid (PZFW15) displays outstanding gemifloxacin detoxification (95%, 60 min) and hydrogen generation (657 μmol h^-1), i.e., 1.5 and 2.2 times higher than the normal S-scheme ZFW15 heterostructure and pure ZnFe₂O₄ (ZnF), respectively, with an apparent conversion efficiency of 4.92%. The ESR and trapping experiments indicate that the generated ^•OH and ^•O₂ ^- radicals from the PZFW15 photocatalyst are responsible for gemifloxacin degradation. This unique PPY-supported S-scheme heterojunction is also beneficial for the enhanced electron-transfer rate and provides abundant active sites for photocatalytic reactions.