ZnxFe3-xO4–ZnO heterojunction interfaced with poly(L-DOPA) electron transfer mediator layer for enhanced visible light photocatalytic activity

Abstract

Z-scheme heterojunctions comprising ZnxFe3-xO4@poly(L-DOPA)@ZnO (ZF@PD@ZnO) were synthesized using solvothermal and precipitation techniques. The study aimed to investigate the impact of the poly(L-DOPA) electron transfer mediator on the photocatalytic performance of ZnxFe3-xO4@ZnO (ZF@ZnO) nanocomposites under visible light irradiation. X-ray diffraction (XRD) and HRTEM analysis confirmed the formation of heterostructures, identifying the crystalline phases of both ZnO and zinc ferrite. BFTEM images revealed a polyhedral shape for all samples, with a tendency toward mild agglomeration. The partial inversion of the zinc ferrite cubic spinel structure was evidenced by FT-IR, XPS, and VSM analyses. Zinc ferrite was found to be ferromagnetic, with cation distributions between tetrahedral (A) and octahedral (B) positions as [Zn0.62+Fe0.43+]A[Fe0.42+Fe1.63+]BO4. The samples exhibited notable photocatalytic activity against Rhodamine B, serving as a model contaminant. Furthermore, the stability and reusability of the samples were examined. Additionally, the study elucidated the photocatalytic mechanism produced by the ternary Z-scheme ZF@PD@ZnO, involving spin-polarized charge carriers. Energy band alignment was evaluated by combining ultraviolet photoelectron spectroscopy (UPS) with UV-Vis spectroscopy. The interplay between band alignment and reactive oxygen species (ROS) generation was discussed in correlation with EPR results. Enhanced ROS generation under visible light illumination, observed in the ZF@PD@ZnO nanocomposite, is mainly due to the addition of the conductive poly(L-DOPA) layer, acting as an electron transfer mediator in the Z-scheme heterojunction, ensuring enhanced charge separation.