High-efficient separation of photoinduced charge carriers in CoFe2O4-ZnO magnetic heterostructures mediated by oxygen vacancies

Abstract

In this work, magnetic heterostructures were obtained by the in-situ growth of various ZnO amounts on the preformed CoFe2O4 nanoparticles. The X-ray diffraction characterization shows the presence of both ZnO and CoFe2O4 crystalline phases, and the crystallite size is about 13–14 nm for both components. X-Ray Photoelectron Spectroscopy (XPS) analysis revealed a CoFe2O4 inversion degree of 0.7. The composite samples demonstrated an extended absorption edge into the visible range. The sample’s magnetic properties were investigated by vibrating-sample magnetometer (VSM) and correlated with Electron Paramagnetic Resonance (EPR) results. The magnetic behavior was attributed to the combination of CoFe2O4 and ferromagnetic ZnO. The emergence of a ferromagnetic phase within ZnO was elucidated to originate from charge/spin transfer of spin-up polarized states from the CoFe2O4 Fermi level into empty oxygen vacancies of ZnO. High efficiency in Rhodamine B (RhB) degradation under visible light was observed in the prepared composite materials, particularly with an optimal CoFe2O4-ZnO ratio of 1:5, achieving an 81 % degradation rate within 6 h. The proposed photodegradation mechanism, based on various spectroscopic and magnetic investigations, highlights the role of spin transfer and oxygen vacancies in facilitating reactive oxygen species (ROS) generation for pollutant degradation.