Interface engineering-induced perovskite/spinel LaCoO₃/Co₃O₄ heterostructured nanocomposites for efficient...

Conventional perovskite oxides (ABO₃) tend to suffer from their inactive surfaces and limited active sites that reduce their catalytic activity and stability, while interface engineering is a facile modulating technique to boost the catalyst's inherent activity by constructing heterogeneous interfaces. In this study, perovskite/spinel LaCoO₃/Co₃O₄ nanocomposites with heterogeneous interfaces were synthesized via sol-gel and in-situ gradient etching methods to activate peroxymonosulfate (PMS) for degrading levofloxacin (LEV). LaCoO₃ on the surface was etched into spinel Co₃O₄, and LaCoO₃/Co₃O₄ nanocomposites with two crystal structures of perovskite and spinel were successfully formed. The surface-modified LaCoO₃/Co₃O₄ exhibited superior catalytic performance with a reaction rate constant more than 2 times that of the original LaCoO₃, as well as excellent pH adaptability (3-11) and reusability (more than 6 recyclings) for LEV degradation. Besides, multiple characterization techniques were carried out to find that LaCoO₃/Co₃O₄ possessed a larger specific surface area and richer oxygen vacancies after surface modification, which provided more active sites and accelerated mass transfer rate. The mechanism of reactive oxygen species involved in the reaction system was proposed that LaCoO₃/Co₃O₄ not only reacted with PMS directly to produce SO₄^•- and ^•OH but also its surface hydroxyl group helped to form the [≡Co(Ⅲ)OOSO₃]⁺ reactive complex with PMS to produce O₂^•- and ¹O₂. In addition, electrochemical experiments demonstrated that the surface electronic structure of LaCoO₃/Co₃O₄ was effectively regulated, exhibiting a faster electron transfer rate and facilitating the redox process. By detecting and identifying degradation intermediates, three degradation pathways for LEV were proposed. Our work provided profound insights into the design of efficient and long-lasting catalysts for advanced oxidation processes.