Photocatalysis Meets Piezoelectricity in a Type-I Oxygen Vacancy-Rich BaTiO₃/BiOBr Heterojunction: Mechanism Insights...

It is a challenging task to design a piezoelectric photocatalyst with excellent performance under mechanical agitation instead of ultrasonic irradiation. Integrating vacancy defects into a heterojunction seems to be an effective strategy for synergistically increasing its piezo-photocatalytic performance. For this goal, a two-step hydrothermal method was adopted to architect a type-I oxygen-vacancy-rich BaTiO₃/BiOBr heterojunction to surge the degradation of Rhodamine B (RhB) under the combined action of simulated sunlight irradiation and mechanical agitation. Various instrumental techniques demonstrated the formation of a BaTiO₃/BiOBr heterojunction with high crystallinity. The existence of surface oxygen vacancies was confirmed by XPS and EPR tests. PFM results manifested that this heterojunction had excellent piezoelectric properties, with a piezoelectric response value of 30.31 pm V^-1. Comparative experiments indicated that RhB degradation efficiency under piezo-photocatalysis over this heterojunction largely exceeded the total sum of those under piezocatalysis and photocatalysis. h⁺, ·O₂^-, and ¹O₂ were the dominant reactive species for RhB degradation. The improved separation efficiency of photogenerated charges was verified by electrochemical measurements. DFT calculations indicated that the polarization of BaTiO₃ could affect the electronic band structure of BiOBr. This work will provide comprehensive insights into piezo-photocatalytic mechanism at a microcosmic level and help to develop new-styled piezoelectric photocatalysts.