Role of oxygen vacancy enriched m-BiVO4/t-BiVO4 isotype heterojunction for enhanced photocatalytic degradation of rhodamine B dye and in ferroelastic to paraelastic phase transition

Abstract

Mixed-phase isotype heterojunction oxide materials with superior photocatalytic activities have recently revealed a significant coupling between individual phases with controlled optical properties. Therefore, we focus on synthesizing a mixed-phase monoclinic-tetragonal (m-t) BiVO4 photocatalyst using hydrothermal method. The increased recombination rate of electron-hole (e−-h+) pairs limits the photocatalytic performance of monoclinic (m) BiVO4 photocatalysts. Therefore, effective spatial charge carrier separation can be improved by creating an isotype heterojunction between the phases m-BiVO4 and t-BiVO4. The precursor pH, mechanical grinding, and calcination temperature regulate the formation of m-t BiVO4. The phase fractions of the two phases in m-t BiVO4 sample are 85% monoclinic and 15% tetragonal. Herein, we demonstrate the optical properties and photocatalytic activity based on the crystal chemistry of m-BiVO4 and m-t BiVO4. Temperature-dependent Raman measurements suggest a second order ferroelastic monoclinic to paraelastic tetragonal phase transition above 530 K owing to optical phonon anharmonic coupling interactions. The small increase (5 °C) in Tc in m-t BiVO4 compared to m-BiVO4 is due to the coexistence of tetragonal and monoclinic phases. The optical band gap of m-t BiVO4 is larger than that of m-BiVO4. Additionally, the evaluation of BiVO4 photocatalytic activity over rhodamine-B (Rh-B) dye suggests that the m-t BiVO4 with 97.5% degradation efficiency is superior compared to m-BiVO4 with 89% degradation efficiency. This is because, the two phases (m and t) of BiVO4 form an isotype heterojunction interface, which results in a high charge separation efficiency, as demonstrated by photocurrent studies and electrochemical impedance spectroscopy. Moreover, oxygen vacancies tune the charge carrier dynamics through the modification of band edges. These findings regarding the isotype phase-junction mechanism provide possibilities for innovative ideas for highly efficient mixed-phase isotype heterojunction photocatalysts for wastewater remediation.