Mott–Schottky heterostructural TiO2@Ag@AgBr nanohybrids for efficient photocatalytic degradation of Cr (VI) and enhanced on-site SERS detection

Abstract

In the study, a novel ternary composite TiO2@Ag@AgBr was successfully prepared by surface modification of complete Ag layer and AgBr particles for photocatalytic degradation of representative heavy metal ions Cr (VI) and on-site Surface-enhanced Raman spectroscopy (SERS) detection of the Cr (VI) reduction process. The Mott–Schottky heterojunction contained structure exhibited remarkable photocatalytic ability for heavy metal ions Cr (VI) by tuning the ratio of Ag and AgBr, which could reduce Cr (VI) ions within 30 min and the reaction rate constant is 0.12 min−1. The remarkable photo-reduction performance is attributed to synergistic effect among the various components: the AgBr decorated on the surface of TiO2@Ag could significantly enhance the absorption of visible light and generate numerous photoexcited electrons and holes. Furthermore, the complete Ag layer was constructed on the TiO2 microspheres surface to form heterojunctions in the photocatalytic system by in-situ deposition of AgNO3. Mott–Schottky junctions formed between AgBr/Ag and Ag/TiO2 interface which could extend the charge transfer pathway and facilitate separation of photoexcited electrons and holes. The plasmonic metal layer of nano Ag could generate significant surface plasmon resonance (SPR) effect which not only enhanced the absorption of visible light but also exhibited remarkable SERS effect for probe molecules. And an amazing detection limit of 1 × 10–10 M could be obtained when using crystal violet (CV) as probe molecules. In addition, the SERS substrates exhibited significant linear relationship between concentration and SERS signal intensity which ensures the accuracy of quantitative analysis and monitoring photoreduction process. The substrates have good cycling stability, enabling it to be reused for SERS detection many times. Thus, the excellent photocatalytic and SERS performance of Mott–Schottky hetero-structural TiO2@Ag@AgBr substrates shows great potential toward rapidly photocatalytic removal Cr (VI) ions and SERS on-site detection reduction process of Cr (VI) in waste water, which is of great significance to environmental protection and ecological restoration.