Bismuth Oxybromide-based Photocatalysts: Syntheses, Characterizations and Application

The increasing intractable crises of environmental pollution and fossil fuels shortage are among the biggest challenges in current society and becoming an overwhelming concern for the development of our future world. Semiconductor photocatalysis has received considerable interdisciplinary attention and research interest owing to their diverse potentials in energy and environmental applications. As an important V-VI-VII ternary semiconductor, BiOBr has been recently received considerable attention owing to its fascinating physicochemical prosperities originated from its unique layered structures. However, existing reports on the photocatalytic bacterial inactivation of BiOBr based photocatalysts are rather limited. In addition, the mechanisms in visible-light-driven (VLD) photocatalytic disinfection systems are far from fully understandable. Moreover, the exploitation of facile ways to make BiOBr photocatalysts harvesting a wide range of solar spectrum with high efficiency remains challenging, yet highly desirable.;In this study, BiOBr based photocatalysts with various nanostructures were synthesized and characterized. Their photocatalytic activities were systematically investigated towards bacterial inactivation, dye degradation and CO2 reduction. The exploration on the photo-excited charge carriers and reactive species were conducted to gain some insight into the corresponding photocatalytic mechanisms.;Firstly, BiOBr 2D nanosheets with a high percentage of exposed {001} and {010} facets were synthesized via a facile hydrothermal method. BiOBr with dominant {001} facet (B001) nanosheets exhibited remarkably higher photocatalytic activity in inactivating E. coli K-12 under visible light irradiation, in comparison with BiOBr with dominant {010} facet (B010) nanosheets. There were 7-log bacterial cells inactivated within 2 h for B001, while B010 needed 6 h irradiation to inactivate 6.5-log bacterial cells. This superior activity was assigned to the more favorable separation and transfer of photogenerated e--/h+ pairs as well as more oxygen vacancies in B001 nanosheets, resulting in faster production and further accumulation of •O2-- and h+ within a short time.;Secondly, B was doped into BiOBr nanosheets without changing the morphology, crystal structure, and {001}-facet exposed features compared with pure BiOBr nanosheets. The photocatalytic activities were investigated by inactivating E. coli K-12 bacteria using fluorescence tubes as visible light sources. Significantly, 0.75B-BiOBr (0.75% molar ratio of B/Bi) showed the best photocatalytic efficiency with 7-log bacterial cells inactivation within 30 min, compared with 2-log for pure BiOBr. Photogenerated h+ was the major reactive species accounting for the B-BiOBr inactivation system. With its electron-deficient characteristics, the B dopant is favorable to accept extra e-- from VB of BiOBr, leading to improved e-- /h+ separation efficiency. In addition, the destruction process of bacterial cell was also observed from the destruction of cell membrane to the intracellular components.;Finally, a simple alkali (NaOH) post-treatment approach was applied to obtain BiOBr-0.01 with brown color. Bi2O4 nanoparticles were in situ formed due to a combined action of NaOH-induced dehalogenation and light triggered photoexcited h+ oxidation processes on the surface of BiOBr nanosheets. Significantly, without any foreign elements, the light absorption of BiOBr-0.01 was extended to the near infrared (NIR) region. Compared with normal BiOBr, BiOBr-0.01 nanosheet showed superior photocatalytic activity for the dye degradation and microbial disinfection. Particularly, it exhibits excellent capability to photocatalytically reduce CO2 into CO and CH4, whereas the normal BiOBr is completely incapable for CO2 conversion under simulated sunlight irradiation. The exceptional enhancement is due to the Bi2O4 extended light absorption, efficient e--/h + separation, and the increased surface-adsorbed ability to reactants. This facile post-treatment method is promising for different bismuth-based systems and hence offers a path to a large variety of materials.