Semiconductor photocatalytic performances can be modulated through morphology modification. Herein porous hierarchical BiOBr microspheres (BiOBr-MS) of ~3 m was firstly self-assembled without the assistance of a template via a facile solvothermal synthesis in triethylene glycol (TEG) at 150 oC for 3 h. KBrO3 was exploited as a bromine source, which slowly provided bromide ions upon reduction in TEG and controlled the growth and self-assembly of primary BiOBr nanoplates. The addition of PVP during solvothermal synthesis of BiOBr-MS reduced the particle size by about three-fold to generate BiOBr sub-microspheres (BiOBr-sMS) of <1 m. BiOBr-sMS exhibited significantly higher photocatalytic activity than BiOBr-MS for aerobic photooxidation of benzyl alcohol (BzOH) to benzaldehyde (BzH) under simulated sunlight irradiation (conversions of BzOH (50 mM) over BiOBr-sMS and BiOBr-MS were respectively 51.3% and 29.6% with 100% selectivity to BzH after Xenon illumination for 2 h at 25 oC). The photogenerated holes and •O2- were found to be main reactive species for the BzOH oxidation over BiOBr spheres by scavenging tests and spin-trapping EPR spectra. The higher photocatalytic activity of BiOBr-sMS was attributed to its more open hierarchical structure, efficient charge separation, more negative conduction band position and generation of larger amounts of •O2-.

The novel ternary composites, BiOBr-TiO2-attapulgite (BTA), were synthesized using a simple hydrothermal and water-bath method, exhibiting excellent photocatalytic performance to mul-tiple xanthates. For BTA photocatalyst, TiO2 and BiOBr were uniformly loaded on the surface of acid-activated attapulgite. As a widely used collector in mining processes, sodium ethyl-xanthate (SEX) was selected as the target pollutant due to its high toxicity. The BTA ternary photocatalyst demonstrated significantly higher adsorption and photocatalytic degradation performance compared to TiO2 nanoparticles, BiOBr nanosheets, and BiOBr-TiO2 heterojunction. Structural characterization and experimental results indicated that the exceptional photocatalytic degrada-tion efficiency of BTA was mainly attributed to the formation of heterojunction between BiOBr and TiO2, as well as the presence of additional active adsorption sites provided by attapulgite. Free radical scavenging experiments and EPR results confirmed that the photogenerated holes were the predominant active species to photodegrade SEX throughout the entire experiment. The LC-MS results provided insight into potential degradation pathways of SEX. This research demonstrates that BTA, as a novel triple composite material, achieves rapid and complete degradation to 20 mg/L SEX within 20 min. This work presents a novel approach to synthesize mineral-based photo-catalysts, which have broad prospects for application in flotation wastewater treatment.