Outstanding photo-thermo synergy in aerobic oxidation of cyclohexane by bismuth tungstate-bismuth oxychloride high-low heterojunction.

The difficulty of achieving both high conversion rate and high selectivity is a huge challenge in the catalytic aerobic oxidation of cyclohexane. In this paper, bismuth tungstate-bismuth oxychloride (BiWO-BiOCl) nanoflower heterojunctions prepared via a one-step solvothermal process were applied in the photo-thermo synergetic catalytic oxidation of cyclohexane in the dried air. With the addition of little water at different reaction temperature, the ratio of bismuth to tungsten and the mass ratio of BiWO to BiOCl can be precisely tailored in the nanoflower sphere composites with thin nanosheets. Their microscopic morphology, elemental composition, crystal structure, and photoelectrochemical characteristics were explored by different characterization methods. The BiWO-BiOCl composites possessed poor photocatalytic and thermal performances with the low conversion rates of 1.43% and 2.68%, respectively. However, through the photo-thermo catalytic oxidation process, an exceptional conversion rate of 13.32% was achieved with excellent selectivity of 99.22% for cyclohexanone and cyclohexanol (KA oil) using the same BiWO-BiOCl composites. This superior performance outstrips BiWO flowers, BiOCl nanosheets and BiWO-BiOCl composites with other compounding ratios. The creation of a high-low heterojunction in the BiWO-BiOCl composite was confirmed by band energy analysis. The opto-electronic analysis, band energy analysis, sacrifice experiments, and active radical analysis were employed to elucidate the mechanism for the exceptional photo-thermo catalytic performance in detail. This work offers an exploratory solution to the challenges of high energy consumption and the difficulty in simultaneously achieving high selectivity and high conversion rates in cyclohexane oxidation, thus holding significant value.