Surfactant free fabrication and improved charge carrier separation induced enhanced photocatalytic activity of {001} facet exposed unique octagonal BiOCl nanosheets.

Unique octagonal shaped BiOCl nanosheets (NS) dominantly exposed with high energy {001} crystal facets have been fabricated via a simple hydrothermal route without using organic surfactants. The dynamics of photogenerated charge carriers have been studied by time-resolved photoluminescence spectroscopy. The fitting parameters of the decay kinetics were used to calculate both the intensity weighted average lifetime (〈τ〉int.), as well as the amplitude weighted average lifetime (〈τ〉amp.) of the photogenerated charge carriers. The 〈τ〉int. and 〈τ〉amp. values for {001} BiOCl NS, i.e., 17.23 ns and 1.94 ns, respectively, were observed to be significantly higher than the corresponding values obtained for pristine BiOCl such as 2.52 ns and 1.07 ns, respectively. Significant quenching of the PL emission intensity of {001} BiOCl NS reflected the enhanced separation of the photogenerated charge carriers. Reduced thickness and in situ iodine doping was favorable to minimize the recombination tendency. The photocatalytic activity was monitored via the photodegradation of RhB under visible light illumination (λ > 400 nm). {001} BiOCl NS exhibited superior performance when compared to pristine BiOCl in terms of the rapid degradation kinetics and higher photonic efficiency. The photocatalytic efficiency of {001} BiOCl NS was 2.8 times higher than pristine BiOCl. Iodine doping induced extended the optical absorption in the visible region and improved the separation of the photogenerated charge carriers, which played an important role to enhance the photocatalytic activity. The photodegradation mechanism was systematically studied using various radical quenchers and it was revealed that photogenerated holes (h(+)) and superoxide radicals (˙O(2-)) actively participated whereas hydroxyl (OH˙) radicals had a negligible contribution in the photodegradation of RhB. {001} BiOCl NS has shown a higher photocurrent density and lower charge transfer resistance analyzed through photoelectrochemical and electrochemical impedance measurements. This study highlights the fabrication of unique octagonal BiOCl NS with improved separation of charge carriers across high energy crystal facts to design a highly efficient photocatalyst.