A New Insight into the Mechanisms Underlying the Discoloration, Sorption, and Photodegradation of Methylene Blue Solutions with and without BNOx Nanocatalysts

Methylene blue (MB) is widely used as a test material in photodynamic therapy and photocatalysis. These applications require an accurate determination of the MB concentration as well as the factors affecting the temporal evolution of the MB concentration. Optical absorbance is the most common method used to estimate MB concentration. This paper presents a detailed study of the dependence of the optical absorbance of aqueous methylene blue (MB) solutions in a concentration range of 0.5 to 10 mg.L-1. The nonlinear behavior of optical absorbance as a function of MB concentration is described for the first time. A sharp change in optical absorption is observed in the range of MB concentrations from 3.33 to 4.00 mg.L-1. Based on the analysis of the absorption spectra, it is concluded that this is due to the formation of MB dimers and trimers in the specific concentration range. For the first time, a strong, thermally induced discoloration effect of the MB solution under the influence of visible and sunlight was revealed: the simultaneous illumination and heating of MB solutions from 20 to 80 degrees C leads to a twofold decrease in the MB concentration in the solution. Exposure to sunlight for 120 min at a temperature of 80 degrees C led to the discoloration of the MB solution by more than 80%. The thermally induced discoloration of MB solutions should be considered in photocatalytic experiments when tested solutions are not thermally stabilized and heated due to irradiation. We discuss whether MB is a suitable test material for photocatalytic experiments and consider this using the example of a new photocatalytic material-boron oxynitride (BNOX) nanoparticles-with 4.2 and 6.5 at.% of oxygen. It is shown that discoloration is a complex process and includes the following mechanisms: thermally induced MB photodegradation, MB absorption on BNO(x )NPs, self-sensitizing MB photooxidation, and photocatalytic MB degradation. Careful consideration of all these processes makes it possible to determine the photocatalytic contribution to the discoloration process when using MB as a test material. The photocatalytic activity of BNO(x )NPs containing 4.2 and 6.5 at.% of oxygen, estimated at similar to 440 mu mol.g(-1).h(-1). The obtained results are discussed based on the results of DFT calculations considering the effect of MB sorption on its self-sensitizing photooxidation activity. A DFT analysis of the MB sorption capacity with BNOx NPs shows that surface oxygen defects prevent the sorption of MB molecules due to their planar orientation over the BNOx surface. To enhance the sorption capacity, surface oxygen defects should be eliminated.

Automated summary

This study provides a detailed examination of the optical absorbance of methylene blue (MB) solutions and the nonlinear relationship between absorbance and concentration. It reveals a significant change in absorbance within a specific concentration range, attributed to the formation of MB dimers and trimers. Additionally, the study highlights the thermally induced discoloration effect in MB solutions and its implications for photocatalytic experiments. Furthermore, the suitability of MB as a test material for photocatalysis is discussed, along with the photocatalytic activity of boron oxynitride nanoparticles.