Reoxidation dynamics of the methylene blue reduced by laser-synthesized silver nanoparticle

The catalytic reduction of methylene blue (MB) by metal nanoparticles and subsequent reoxidation is widely recognized and often referred to as a "redox reaction." The reduction mechanism of MB has been extensively studied and is well understood but its reoxidation has received little attention. Here we report an experimental study on the reoxidation dynamics of MB reduced by silver nanoparticles (Ag NPs). Ag NPs synthesized using the Pulsed Laser Ablation (PLAL) technique are used to reduce MB in the presence of the reducing agent NaBH4. The reduction/reoxidation dynamics are monitored using UV−Vis spectroscopy through the decrease/increase of characteristic MB absorbance peak and color switching between methylene blue and leucomethylene (LMB). The influence of the various volumetric concentrations of Ag NPs and NaBH4 on reoxidization dynamics of reduced MB is investigated. The reoxidation of reduced MB exhibited almost linear growth over time for different concentrations of both Ag NPs and NABH4 used in the reduction process. Higher NaBH4 concentrations appeared to decelerate the reoxidation process, while the concentration of Ag NPs had no discernible impact on the reoxidation rate. The reduction of reoxidized MB after adding additional amounts of Ag NPs and NaBH4 revealed that Ag NPs remained stable in the reaction medium but NaBH4 deteriorated. Therefore, the deterioration of the NaBH4 is identified as the major cause of the reoxidation of the reduced MB. A series of reduction-reoxidation experiments using chemically synthesized Ag NPs indicated that MB reoxidation is not limited to laser-synthesized Ag NPs.