Mechanisim investigation on the enhanced and selective photoelectrochemical oxidation of atrazine on molecular imprinted mesoporous TiO2

Abstract

In this work, enhanced and selective photoelectrochemical (PEC) oxidation of atrazine was realized on molecular imprinted mesoporous TiO2 (MI-meso-TiO2). The investigation revealed that, for one hand, the surface MI sites could function as surface defects for accelerating the separation of photogenerated holes and electrons, leading to enhanced generation of hydroxyl radicals. For the other hand, the MI sites showed enhanced binding affinity toward atrazine, resulted from the formation of multiple hydrogen bonds and halogen bonds etc., which was testified by in situ ATR-FTIR spectra. It led to the enhanced adsorption and improved local concentration of atrazine on the electrode surface. Both the two factors contributed to the improved PEC oxidation activity for atrazine on MI-meso-TiO2 compared with that on meso-TiO2. Moreover, the high binding affinity between MI sites and atrazine resulted in the selective recognition ability toward atrazine in the presence of the coexisting pollutants, so that selective PEC oxidation of atrazine in complex polluted water samples was successfully achieved on MI-meso-TiO2 with the apparent rate constant of 0.25 h−1, whereas that on meso-TiO2 was only 0.08 h−1. This work provided something new for explaining the selective and enhanced PEC performance on molecular imprinting catalyst.