Photoelectrochemical detection of the herbicide clethodim by using the modified metal-organic framework amino-MIL-125(Ti)/TiO2

We describe a sensitive photoelectrochemical (PEC) sensor for the determination of the herbicide clethodim. The PEC sensor was constructed by using amino-MIL-125/TiO2 (MIL stands for Materials from Institute Lavoisier), an amino-functionalized metal-organic framework (MOF) modified with TiO2. The amino-MIL-125/TiO2 was synthesized by a simple one-step solvothermal method and placed on a glassy carbon electrode where it displays photoelectrocatalytic activity. Scanning electron microscopy (SEM), Fourier-transform infrared (FTIR) spectroscopy and X-ray diffractometry (XRD) were used to characterize the amino-MIL-125/TiO2. In the sensing process, amino-MIL-125/TiO2 is illuminated by visible light to produce electrons. These excited electrons are delivered to the glassy carbon electrode, leaving positively charged holes (h+) on the surface of the amino-MIL-125/TiO2. The holes react with H2O to generate hydroxy radicals (•OH). Clethodim rapidly attacks the hydroxy radicals and improves the efficiency of charge separation, this leading to an enhanced photocurrent. Under the optimal experimental conditions, this photoelectrochemical method enables clethodim to be quantified in the concentration range from 0.2 to 25 μmol L−1, with a detection limit (3 S/N) of 10 nmol L−1. The assay was applied to the determination of clethodim in soil samples, and results were in acceptable agreement with data obtained by liquid chromatography/mass spectrometry.