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

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Abstract

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.

An amino-functionalized metal-organic framework (MOF) modified with titanium dioxide was synthesized and used as a new platform for photoelectrochemical sensing of the herbicide clethodim.

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Acknowledgments

We gratefully acknowledge the financial support from the National Natural Science Foundation of China (No. 21275124 and 21275125), PAPD of Jiangsu Higher Education Institutions, Qing Lan Project of Jiangsu Province (2014-23, 11KJB150019), China Senior Visiting Scholar Program Projects of Jiangsu Province Vocational Colleges (2014FX085), Graduate Innovation Project Foundation of Jiangsu province (KYLX_1333 and KYLX_1334), and The High-End Talent Project of Yangzhou University.

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Authors and Affiliations

  1. College of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, People’s Republic of China

    Dangqin Jin, Qin Xu, Liangyun Yu & Xiaoya Hu

  2. Department of Chemical Engineering, Yangzhou Polytechnic Institute, Yangzhou, 225127, People’s Republic of China

    Dangqin Jin

  3. School of Textiles and Clothing, Yancheng Institute of Technology, Yancheng, 224051, People’s Republic of China

    Liangyun Yu

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  1. Dangqin Jin
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Correspondence to Xiaoya Hu.

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Jin, D., Xu, Q., Yu, L. et al. Photoelectrochemical detection of the herbicide clethodim by using the modified metal-organic framework amino-MIL-125(Ti)/TiO2 . Microchim Acta 182, 1885–1892 (2015). https://doi.org/10.1007/s00604-015-1505-9

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  • DOI: https://doi.org/10.1007/s00604-015-1505-9

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