ARTICLE pubs.acs.org/ac
Poly(3-hexylthiophene)/TiO2 Nanoparticle-Functionalized Electrodes for Visible Light and Low Potential Photoelectrochemical Sensing of Organophosphorus Pesticide Chlopyrifos Hongbo Li,†,‡ Jing Li,‡ Qin Xu,† and Xiaoya Hu*,† † ‡
College of Chemistry and Engineering, Yangzhou University, 88 South University Avenue, Yangzhou 225002, PR China College of Chemistry and Biology Engineering, Yancheng Institute of Technology, 9 Yingbin Avenue, Yancheng 224051, PR China ABSTRACT: A dramatic visible light photoelectrochemical sensing platform for the detection of pesticide molecules at zero potential (versus saturated calomel electrode) was first constructed using poly(3-hexylthiophene)-functionalized TiO2 nanoparticles. Poly(3-hexylthiophene) (P3HT) was synthesized via chemical oxidative polymerization with anhydrous FeCl3 as the oxidant, 3-hexylthiophene as the monomer, and chloroform as the solvent, and the functional TiO2 nanoparticles were facilely prepared by blending TiO2 nanoparticles and P3HT in chloroform solution. The resulting photoelectrocatalysts were characterized by scanning electron microscopy, Raman spectroscopy, and X-ray diffractometry. Under visible light irradiation, P3HT generated the transition from the valence band to the conduction band, delivering the excited electrons into the conduction band of TiO2 and then to the glassy carbon electrode. Simultaneously, a positive charged hole (h+) of TiO2 may form and migrate to the valence band of P3HT, which can react with H2O to generate •OH, and then it converted chlopyrifos into chlopyrifos• that promoted the amplifying photocurrent response. On the basis of the proposed photoelectrochemical mechanism, a methodology for sensitive photoelectrochemical sensing for chlopyrifos at zero potential was thus developed. Under optimal conditions, the proposed photoelectrochemical method could detect chlopyrifos ranging from 0.2 to 16 μmol L 1 with a detection limit of 0.01 μmol L 1 at a signal-to-noise ratio of 3. The photoelectrochemical sensor had an excellent specificity against the other pesticides and could be successfully applied to the detection of reduced chlopyrifos in green vegetables, showing a promising application in photoelectrochemical sensing.
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hotoelectrochemical measurement is a newly developed technique for the sensing platform, which is based on the electron transfer among analyte, semiconductor, and electrode with photoirradiation.1,2 Coupling photoirradiation with electrochemical detection, photoelectrochemical sensors have the advantages of both optical methods and electrochemical sensors.3,4 Thus, this technique shows promising analytical applications and has attracted considerable interest. During the recent decades, the fascinating inorganic semiconductor titanium dioxide (TiO2) has attracted extensive attention in the photocatalytic area for decomposition of organic compounds, sterilization, cancer treatment, etc. due to its high photocatalytic activity, abundant resource, biological and chemical inertness, and nontoxicity.5 8 However, the wide band gap of TiO2 (∼3.2 eV, anatase) only allows it to absorb the ultraviolet light (
