Polymer-Functionalized Single-Walled Carbon Nanotubes as a Novel Sol−Gel Solid-Phase Micro-extraction Coated Fiber for Determination of Poly-brominated Diphenyl Ethers in Water Samples with Gas Chromatography−Electron Capture Detection

Abstract

Single-walled carbon nanotubes (SWNTs) were functionalized with a hydroxyl-terminated silicone oil (TSO-OH). It is synthesized by the reactions of carbonyl chloride groups on the surface of SWNTs and hydroxyl groups of silicone oil (TSO-OH). The functionalized product SWNTs-TSO-OH was first used as precursor and selective stationary phase to prepare the sol-gel derived poly(SWNTs-TSO-OH) solid-phase microextraction (SPME) fiber for determination of polybrominated diphenyl ethers (PBDEs) in water samples. The possible major reaction of the sol-gel coating process was discussed and confirmed by IR spectra, Raman spectroscopy, and scanning electron microscopy. Some parameters of SPME fiber for the determination of PBDEs were investigated by headspace SPME/gas chromatography with electron-capture detection (HS-SPME/GC-ECD). Compared with the commercial SPME fiber, the new coated fiber showed higher extraction efficiency to PBDEs, better thermal stability (over 340 degrees C), and longer life span (over 200 times). All of these advantages are mainly due to the incorporation of SWNTs, which enhanced the pi-pi interaction with PBDEs and increased the surface area of extraction in contact with the sample. Moreover, the sol-gel coating technology additionally provided the porous structure of the 3-D silica network and the strong chemical binding provided which also will improve the extraction efficiency. Under optimized conditions, the method detection limits for seven PBDEs were 0.08-0.8 ng/L (S/N = 3) and the precision (RSD, n = 5) was 2.2-7.5% at the 50 ng/L level. The linearity of the developed method is in the range of 5-500 ng/L with coefficients of correlation greater than 0.995. The developed method was successfully applied for the analysis of trace PBDEs in reservoir water and wastewater samples. The recoveries obtained at spiking 50 ng/L were between 74% and 109% (n = 5) for PBDEs in water samples.