Electrodeposition of self-assembled poly(3,4-ethylenedioxythiophene) @gold nanoparticles on stainless steel wires for the headspace solid-phase microextraction and gas chromatographic determination of several polycyclic aromatic hydrocarbons
Introduction
Polycyclic aromatic hydrocarbons (PAHs) are a group of organic pollutants. In the environment they generally come from the incomplete combustion of organic materials and the sources include volcano, forest fire, industrial process, vehicle emission, refinery, incineration and burning tobacco [1]. PAHs exhibit significant hazard to the environment and human health as they have high toxicity, mutagencity and carcinogenicity. Especially, they are persistent and bioaccumulative, giving rising to their danger. In 2011, EU Regulation 835/2011 established the upper limits for a subset of four specific PAHs in various food matrices [2]. Owing to the low contents of PAHs in the environmental matrix, enrichment is usually required before their detection.
For their enrichment the most frequently employed technique is solid phase extraction (SPE), generally followed by GC/MS analysis [3], [4], [5]. For examples, molecularly imprinted polymers (MIPs) based SPE was used for the detection of PAHs in seawater [6], [7]; stir bar sorptive extraction (SBSE) was employed to the analysis of PAHs in soil eluates [8]; air-assisted dispersive micro solid phase extraction (A-dμ-SPE) was applied for the detection of PAHs in biological samples [9]. Solid phase microextraction (SPME) has also been used for the analysis of PAHs [10], [11], [12], [13], which is a sensitive technique and usually performed by using a polymer coated fiber [14], [15], [16], [17]. But the available commercial fibers, such as polydimethylsiloxane (PDMS), polyacrylate (PA), and polydimethylsiloxane/divinylbenzen (PDMS/DVB), are moderately expensive and fragile, and have limited lifetime at high temperatures and in organic solvents. In addition, the variety of commercial fibers is rather limited and they lack high selectivity. For these reasons, many researchers focused on developing new fibers with better performance.
In recent years, organic-inorganic hybrid materials have received considerable attention because they can combine the advantages of organic and inorganic materials to some extent [18], [19]. Some hybrid materials, especially the hybrid nanomaterials, are considered to be high-efficiency sorbents due to their high specific surface area, and excellent thermal and mechanical stability [20], [21], [22]. For instance, Ali et al. prepared a polyaminithiophenol (PATP) with Au coating by layer-by-layer self-assembly for the extraction of PAHs in aqueous solution [23]. It showed excellent properties, but the layer-by-layer self-assembly process was cumbersome and time-consuming. Wu et al. fabricated a poly(3,4-ethylenedioxythiophene)-ionic liquid polymer functionalized multiwalled carbon nanotubes (PEDOT-PIL/MWCNTs) composite coating for the extraction of carbamate pesticides in apple and lettuce samples, which exhibited much higher sensitivity than commercial coatings [24]. In addition, for PEDOT the introduction of conductive nanomaterials benefited the control of its thickness and structure as its conductivity was poor and it tended to crack with its thickness increasing. As we all know, nanoparticles easily aggregate due to high surface energy, high adsorption etc, especially in organic media. PEDOT is one of the few electropolymers that present similar property and structure no matter whether prepared in neutral aqueous solution or in organic media. To the best of our knowledge, there are no reports about the preparation of gold nanoparticals (AuNPs) doped PEDOT coating through electrochemical method in aqueous solution.
In this study, a poly(3,4-ethylenedioxythiophene)@AuNPs (PEDOT@AuNPs) hybrid coating was prepared. Firstly, the monomer 3,4-ethylenedioxythiophene (EDOT) was self-assembled on AuNPs, and then electropolymerization was performed on a stainless steel wire by cyclic voltammetry. The developed fiber demonstrated high selectivity toward PAHs due to hydrophobic interaction and the effect of AuNPs. The organic-inorganic hybrid coating was characterized and its extraction property was explored by using model analytes, including benzenes, phenols, amines and PAHs. The conditions were optimized for the extraction of PAHs, and environmental water samples were determined by coupling with GC.
Section snippets
Reagents and materials
All chemicals and reagents were of analytical grade. 3,4-Ethylenedioxythiophene, 3-methylthiophene, 2,2′-bithiophene and chloroauric acid (HAuCl4·4H2O) were purchased from Aladdin Chemistry Co., Ltd. (Shanghai, China). Trisodium citrate dehydrate (Na3C6H5O7·2H2O), sodium dodecylbenzenesulfonate (SDBS), sodium chloride (NaCl), potassium ferricyanide (K3[Fe(CN)6]), potassium hexacyanoferrate(II) (K4[Fe(CN)6]), potassium chloride (KCl), naphthalene (NAP), 2-methylnaphthalene (2-MNAP), acenaphthene
Optimization of AuNPs concentration
In order to achieve high extraction efficiency, several PEDOT@AuNPs fibers were prepared by varying the AuNPs concentration (i.e. HAuCl4 concentration, instead of AuNPs concentration), while the concentration of EDOT was kept unchanged (i.e. 0.050 M). When the concentration ratios (mM/M) of AuNPs and EDOT were 2/1, 4/1, 6/1, 8/1, 10/1, 15/1 and 20/1, the resulting fibers were denoted as PEDOT@AuNPs-2/1, PEDOT@AuNPs-4/1, PEDOT@AuNPs-6/1, PEDOT@AuNPs-8/1, PEDOT@AuNPs-10/1, PEDOT@AuNPS-15/1,
Conclusions
In summary, self-assembled AuNPs@EDOT was electropolymerized on a stainless steel wire as SPME coating. It presented cauliflower-like micro-structure and had plentiful access sites for the adsorption of target analytes. Owing to the synergetic effect of hydrophobic PEDOT and AuNPs, the PEDOT@AuNPs coating exhibited high extraction efficiency and good selectivity for PAHs. Besides that, the PEDOT@AuNPs coating displayed good durable property (could be used for more than 160 times) and
Acknowledgement
The authors appreciate the support of the National Natural Science Foundation of China (Grant No. 21275112).
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