One-Step UV-Induced Synthesis of Polypyrrole/Ag Nanocomposites at the Water/Ionic Liquid Interface
© The Author(s) 2009
Received: 1 September 2009
Accepted: 19 November 2009
Published: 28 November 2009
Polpyrrole (PPy)/Ag nanocomposites were successfully synthesized at the interface of water and ionic liquid by one-step UV-induced polymerization. Highly dispersed PPy/Ag nanoparticles were obtained by controlling the experimental conditions. The results of Fourier-transform infrared spectroscopy, X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy revealed that the UV-induced interface polymerization leaded to the formation of PPy incorporating silver nanoparticles. It was also found that the electrical conductivity of PPy/Ag nanocomposite was about 100 times higher than that of pure PPy.
KeywordsPolypyrrole Ag Ionic liquid Nanocomposites
Nanocomposites of conducting polymers and metallic nanoparticles have attracted considerable attention in recent years because of their potential applications in various areas, such as electrocatalysis, chemical sensors and optoelectronic devices [1–4]. They have synergistic chemical and physical properties based on the constituent polymer and introduced metal. Extraordinary physicochemical properties of such nanocomposites can be attributed to high surface area and quantum size effect [5–8]. Various methods for the preparation of these composites have been described. In general, these following routes are used: (a) where the monomer or polymer acts as a reductant for the metal, yielding the nanocomposite in powder or thin film forms [9, 10] or (b) preparation of the nanoparticles followed by either chemical polymerization around the particles or dispersion of the nanoparticles in a polymer matrix [11, 12].
In parallel with the development of the above nanocomposites, the topic of “green” chemistry and chemical processes has been emphasized . Ionic liquids, defined herein as salts that melt at or below 100°C, can provide unique properties, such as non-flammability, low volatility, high thermal and electrochemical stability, and ionic conductivity [14–17]. They are regarded as environmentally friendly solvents. In particular, the imidazolium ionic liquids associated with specific anions are known to self-organize in a way that is adaptable to the fabrication of nanostructures of metal and conducting polymers [18–22]. However, it is still appealing to study the relationship between the different ionic liquids and the structures of the nanomaterials fabricated in them.
In this paper, we presented a simple and environmentally friendly method to synthesize PPy/Ag nanocomposites at the interface of water and ionic liquid. During the formation process of PPy/Ag, ultraviolet light was introduced in order to improve the reaction rate and distribution level of Ag nanoparticles. Fourier-transform infrared (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) were used to characterize the PPy/Ag nanocomposites. It was observed that PPy/Ag nanocomposites possess enhanced higher conductivity since silver was a conductor.
Polyvinylpyrrolidone (PVP), 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) and AgNO3 were purchased from Aldrich. Pyrrole was distilled twice under reduced pressure, stored under nitrogen and refrigerated in the dark. Other reagents were used as received without further treatment.
In a typical synthesis of PPy/Ag nanocomposites, 2 mmol of pyrrole was dissolved in 10 mL of BmimBF4. Then, AgNO3 was dissolved in aqueous solution with or without 0.1 M PVP. The two solutions were then carefully transferred to a beaker and an interface was generated between two layers. The solutions were placed under a UV lamp (500 W) set at 254 nm for 60 min at room temperature. After that, the UV-light was removed and the reaction was continued for 10 h. The precipitate was centrifuged and washed with distilled water and ethanol for several times, respectively. The final product was dried under vacuum at 40°C for 24 h.
The morphologies were measured by transmission electron microscopy (TEM, JEM-200CX). Fourier-transform infrared spectra (FTIR) of the samples were recorded on a Bruker VECTOR22 spectrometer using KBr pressed disks. XRD patterns were taken with a Shimadzu XD-3A instrument with a Cu Ka X-ray source. XPS was performed using a Kratos AXIS HSi spectrometer equipped with a monochromatized Al Kα X-ray source (1,486.6 eV photons). The conductivities were measured by using the standard four-probe method at room temperature.
Results and Discussion
Conductivities of the products prepared at different ratios of AgNO3 and pyrrole monomer
A simple one-step strategy for synthesizing PPy/Ag nanocomposites in the presence of PVP has been demonstrated. The oxidation of pyrrole and the formation of silver were initiated by UV irradiation, and then occurred simultaneously at the interface of water and ionic liquid. The formation of the nanocomposites was confirmed by TEM, XPS, FTIR and XRD analysis. Our method showed the merits of easier preparation and more environmental harmony. The nanocomposites may have potential application in many fields of biological separation, enzyme immobilization and biosensors.
An erratum to this article can be found athttp://dx.doi.org/10.1007/s11671-010-9759-y
The work is supported by Educational Bureau of Hubei Province (Q20091508), Scientific Research Key Project of Ministry of Education of China (209081), National Natural Science Foundation of China (20904044) and State Key Laboratory of Coordination Chemistry (Nanjing University).
This article is distributed under the terms of the Creative Commons Attribution Noncommercial License which permits any noncommercial use, distribution, and reproduction in any medium, provided the original author(s) and source are credited.
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