Dušan Kopecký

Polypyrrole nanotubes: mechanism of formation

This article presents a contribution to better understanding of the processes which take place during the synthesis of polypyrrole nanotubes using a structure-guiding agent, methyl orange. Polypyrrole was prepared by oxidation of pyrrole monomer with iron(III) chloride. In the presence of methyl orange, the formation of nanotubes was observed instead of the globular morphology. Two reaction schemes with reversed additions of oxidant and monomer have been tested and they show remarkable influence on the produced morphology. Nanotubes with circular or rectangular profiles and diameters from tens to hundreds of nanometres have been obtained. FTIR and Raman spectra were used to assess the molecular structure of polypyrrole and detect residual methyl orange in the samples. The conductivity of nanotubes compressed into pellets was as high as 68 S cm−1. The mechanism of nanotubular formation starting at the nucleus produced with the participation of organic dye is proposed. The growth of a nanotube, however, proceeds in the absence of a template. An alternative mechanism for the formation of nanotubes, the coating of solid templates with a polypyrrole overlayer, is also discussed.

Polypyrrole–silver composites prepared by the reduction of silver ions with polypyrrole nanotubes

Polypyrrole nanotubes were prepared by the oxidation of pyrrole with iron(III) chloride in the presence of methyl orange. They were subsequently used for the reduction of silver ions to silver nanoparticles. The nanotubular form of polypyrrole is compared with the classical globular morphology in its ability to reduce silver ions. Both polypyrrole salts and bases were used in the experiments. The content of metallic silver in the resulting composite, determined by thermogravimetric analysis, was 21–31 wt%. Elemental composition is also discussed on the basis of energy-dispersive X-ray spectroscopy. Contrary to the expectation, the conductivity of polypyrrole nanotubes in salt form, 35.7 S cm−1, was reduced to 20.9 S cm−1 after the incorporation of silver. The presence of silver had generally little effect on the conductivity. The temperature dependence of conductivity reveals that the composites maintain the semiconducting character of polypyrrole and their conductivity increased with increasing temperature. The conductivity of the composites surprisingly increased when the samples were placed in vacuo.

Polypyrrole salts and bases: superior conductivity of nanotubes and their stability towards the loss of conductivity by deprotonation

Polypyrrole nanotubes exhibit conductivity of tens S cm−1 which is one of the highest among the current conducting polymers. They are thus superior to the common globular form with the conductivity of units of S cm−1 or lower. The conductivity of both forms is reduced after treatment with alkalis but still remains high, units of S cm−1 and 10−2 S cm−1, respectively. The deprotonation, which is responsible for conductivity reduction, is discussed on the basis of salt–base transition in polypyrrole. It is not fully reversible, and the reprotonation with acids recovers the conductivity only in part. The role of methyl orange, which was used to support the formation of nanotubes, is proposed to be similar to that of surfactants. FTIR and Raman spectroscopies prove that methyl orange is strongly bound to polypyrrole in its acid form, and an “insertion” mechanism is proposed to explain the resistance towards the deprotonation of nanotubes. The spectra also illustrate that the molecular structure of nanotubular polypyrrole is preserved even under highly alkaline conditions at a pH close to 14, where the globular form becomes damaged. Polypyrrole, especially in its nanotubular form, is of promise in applications requiring electrical conduction even under neutral or alkaline conditions, where other conducting polymers, such as polyaniline, lose their exploitable conductivity.

Polypyrrole Nanotubes and Their Carbonized Analogs: Synthesis, Characterization, Gas Sensing Properties.

Polypyrrole (PPy) in globular form and as nanotubes were prepared by the oxidation of pyrrole with iron(III) chloride in the absence and presence of methyl orange, respectively. They were subsequently converted to nitrogen-containing carbons at 650 °C in an inert atmosphere. The course of carbonization was followed by thermogravimetric analysis and the accompanying changes in molecular structure by Fourier Transform Infrared and Raman spectroscopies. Both the original and carbonized materials have been tested in sensing of polar and non-polar organic vapors. The resistivity of sensing element using globular PPy was too high and only nanotubular PPy could be used. The sensitivity of the PPy nanotubes to ethanol vapors was nearly on the same level as that of their carbonized analogs (i.e., ~18% and 24%, respectively). Surprisingly, there was a high sensitivity of PPy nanotubes to the n-heptane vapors (~110%), while that of their carbonized analog remained at ~20%. The recovery process was significantly faster for carbonized PPy nanotubes (in order of seconds) compared with 10 s of seconds for original nanotubes, respectively, due to higher specific surface area after carbonization.

Synthesis of silver-anchored polyaniline–chitosan magnetic nanocomposite: a smart system for catalysis

A simple route was employed for the fabrication of a polyaniline (PANI)–chitosan (CS)–magnetite (Fe3O4) nanocomposite (PANI–CS–Fe3O4) via the in situ polymerization of aniline in the presence of CS using anhydrous iron(III) chloride as an oxidizing agent. The magnetic character of the nanocomposite results from the presence of iron oxide nanoparticles, which were formed as side products during the synthesis of the PANI–CS nanocomposite. The synthesized PANI–CS–Fe3O4 nanocomposite was fully characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), energy dispersive X-ray (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM). The reduction of silver nitrate by the synthesized nanocomposite enables the anchoring of silver (Ag) nanoparticles onto its surface. The catalytic properties of the Ag-decorated nanocomposite (Ag@PANI–CS–Fe3O4) toward the reduction of 4-nitrophenol was investigated using sodium borohydride as a reducing agent.

Polypyrrole active layers of gas sensors prepared by MAPLE technology

Thin layers of polypyrrole (PPY) were deposited by MAPLE (Matrix Assisted Pulse Laser Evaporation) technology. The deposition was carried out by KrF excimer laser from water and dimethylsulfoxide matrixes. Ablation thresholds (Fth) were determined to be Fth ~ 0.3 J.cm−2for dimethylsulfoxide matrix and Fth ~ 0.45 J.cm−2for water matrix. The roughness of deposited layers was measured by AFM and their chemical composition was characterized by FTIR spectroscopy. Finally, resistance of sensors with PPY active layer was measured in dependence on working temperature and relative humidity of surrounding atmosphere.

Dye-stimulated control of conducting polypyrrole morphology

Azo dyes represent important structure-guiding agents which exhibit non-covalent interactions of various types (ionic and hydrogen bonding, π–π stacking, hydrophobic interactions, etc.) allowing for their self-assembly in aqueous solutions and the subsequent formation of seeds or templates for the preparation of supramolecular structures of conducting polymers, especially polypyrrole (PPy). Three azo dyes (Acid Red 1, Orange G and Sunset Yellow FCF) bearing hydrophilic functional groups, with mutually different positions on a hydrophobic naphthylphenyldiazene skeleton, were used as structure-guiding agents in the synthesis of highly organized supramolecular structures of PPy in aqueous media. The synthesized polymers were studied by scanning electron microscopy, energy dispersive X-ray, and Fourier-transform infrared and Raman spectroscopies. Measurement of the conductivity revealed a moderate value of conductivity (around units of S cm−1) and reduced stability indicated by relatively fast conductivity decay. Infrared spectroscopy indicated a lower doping level of all PPy prepared in the presence of tested dyes compared to that of standard globular PPy. In contrast, Raman spectroscopy, which is a surface-sensitive method, indicated a slightly higher protonation level compared to that of standard globular PPy or nanotubular PPy synthesized in the presence of the well-known structure-guiding agent methyl orange. This discrepancy in the obtained doping levels is discussed and some consequences between the doping level of PPy and its conductivity are also pointed out.

Influence of non-thermal plasma on structural and electrical properties of globular and nanostructured conductive polymer polypyrrole in water suspension

Non-thermal plasma has proved its benefits in medicine, plasma assisted polymerization, food industry and many other fields. Even though, the ability of non-thermal plasma to modify surface properties of various materials is generally known, only limited attention has been given to exploitations of this treatment on conductive polymers. Here, we show study of non-thermal plasma treatment on properties of globular and nanostructured polypyrrole in the distilled water. We observe that plasma presence over the suspension level doesn’t change morphology of the polymer (shape), but significantly influences its elemental composition and physical properties. After 60u2009min of treatment, the relative concentration of chloride counter ions decreased approximately 3 and 4 times for nanostructured and globular form, respectively and concentration of oxygen increased approximately 3 times for both forms. Simultaneously, conductivity decrease (14 times for globular and 2 times for nanostructured one) and changes in zeta potential characteristics of both samples were observed. The modification evolution was dominated by multi-exponential function with time constants having values approximately 1 and 10u2009min for both samples. It is expected that these time constants are related to two modification processes connected to direct presence of the spark and to long-lived species generated by the plasma.