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.
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.
Polypyrrole one-dimensional nanostructures (nanotubes, nanobelts and nanofibers) were prepared using three various dyes (Methyl Orange, Methylene Blue and Eriochrome Black T). Their high electrical conductivity (from 17.1 to 60.9 S cm−1), good thermal stability (in the range from 25 to 150 °C) and resistivity against ageing (half-time of electrical conductivity around 80 days and better) were used in preparation of lightweight and flexible composites with silicone for electromagnetic interference shielding in the C-band region (5.85–8.2 GHz). The nanostructures’ morphology and chemical structure were characterized by scanning electron microscopy, Brunauer–Emmett–Teller specific surface measurement and attenuated total reflection Fourier-transform infrared spectroscopy. DC electrical conductivity was measured using the Van der Pauw method. Complex permittivity and AC electrical conductivity of respective silicone composites were calculated from the measured scattering parameters. The relationships between structure, electrical properties and shielding efficiency were studied. It was found that 2 mm-thick silicone composites of polypyrrole nanotubes and nanobelts shield almost 80% of incident radiation in the C-band at very low loading of conductive filler in the silicone (5% w/w). Resulting lightweight and flexible polypyrrole composites exhibit promising properties for shielding of electromagnetic interference in sensitive biological and electronic systems.
The carbonization of collagen-based leather waste to nitrogen-containing carbon is reviewed with respect to the preparation, characterization of carbonized products, and applications proposed in the literature. The resulting nitrogen-containing carbons with fibrous morphology have been used as adsorbents in water pollution treatment, in electrocatalysis, and especially in electrodes of energy-storage devices, such as supercapacitors and batteries. Although electrical conductivity has been implicitly exploited in many cases, the quantitative determination of this parameter has been addressed in the literature only marginally. In this report, attention has been newly paid to the determination of conductivity and its dependence on carbonization temperature. The resulting powders cannot be compressed into pellets for routine conductivity determination. A new method has been used to follow the resistivity of powders as a function of pressure up to 10 MPa. The conductivity at this pressure increased from 9.4 × 10−8 S cm−1 for carbonization at 500 °C to 5.3 S cm−1 at 1000 °C. The conductivity of the last sample was comparable with conducting polymers such as polypyrrole. The carbonized leather thus has the potential to be used in applications requiring electrical conduction.