Highly Electroactive Frozen-State Polymerized Polypyrrole Nanostructures for Flexible Supercapacitors.

The polymerization of pyrrole in the frozen state with the presence of organic dyes (methyl orange (MO) and Acid Blue 25 (AB)) has proven to produce polypyrrole (PPy) nanostructures. Herein, we explore the electrochemical properties of PPy prepared under frozen-state conditions (-24 °C) with and without the presence of organic dyes. The electroactivity of PPy prepared with MO and AB significantly increased in all electrolytic media with a capacitance higher than this of the PPy prepared at room temperature. The highest capacitance (1914 F g-1) was obtained for PPy-MO in 0.2 M HCl solution. The impedance spectra of PPy showed a decrease in charge transfer resistance when the dyes were present. This indicates a conductivity increase of PPy. Improved electrochemical stability was observed for PPy, PPy-MO, and PPy-AB prepared at -24 °C, wherein a steady gain of capacitance was maintained during 5000 potential cycling. In addition, a PPy-based supercapacitor device was fabricated to demonstrate the energy storage characteristics of PPy, where it showed good capacitive behavior and stability. Overall, frozen-state polymerized PPy posed an impressive capacitive performance for flexible supercapacitors.

Polypyrrole Aerogels: Efficient Adsorbents of Cr(VI) Ions from Aqueous Solutions.

Three-dimensional and porous polypyrrole (PPy) aerogels were prepared using a facile two-step procedure in which cryogels were synthesized via the cryopolymerization of pyrrole with iron (III) chloride in the presence of supporting water-soluble polymers (poly(N-vinylpyrrolidone), poly(vinyl alcohol), gelatin, methylcellulose or hydroxypropylcellulose), followed by freeze-drying to obtain aerogels. The choice of supporting polymers was found to affect the morphology, porosity, electrical conductivity, and mechanical properties of PPy aerogels. PPy aerogels were successfully used as adsorbents to remove toxic Cr(VI) ions from aqueous solutions.

One-Step Accelerated Synthesis of Conducting Polymer/Silver Composites and Their Catalytic Reduction of Cr(VI) Ions and p-Nitrophenol.

In this paper, silver nitrate was used as an oxidant to prepare polyaniline, polypyrrole, and poly(3,4-ethylene dioxythiophene)/silver composites through a simultaneous oxidation/reduction process. In addition, p-phenylenediamine was added with 1 mole% relative to the concentrations of the monomers to accelerate the polymerization reaction. The prepared conducting polymer/silver composites were characterized by scanning and transmission electron microscopies to study their morphologies; Fourier-transform infrared and Raman spectroscopies to confirm their molecular structures; and thermogravimetric analysis (TGA) to study their thermal stabilities. The silver content in the composites was estimated by energy-dispersive X-ray spectroscopy, ash analysis, and TGA. The conducting polymer/silver composites were utilized for the remediation of water pollutants through catalytic reduction. Hexavalent chromium ions (Cr(VI)) were photocatalytically reduced to trivalent chromium ions, and p-nitrophenol was catalytically reduced to p-aminophenol. The catalytic reduction reactions were found to follow the first-order kinetic model. Among the prepared composites, polyaniline/silver composite has shown the highest activity for the photocatalytic reduction of Cr(VI) ions with an apparent rate constant of 0.226 min-1 and efficiency of 100% within 20 min. Additionally, poly(3,4-ethylene dioxythiophene)/silver composite showed the highest catalytic activity towards the reduction of p-nitrophenol with an apparent rate constant of 0.445 min-1 and efficiency of 99.8% within 12 min.

Frozen-State Polymerization as a Tool in Conductivity Enhancement of Polypyrrole.

Polypyrrole (PPy) is oxidatively polymerized in the frozen state at -24 °C in the presence of various organic dyes as morphology guiding agents in order to form homogeneous 1D PPy nanoforms. The freezing polymerization of pyrrole has a significant influence on the electrical conductivity and thermal stability but negligible influence on the yield compared to widely used room temperature polymerization.

pH-responsive and antibacterial properties of self-assembled multilayer films based on chitosan and tannic acid.

Polyelectrolyte layer-by-layer (LbL) films that disintegrate under physiological conditions are intensively studied as coatings to enable the release of bioactive components. Herein, we report on the interactions and pH-stability of LbL films composed of chitosan (CH) or N-(2-hydroxypropyl)-3-trimethylammonium chitosan chloride (CMCH) and tannic acid (TA), employed to guarantee the film disintegration. The self-assembly of TA with CH and CMCH at pH 5 and with CMCH at pH 7.4 were proven by turbidimetric, surface plasmon resonance and UV-Vis analyses. The LbL films exhibited pH-dependent properties; CMCH/TA films prepared at pH 7.4 showed exponential growth as well as a higher layer thickness and surface roughness, whereas films prepared at pH 5 grew linearly and were smoother. The film stability varied with the pH used for film assembly; CH/TA films assembled at pH 5 were unstable at pH 8.5, whereas CMCH/TA films assembled at pH 7.4 disintegrated at pH 4. All films exhibited a similar disassembly at pH 7.4. The coatings reduced the adhesion of E. coli and S. aureus by approximately 80%. CMCH-terminated CMCH/TA films were more resistant to bacterial adhesion, whereas CH-terminated CH/TA films demonstrated stronger killing activity. The prepared pH-triggered decomposable LbL films could be used as degradable coatings that allow the release of therapeutics for biomedical applications and also prevent bacterial adhesion.

Tailoring of carbonized polypyrrole nanotubes core by different polypyrrole shells for oxygen reduction reaction selectivity modification.

By using methyl orange template, polypyrrole nanotubes were obtained by the oxidative polymerization of pyrrole. The nanotubes were carbonized in inert atmosphere to nitrogen-enriched carbon nanotubes. These were subsequently coated with 20 wt% of polypyrrole prepared in the absence or the presence of anionic dyes (methyl orange or Acid Blue 25). The morphology of all the samples was examined by the electron microscopies, FTIR and Raman spectroscopies. Moreover, X-ray photoelectron spectroscopy and elemental analysis were used to prove the chemical structure and the successful coating process. Electron paramagnetic resonance analysis was used to calculate the spin concentrations. Significant impact of coating method is evidenced with neat polypyrrole coating providing a two-fold capacitance increase compared to uncoated nanotubes, while coating in the presence of Acid Blue 25 decreasing it slightly. With respect to oxygen reduction reaction, coatings irreversibly transformed in the first few cycles in the presence of the products of O2 reduction, presumably hydrogen peroxide, altering the oxygen reduction mechanism. This transformation allows the tailoring of the polymeric shell, over ORR active carbonaceous core, and tuning of the catalyst selectivity and optimization of materials performance for a given application - from alkaline fuel cells to hydrogen peroxide generation.