Magnetic Polypyrrole-Gelatin-Barium Ferrite Cryogel as an Adsorbent for Chromium (VI) Removal.

Polypyrrole-gelatin aerogels, containing magnetic barium ferrite (BaFe) particles, (PPy-G-BaFe) were synthesized by oxidative cryopolymerization and used as adsorbents for the removal of Cr(VI) from aqueous media. The removal was performed at pH 4, which was shown to be the optimal value, due to HCrO4- being the dominant species in these conditions and its more favorable adsorption and reduction compared to CrO42-, present at pH > 4. It was found that the presence of magnetic BaFe particles had no effect on the adsorption performance of PPy aerogels in terms of capacity and kinetics, which was attributed to its relatively low content in the composite. After the adsorption, the presence of chromium in the composites was confirmed by EDX and its electrostatic interaction with the adsorbent was pointed at by vibrational spectroscopy, corresponding to the accepted adsorption mechanism. The adsorption kinetics followed the pseudo-second-order model pointing at chemisorption being the rate-limiting step. The adsorption isotherm data was best fitting with the Temkin model. The maximum adsorption capacity, calculated using the Langmuir model, was 255.8 mg g-1 (the maximum experimental value was 161.6 mg g-1). Additionally, the possibility of Cr(VI) adsorption in the presence of Cl-, Br-, NO3- and SO42- as interfering ions was shown.

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.

Tuning of Morphological and Antibacterial Properties of Poly(3,4-ethylenedioxythiophene):Peroxodisulfate by Methyl Violet.

This study demonstrates a one-step synthesis of poly(3,4-ethylenedioxythiophene) (PEDOT) in the presence of the methyl violet (MV) dye. The structural properties of PEDOT:peroxodisulfate were studied using Raman and MALDI-TOF spectroscopies. The use of the MV dye in the polymerization process resulted in a change in the typical irregular morphology of PEDOT:peroxodisulfate, leading to the formation of spherical patterns. SEM and TEM analyses revealed that increasing the dye concentration can produce larger spherical aggregates probably due to the hydrophobic and π-π interactions. These larger aggregates hindered the charge transport and reduced the electrical conductivity. Interestingly, at higher dye concentrations (0.05 and 0.075 M), the PEDOT:peroxodisulfate/MV films exhibited significantly improved antibacterial activity against Staphylococcus aureus and Escherichia coli. Furthermore, the PEDOT:peroxodisulfate films with the incorporated MV dye exhibited a well-defined and repeatable redox behavior. The remarkable amalgamation of their optical, electrochemical and antibacterial properties provides the PEDOT:peroxodisulfate/MV materials with an immensely diverse spectrum of applications, including in optical sensors and medical devices.

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.

Effect of a Zr-Based Metal-Organic Framework Structure on the Properties of Its Composite with Polyaniline.

Composites of polyaniline (PANI) and Zr-based metal-organic frameworks (MOFs), UiO-66 and UiO-66-NH2, were synthesized by the oxidative polymerization of aniline in the presence of MOF templates with the MOF content in the resulting materials (78.2 and 86.7 wt %, respectively) close to the theoretical value (91.5 wt %). Scanning electron microscopy and transmission electron microscopy showed that the morphology of the composites was set by the morphology of the MOFs, whose structure was mostly preserved after the synthesis, based on the X-ray diffraction data. Vibrational and NMR spectroscopies pointed out that MOFs participate in the protonation of PANI and conducting polymer chains were grafted to amino groups of UiO-66-NH2. Unlike PANI-UiO-66, cyclic voltammograms of PANI-UiO-66-NH2 showed a well-resolved redox peak at around ≈0 V, pointing at the pseudocapacitive behavior. The gravimetric capacitance of PANI-UiO-66-NH2, normalized per mass of the active material, was also found to be higher compared to that of pristine PANI (79.8 and 50.5 F g-1, respectively, at 5 mV s-1). The introduction of MOFs into the composites with PANI significantly improved the cycling stability of the materials over 1000 cycles compared to the pristine conducting polymer, with the residual gravimetric capacitance being ≥100 and 77%, respectively. Thus, the electrochemical performance of the prepared PANI-MOF composites makes them attractive materials for application in energy storage.

Polypyrrole-Barium Ferrite Magnetic Cryogels for Water Purification.

Magnetic polypyrrole-gelatin-barium ferrite (PPy-G-BaFe) cryogels/aerogels were synthesized by one-step oxidative cryopolymerization of pyrrole in the presence of various fractions of barium ferrite (BaFe) nanoparticles, dispersed in aqueous gelatin solution. The successful incorporation of BaFe into the composites was confirmed by elemental analysis and scanning electron microscopy paired with an energy-dispersive X-ray detector. The maximum achieved content of BaFe in the resulting material was 3.9 wt%. The aerogels with incorporated BaFe had significantly higher specific surface area and conductivity, reaching 19.3 m2 g-1 and 4 × 10-4 S cm-1, respectively, compared to PPy-G aerogel, prepared in the absence of BaFe (7.3 m2 g-1 and 1 × 10-5 S cm-1). The model adsorption experiment using an anionic dye, Reactive Black 5, showed that magnetic PPy-G-BaFe aerogel, prepared at 10 wt% BaFe fraction, had significantly higher adsorption rate and higher adsorption capacity, compared to PPy-G (dye removal fraction 99.6% and 89.1%, respectively, after 23 h). Therefore, the prepared PPy-G-BaFe aerogels are attractive adsorbents for water purification due to their enhanced adsorption performance and the possibility of facilitated separation from solution by a magnetic field.