The Oxidation Mechanism of Aniline by Ozone Water and Ozone Micro-nano Bubble Water and Its Influencing Factors

Aniline is a kind of refractory contaminant that is difficult to be degraded by microorganisms. Ozone is a green and efficient reagent to oxidize aniline, while the ozone oxidation efficiency is restricted by the low ozone mass transfer rate. Micro-nano bubble ozonation has been developed as a new method to significantly improve the ozone utilization rate, while the characteristics of ozone micro-nano bubble when compared with dissolved ozone is not clear. The paper carried out batch experiments to research the oxidation effect of aniline by ozone water (OW) and ozone micro-nano bubble water (OMNBW), and found that the degradation rate of aniline by OMNBW was 2.8~5.9% higher than that by OW. The increase of pH had a negative effect on the degradation of aniline by OW and OMNBW. SO42-, Cl-, HCO­3- and Mg2+ could inhibit the degradation efficiency by 0.04%, 0.99%, 0.44% and 10.4% for OW, while the ratios were 1.1%, 6.4%, 4.1% and 1.5% for OMNBW. The addition of humic acid and fulvic acid could decrease the oxidation rate of aniline by 35% and 49% for OW, while the ratios were 41% and 62% for OMNBW. Through quenching experiment, it was found that the direct oxidation by ozone molecules and the indirect oxidation by superoxide radicals were main pathways for aniline oxidation by OW and OMNBW. This work provided a practical guide for the application of OMNBW in wastewater and groundwater treatment process.

The Impact of In Situ Polymerization Conditions on the Structures and Properties of PANI/ZnO-Based Multiphase Composite Photocatalysts

We have synthesized polyaniline/ZnO-based (PANI/ZnO) multiphase composite photocatalysts from acid media by a newly proposed two-step in situ polymerization. The first step of synthesis yielded PANI salt required for the PANI/ZnO synergistic effect. In the second step, the aniline oxidation continued, without ZnO dissolution, and it produced PANI base. Thus, both PANI salt and base phases in the composites were detected by FTIR and UV/Vis, while the presence of both ZnO and PANI polymer was confirmed by XRD. Additionally, XRD also showed Zn5(OH)8(NO3)2·2H2O and Zn(SO4)(H2O) phases in PANI/ZnO-based multiphase composites. Furthermore, the impact of the synthesis conditions on the morphology of the composites was investigated by FE-SEM. The images displayed that ZnO particles were encapsulated in PANI sheets that were formed by the aniline oligomers. Photocatalytic evaluation of PANI/ZnO-based catalysts (i.e., degradation of Acid Blue 25 dye) was conducted and the obtained results confirmed that all the studied composites experienced the PANI/ZnO synergistic effect. It was observed that the best photocatalytic properties were held by the PANI/ZnO_2 sample due to its optimal particle size.

The First Stages of Chemical and Electrochemical Aniline Oxidation—Spectroscopic Comparative Study

There are several types of aniline oligomers that can be formed in the early stages of aniline oxidation: linear oligomers with repeating units joined in para positions, and various branched and polycyclic oligomers, being the two most important groups. The fraction of these different oligomeric groups depends upon the reaction conditions of aniline oxidation. The aim of this study was to analyze the first products of the chemical and electrochemical oxidation of aniline at the (starting) pH 1 and 7, in order to specify the conditions of the formation of phenazine-like oligomers, and to test the theory that they have an important role in polyaniline film formation. We have confirmed that phenazine-like oligomers do not form at pH 1, neither in the chemical nor the electrochemical oxidation of aniline; however, they form in both chemical and electrochemical oxidation of aniline at pH 7. Phenazine-like oligomers are thus definitely not necessary intermediates for PANI film formation, not even in the chemical polymerization of aniline. Finally, the redox behavior of phenazine-like oligomers was demonstrated in a medium at pH 1.

The Applications of Solid-State NMR to Conducting Polymers. The Special Case on Polyaniline

Polyaniline is one of the most well studied conducting polymers due to its advanced electrical, chemical, redox and morphological properties. The high conductivity of regular polyaniline, when partially oxidized and doped under acidic conditions, has been associated with the formation of unique electronic states known as polarons and bipolarons. Alternative aniline oxidation products and interesting nanotube and nanorod forms have been observed as the synthesis conditions are varied. Solid-state NMR has offered great opportunities for structural investigations and the determination of molecular dynamics in such a complex and diverse material. This review summarizes various applications of solid-state NMR techniques to polyaniline and its derivatives and the information that can be obtained by solid-state NMR.

Conductive Cotton by In Situ Laccase-Polymerization of Aniline

Conductive cotton fabrics were obtained via in situ aniline polymerization by laccase from Myceliophthora thermophila under mild reaction conditions without the addition of strong proton acids. The reactions were conducted using two types of reactors, namely a water bath (WB) and an ultrasonic bath (US), and the role of a mediator, 1-hydroxybenzotriazol (HBT), on the laccase-assisted polymerization of aniline was investigated. A similar polymerization degree was obtained when using both reactors—however, the ultrasonic bath allowed the experiments to be conducted in shorter periods of time (24 h for WB vs. 2 h for US). The data obtained also revealed that the mediator (1-hydroxybenzotriazol-HBT) played a crucial role in aniline oxidation. A higher conversion yield and polymerization degree were obtained when the reaction was conducted in the presence of this compound, as confirmed by MALDI-TOF analysis. The cotton fabrics coated with polyaniline presented deep coloration and conductivity, especially when the mediator was included on the reactional system. The results obtained are a step forward in the enzymatic polymerization of aniline with the purpose of obtaining coloured conductive textile surfaces, with potential applications in wearable electronics.