Polyaniline/zinc oxide (PANI/ZnO) composite photocatalysts were prepared from neutral media by in situ chemical oxidation of aniline (ANI) in the presence of different amounts of diethylene glycol (DEG). The PANI/ZnO composite photocatalysts were synthesized to efficiently remove organic dye (acid blue, AB25) from model wastewater. The PANI/ZnO composite photocatalysts were studied with the intention of efficient removal of organic dye (acid blue, AB25) from wastewater to obtain low-cost heterogeneous catalysts that offer high catalytic activity and stability. The conductive PANI polymer, which absorbs Vis irradiation, was used in this work as ZnO absorbs only ultraviolet (UV) irradiation; thus, the composite photocatalysts’ activity was broadened into the Vis region. Characterization of the composite photocatalysts was done by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, scanning electron microscopy, electric conductivity, UV-Vis spectroscopy, and by specific surface area (SBET) measurements. The composites’ photocatalytic activity under solar irradiation was validated by monitoring degradation of the AB25 dye. This study presented that it was possible both to prepare PANI and to prevent ZnO dissolution if in situ polymerization starts from neutral media with the addition of DEG. Additionally, efficient removal of AB25 dye, about 90% in 60 min, was achieved. The first-order rate constants of the photodegradation of AB25 by PANI/ZnO 0.02/0.024/0.04 DEG (and pure ZnO)) were computed to be 0.0272/0.0281/0.0325 (and 0.0062) min−1, indicating that the morphology and surface of the photocatalysts have significantly influenced the catalytic activity.
The polyaniline/TiO2 (PANI/TiO2) composite photocatalysts were prepared by the in situ chemical oxidation of aniline (An) in the presence of TiO2 particles. For this purpose, photocatalysts with different amounts of PANI polymer were prepared and analysed. Fourier-transform infrared (FT-IR) spectroscopy and thermogravimetric (TG) analysis indicated successful synthesis of the PANI polymer and its conductivity was also determined. The micrographs of field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) were used to explain the impact of the aniline amount on the aggregation process during the synthesis of the composites. The smallest size of aggregates was obtained for the photocatalysts with 15% of PANI (15PANI/TiO2) due to the formation of homogenous PANI. The photocatalytic activity of studied PANI/TiO2 photocatalysts was validated by monitoring the discoloration and mineralization of Reactive Red azo dye (RR45) in wastewater. The 15PANI/TiO2 sample presented the highest photocatalytic efficiency under ultraviolet A (UVA) irradiation, in comparison to pure TiO2. This was explained by the formation of uniformly dispersed PANI on the TiO2 particles, which was responsible for the synergistic PANI-TiO2 effect.
Determination of the distribution function of relaxation times (DFRT) is an approach that gives us more detailed insight into system processes, which are not observable by simple electrochemical impedance spectroscopy (EIS) measurements. DFRT maps EIS data into a function containing the timescale characteristics of the system under consideration. The extraction of such characteristics from noisy EIS measurements can be described by Fredholm integral equation of the first kind that is known to be ill-posed and can be treated only with regularization techniques. Moreover, since only a finite number of EIS data may actually be obtained, the above-mentioned equation appears as after application of a collocation method that needs to be combined with the regularization. In the present study, we discuss how a regularized collocation of DFRT problem can be implemented such that all appearing quantities allow symbolic computations as sums of table integrals. The proposed implementation of the regularized collocation is treated as a multi-parameter regularization. Another contribution of the present work is the adjustment of the previously proposed multiple parameter choice strategy to the context of DFRT problem. The resulting strategy is based on the aggregation of all computed regularized approximants, and can be in principle used in synergy with other methods for solving DFRT problem. We also report the results from the experiments that apply the synthetic data showing that the proposed technique successfully reproduced known exact DFRT. The data obtained by our techniques is also compared to data obtained by well-known DFRT software (DRTtools).
Electrochemical impedance spectroscopy is attracting more attention due to an increasing production of power sources. One highly popular tool for diagnosing diverse power sources is distribution function of relaxation times (DRT), which has led to numerous approaches for extracting DRT from impedance data. The majority of these are based on the numerical approximation of integral. However, herein we have applied an analytical approximation of the EIS integral. For the first time, we have employed Levenberg-Marquardt algorithm (LMA) to extract the applicable DRT from impedance data by using the Jacobian matrix that was obtained without any discretization errors. Although LMA was previously used to fit EIS data by DRT characteristics, the DRT profile was not applicable due to discretization errors. In this work, LMA was applied as it has an automatic update of the regularization λ parameter. Tests conducted in this work have shown that LMA is capable of extracting DRT from ZARC and FRAC synthetic data.
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