Ozonation of Two Acidic Azo Dyes with Different Substituents

The ozonation of two differently substituted azo dyes (Schwarz GRS and Orange Acid 8) in water media is studied. The influence of pH on the effectiveness of the ozonation at various initial concentrations of each dye is explored. It was found out that the rates of decolorization for amino-group substituted dyes reflect the considerable influence by the widely varying initial pH from 4.5 to 10. Specifically, the highest effect of decolorization of this dye was obtained at the highest pH studied (pH 10) for all initial concentrations of the solutions. Considering the dye without an amino-group substitute, the rates of color disappearance in ozonation reflected to a lower degree the variations of the initial pH. Pseudo-first-order trends of decolorization were observed in all the experimental runs. Regarding the kinetic results obtained, an attempt to explain the different dyes reactivity was made based on the absolute electronegativity (E_lumo + E_homo) of both dyes. The COD/BOD analysis shows that the ozonation of both azo dyes can reduce the sample COD but it could not improve the biodegradability ratio (BOD₅/COD). BOD decrease with ozonation time indicates that the intermediates of the ozonation are of lower biodegradability. Oxalic acid was found as the final product of ozonation of both dyes.     

Mixtures of tertiary amine functionalized azo-containing mesogens with acid-functionalized polymers

A tertiary amine functionalized 4-nitro-4′-alkoxy azobenzene mesogen with a 10 or 12 carbon spacer (azo-nN) was synthesized and complexed in equimolar proportions with poly(acrylic acid) (PA-H) and poly(sulfonic acid) (PSS-H), and investigated by thermogravimetric analysis, differential scanning calorimetry, polarizing optical microscopy, Fourier transform infrared spectroscopy and X-ray diffraction. The neat azo-nN is characterized by a partial bilayer S_A mesophase at higher temperatures, and a highly ordered phase, in which the molecules are stacked orthogonally in bilayers, at lower temperatures. As supported by infrared analysis, for the azo-nN/PA-H mixture, the complexation is partial while for the same azo-nN/PSS-H mixture, complete proton transfer occurs. When the azo-nN is blended with the PA-H, regarded as a weak acid, a biphasic system is generated and the thermotropic behavior of neat mesogen is not significantly affected. In contrast, by mixing the same mesogen with a PSS-H (regarded as a strong acid), the thermotropic behavior is significantly influenced: the complexation generated a partial or interdigitated smectic A or tilted smectic C lamellar phase.     

Transformation of Crystal Phase of Micron-sized Rutile TiO2 and Investigation on its Sonocatalytic Activity

The partial transformation of crystal phase of micron-sized TiO₂ powder from rutile to anatase was realized utilizing microwave irradiation in hydrogen peroxide solution. Afterwards, the ultrasound of low power was used as an irradiation source to induce the transition crystal TiO₂ powder to perform the sonocatalytic activity through the degradation of azo fuchsine in aqueous solution. The results show that the sonocatalytic activity of the transition crystal TiO₂ powder is obviously higher than that of pure micron-sized rutile and anatase TiO₂ powders. The degradation ratio of azo fuchsine in the presence of the transition crystal TiO₂ powder attains nearly 80% within 80 min ultrasonic irradiation.     

Photocatalytic decoloration of water-soluble azo dyes by reduction based on bisulfite-mediated borohydride

Investigation of the photocatalytic decoloration of nine water-soluble anionic azo dyes widely used for the coloration of textiles was conducted in a photoreactor by a selected reduction based on bisulfite-mediated borohydride. The influence of the irradiation power on their decoloration was discussed in this work. The decoloration processes of two typical azo dyes, Reactive Red MS and C.I. Direct Blue 15 were examined with UV–vis measurement and their decoloration kinetics was also investigated. Moreover, identification of benzidine compounds released from the photoreduction of four direct dyestuffs was undertaken. The results indicated that the reduction of the dyes was significantly enhanced under the increasing irradiation. It was found that the overall degradation followed pseudo-first-order kinetics and two distinct stages were observed in the decoloration processes of Reactive Red MS and C.I. Direct Blue 15. The decay rates at first stage were slightly changed, but the decay rates at second stage were significantly affected by the light intensity. In addition, UV–vis spectra showed that the azo linkages in molecule structure of the dyes were destroyed during the decoloration. Finally, dimethoxyl benzidine or benzidine produced from the photoreduction of four direct dyes was identified as the decoloration products through a rapid spectrophotometric method.     

Degradation of a textile azo dye by pulsed arc discharge to the surface of wastewater

The pulsed arc discharge to the surface of wastewater was applied to the degradation of a textile azo dye (Acid Red 27). A high-voltage electrode (discharging electrode) was vertically placed above the surface of the wastewater while the wastewater itself was grounded. The pulsed arc discharge occurred between the tip of the discharging electrode and the surface of the wastewater, producing various oxidative species. Oxygen was used as the working gas instead of air to prevent nitrogen oxides from forming. The effect of several parameters on the chromaticity and chemical oxygen demand (COD) removal was examined. The results obtained showed that the chromaticity of the wastewater was completely removed by this process and the COD also decreased significantly. It has been found that ozone formed in the gas phase mainly affects the removal of the dye. The contribution of other effects such as ultraviolet light emission and OH radical formation during the arc discharge to the degradation of the dye was found to be less than 15%. For the present reactor system, the optimum pH, pulse repetition rate and agitation speed were found to be 3.0, 110 Hz and 300 rpm, respectively.     

Density functional theory study of adsorption geometries and electronic structures of azo-dye-based molecules on anatase TiO2 surface for dye-sensitized solar cell applications

Structural and electronic properties of eight isolated azo dyes (ArNNAr′, where Ar and Ar′ denote the aryl groups containing benzene and naphthalene skeletons, respectively) were investigated by density functional theory (DFT) based on the B3LYP/6-31G(d,p) and TD-B3LYP/6-311G(d,p) methods The effect of methanol solvent on the structural and electronic properties of the azo dyes was elucidated by employing a polarizable continuum model (PCM). Then, the azo dyes adsorbed onto the anatase TiO₂ (101) slab surface through a carboxyl group. The geometries and electronic structures of the adsorption complexes were determined using periodic DFT based on the PWC/DNP method. The calculated adsorption energies indicate that the adsorbed dyes preferentially take configuration of the bidentate bridging rather than chelating or monodentate ester-type geometries. Furthermore, the azo compounds having two carboxyl groups are coordinated to the TiO₂ surface more preferentially through the carboxyl group connecting to the benzene skeleton than through that connecting to the naphthalene skeleton. The dihedral angles (Φ_B-N) between the benzene- and naphthalene-skeleton moieties are smaller than 10° for the adsorbed azo compounds containing one carboxyl group. In contrast, Φ_B-N > 30° are obtained for the adsorbed azo compounds containing two carboxyl groups. The almost planar conformations of the former appear to strengthen both π-electrons conjugation and electronic coupling between low-lying unoccupied molecular orbitals of the azo dyes and the conduction band of TiO₂. On the other hand, such coupling is very weak for the latter, leading to a shift of the Fermi level of TiO₂ in the lower-energy direction. The obtained results are useful to the design and synthesize novel azo-dye-based molecules that give rise to higher photovoltaic performances of the dye-sensitized solar cells.     

Cathode modification with peptide nanotubes (PNTs) incorporating redox mediators for azo dyes decolorization enhancement in microbial fuel cells

To enhance azo dye reduction in cathode of microbial fuel cells (MFCs) and power generation, a novel cathode modification method was developed on carbon paper (CP) through immobilization of redox mediators (RMs) with self-assembled peptide nanotubes (PNTs) as the carrier. Results showed that the optimum peptide concentration for PNT self-assembly on electrode and Orange II decolorization in MFCs was 2 mg mL^?1. The PNT/RMs/CP electrodes exhibited higher electrocatalytic activities than PNT or RM solely modified electrodes and raw carbon paper electrode. MFCs loaded with the riboflavin (RF)/PNT modified cathode (PNT/RF/CP) or anthraquinone-2, 6-disulfonate (AQDS)/PNT modified cathode (PNT/AQDS/CP) showed an enhanced decolorization rate to Orange II compared to that with the control electrode, with the reduction kinetic constants increased by 1.3 and 1.2 folds, respectively. Furthermore, the MFCs with the PNT/AQDS/CP cathode and PNT/RF/CP cathode generated a higher maximum power density of 55.5 mW m^?2 and 72.6 mW m^?2, respectively, compared to the control (15.5 mW m^?2). The PNT/RMs modification could reduce cathode total internal resistance and accelerate electron transfer from electrodes to dyes, which may result in the enhanced performance of MFCs.     

On-off switching properties of one-dimensional photonic crystals consisting of azo-functionalized polymer liquid crystals having different methylene spacers and polyvinyl alcohol

In this paper, photoresponsive behavior of multi-bilayered films having precisely controlled layer thickness prepared by stacking an azo-functionalized polymer liquid crystal, PMAzXAc, and polyvinyl alcohol alternatively, PVA, is described. The multi-bilayered films were found to reflect a light of specific wavelength depending on the layer thickness and refractive index, and showed the reversible change in the reflection intensity by irradiation with visible and UV lights. The change in the reflection intensity was brought about by change in the molecular orientation of PMAzXAc between an out-of-plane orientation and a photo-induced isotropic state, and was strongly dependent on the number of methylene spacer of PMAzXAc linking the azobenzene side group with the acrylate polymer main chain. PMAz6Ac with hexa-methylene spacer showed the largest change in the reflection intensity, while smaller change in the reflection intensity was observed for PMAzXAc having shorter or longer methylene spacer than 6. The effect of the methylene spacers on the photochemical change in the molecular orientation of azobenzene chromophores in the multi-bilayered films will be discussed.     

对羟基偶氮苯甲酸的合成及光致变色性能研究

研究对羟基偶氮苯甲酸(PHABA)的合成方法及其光响应性能。在低温盐酸条件下,完成对氨基苯甲酸与亚硝酸钠的重氮化反应,再与苯酚pH=9条件下完成偶合反应,产品收率82.6%。氯仿溶剂中,PHABA特征吸收波长为357 nm和240 nm,紫外光照射实验显示,PHABA具备动力学一级反应特征的顺反异构光致变色特性,速率常数为7.46×10-4 min-1。