Effect of a sulfonated azo dye and sulfanilic acid on nitrogen transformation processes in soil

Introduction of organic dyes into soil via wastewater and sludge applications has been of increasing concern especially in developing or under-developed countries where appropriate management strategies are scarce. Assessing the response of terrestrial ecosystems to organic dyes and estimating the inhibition concentrations will probably contribute to soil remediation studies in regions affected by the same problem. Hence, an incubation study was conducted in order to investigate the impact of a sulfonated azo dye, Reactive Black 5 (RB5) and sulfanilic acid (SA), a typical representative of aromatic sulfonated amines, on soil nitrogen transformation processes. The results apparently showed that nitrogen related processes in soil can be used as bioindicators of anthropogenic stress caused by organic dyes. It was found that urease activity, arginine ammonification rate, nitrification potential and ammonium oxidising bacteria numbers decreased by 10–20% and 7–28% in the presence of RB5 (>20 mg/kg dry soil) and SA (>8 mg/kg dry soil), respectively. Accordingly, it was concluded that organic dye pollution may restrict the nitrogen-use-efficiency of plants, thus further reducing the productivity of terrestrial ecosystems. Furthermore, the response of soil microbiota to SA suggested that inhibition effects of the organic dye may continue after the possible reduction of the parent dye to associated aromatic amines.     

The synthesis, characterization, thermal and optical properties of copper, nickel, and vanadyl complexes derived from azo dyes

Two, novel, tetradentate Schiff-base ligands, namely bis-5-phenylazosalicylaldehyde diethylenetriimine and bis-5-[(4-methoxyphenyl)azo]salicylaldehyde diethylenetriimine, as well as their Cu²⁺, Ni²⁺, and VO²⁺ complexes, were synthesized and characterized using elemental analysis, infrared and also UV–Visible spectroscopy, ¹HNMR and mass spectra. The thermal stability of the free ligands and the related metal complexes, as determined using differential scanning calorimetry and thermal gravimetric analysis, were found to be thermally stable upto 240–275 °C depending on the type of ligand and the central metal atom. The λ_max of the ligands and their transition metal complexes in the region 300–800 nm are discussed. The novel metal complexes offer potential for application as recording media owing to both their absorption spectra in the blue-violet light region and high thermal stability.     

Integration of photocatalysis and membrane distillation for removal of mono- and poly-azo dyes from water

The paper reports investigations on the application of anatase-phase TiO₂ for the removal of azo dyes in a hybrid system coupling photocatalysis with direct contact membrane distillation (DCMD, MD). The process was conducted in a laboratory-scale installation equipped with a PP capillary module. The influence of reaction temperature and initial concentration of azo dyes on the effectiveness of their photodegradation was especially investigated. Two mono-azo dyes: Acid Red 18 (AR18) and Acid Yellow 36 (AY36) and one poly-azo dye, Direct Green 99 (DG99) were applied as model compounds. The increase of the reaction temperature from 313 to 333 K resulted in an improvement of the efficiency of photodecomposition of the dyes, as was found on the basis of changes of their masses in the feed solution. The comparison of the results obtained during photocatalysis alone and hybrid photocatalysis-MD process revealed that the reduction of feed volume in MD did not affect the photodegradation rate of the azo dyes. An improvement of the effectiveness of the degradation of dyes was obtained by an application of solutions with lower initial concentration (10 instead of 30 mg/dm³). Regardless of the process parameters applied, the product (distillate) was almost pure water with conductivity lower than 0.3 mS/m and pH above 5.2.     

The synthesis and structural study of two benzothiazolyl azo dyes: X-ray crystallographic and computational study of azo–hydrazone tautomerism

The synthesis, FT-IR, ¹H and ¹³C NMR characterisation, as well as crystal and molecular structure determined by single-crystal X-ray diffraction data, of two azo dyes derived from 6-aminobenzothiazole: 6-[(4-N,N-dimethylaminophenyl)diazenyl]benzothiazole and 6-[(2-hydroxy-1-naphthyl)diazenyl]benzothiazole are reported. Both dyes are essentially planar with the exclusion of methyl groups in 6-[(4-N,N-dimethylaminophenyl)diazenyl]benzothiazole, which exibits 100% E-configuration in terms of orientation of the substituents about the central azo linkage. Single-crystal X-ray study of 6-[(2-hydroxy-1-naphthyl)diazenyl]benzothiazole was undertaken to established whether the hydrazone or azo tautomer was present in the solid state as well as any potential shift in tautomeric equilibrium imparted by temperature variation (296 and 100 K). Density functional theory calculations revealed that the hydrazone tautomer was more stable than the azo tautomer and that the tautomeric equilibrium was shifted towards the hydrazone form at lower temperature.     

Mn(II), Co(II) and Ni(II) complexes of 4-(2-thiazolylazo)resorcinol: Syntheses, characterization, catalase-like activity, thermal and electrochemical behaviour

Manganese(II), cobalt(II) and nickel(II) acetates react with the ligand, 4-(2-thiazolylazo)resorcinol, to form complexes of general formula [ML₂] for MCo(II), Ni(II) and [ML₂]·2H₂O for MMn(II). Each of the azo complexes was characterized using elemental analysis, electrolytic conductance, UV–visible spectroscopy and magnetic susceptibility. An octahedral structure is proposed for all complexes prepared, which molar conductance data revealed to be non-electrolytes. IR spectra reveal that the ligand is coordinated to the metal ions in a tridentate manner via the resorcinol OH, azo N and thiazole N groups as donor sites. The electrochemical behaviour of the ligand and its complexes were obtained by cyclic voltammetry. Thermal decomposition studies were undertaken to secure additional information on the structure of the investigated compounds. The manganese(II) complex catalysed the disproportionation of hydrogen peroxide in the presence of imidazole.     

Kinetics and equilibrium studies of removal of an azo dye from aqueous solution by adsorption onto scallop

In the present work removal of an azo dye (Reactive Black 5) was investigated from aqueous solution by adsorption onto scallop as a low-cost and widely available adsorbent. The effect of various operational parameters, such as contact time, pH, initial dye concentration and adsorbent dosage on the removal efficiency of dye was studied. Removal efficiency declined with the increase in solution pH and initial dye concentration but with the decrease in adsorbent dosage. Experimental equilibrium and kinetics data were fitted by Langmuir and Freundlich isotherms and pseudo-first-order and pseudo-second-order kinetic models, respectively.     

Fe掺杂g⁃C3N4光催化活化过硫酸钠降解偶氮染料

以硝酸铁为铁源,通过浸渍法制备Fe?C₃N₄复合材料。采用FT?IR对Fe?C₃N₄材料进行了表征分析。结果表明,Fe掺杂不改变g?C₃N₄的骨架结构,可以增加g?C₃N₄材料的光催化性能。以橙黄II为目标污染物,在可见光下Fe?C₃N₄催化活化过硫酸钠降解偶氮染料,考察了过硫酸钠物质的量、Fe?C₃N₄质量浓度、橙黄II质量浓度及pH对降解效果的影响,并对反应进行了动力学研究,分析了所制备的催化材料的稳定性。结果表明,在Fe?C₃N₄质量浓度为2.0 g/L、过硫酸钠与污染物物质的量比为1 200∶1和pH=3的条件下,降解效果最好,降解率为77.8%;Fe?C₃N₄/过硫酸钠体系对偶氮染料的降解满足准二级动力学方程;Fe?C₃N₄材料具有可重复利用性。     

Synthesis and the third-order non-linear optical properties of new azobenzene-containing side-chain polymers

A new series of aromatic azobenzol compounds containing vinyl have been designed as monomers. The azobenzene-containing side-chain polymers containing azo NLO chromophore in each side chain have been synthesized via free radical polymerization. FT-IR, elemental analysis and ¹H NMR were performed to characterize the azo monomers. The molecular weight of the polymers and their distribution were determined by gel permeation chromatography (GPC). The third-order NLO coefficient of azo monomers and their polymers were measured by degenerated four wave mixing (DFWM) technique. As a result, the enhancement of the molecular conjugation and the increase of the NLO chromophore concentration in the molecular chain contribute much to heightening the third-order NLO effect. The electronic effect of substituent on the azobenzol group and the push–pull electronic structure contributes much to enhancing the NLO property.     

Discoloration process modeling by neural network

The photo-oxidation of acid orange 52 dye was performed in the presence of H₂O₂, utilizing UV light, aiming the discoloration process modeling and the process variable influence characterization. The discoloration process was modeled by the use of feedforward neural network. Each sample was characterized by five independent variables (dye concentration, pH, hydrogen peroxide volume, temperature and time of operation) and a dependent variable (absorbance). The neural model has also provided, through Garson Partition coefficients and the Pertubation method, the independent variable influence order determination. The results indicated that the time of operation was the predominant variable and reaction mean temperature was the lesser influent variable. The neural model obtained presented coefficients of correlation on the order 0.98, for sets of trainability, validation and testing, indicating the power of prediction of the model and its character of generalization.     

Development of a TiO2 modified optical fiber electrode and its incorporation into a photoelectrochemical reactor for wastewater treatment

Electrochemical advanced oxidation processes (EAOPs) are used to chemically burn non biodegradable complex organic compounds that are present in polluted effluents. A common approach involves the use of TiO₂ semiconductor substrates as either photocatalytic or photoelectrocatalytic materials in reactors that produce a powerful oxidant (hydroxyl radical) that reacts with pollutant species. In this context, the purpose of this work is to develop a new TiO₂ based photoanode using an optic fiber support. The novel arrangement of a TiO₂ layer positioned on top of a surface modified optical fiber substrate, allowed the construction of a photoelectrochemical reactor that works on the basis of an internally illuminated approach. In this way, a semi-conductive optical fiber modified surface was prepared using 30 μm thickness SnO₂:Sb films on which the photoactive TiO₂ layer was electrophoretically deposited. UV light transmission experiments were conducted to evaluate the transmittance along the optical fiber covered with SnO₂:Sb and TiO₂ showing that 43% of UV light reached the optical fiber tip. With different illumination configurations (external or internal), it was possible to get an increase in the amount of photo-generated H₂O₂ close to 50% as compared to different types of TiO₂ films. Finally, the electro-Fenton photoelectrocatalytic Oxidation process studied in this work was able to achieve total color removal of Azo orange II dye (15 mg L⁻¹) and a 57% removal of total organic carbon (TOC) within 60 min of degradation time.