不同结构偶氮染料在TiO2纳米颗粒表面的吸附和光催化降解

为研究不同结构的水溶性偶氮染料在TiO2光催化剂表面的吸附和光催化降解行为,选择4种在印染工业中常用的水溶性偶氮染料：活性红MS、活性蓝B、酸性媒介黑PV和酸性橙156作为研究对象,分别考察在不同pH值和氯化钠存在条件下,TiO2光催化剂对它们的吸附行为和吸附模式,并通过数学模拟方法计算了其在TiO2光催化剂表面的吸附参数,还研究了它们在TiO2光催化剂表面的光催化降解反应. 实验结果表明,4种水溶性偶氮染料在TiO2表面的吸附量随着pH值的升高逐渐降低,而且当pH值处于4~8之间时吸附量下降最为显著. 在相同的吸附条件下,2种酸性染料在TiO2表面的吸附量高于2种活性染料,并且在氯化钠存在下它们的吸附量都得到不同程度的提高. 水溶性偶氮染料的吸附过程符合Langmuir等温吸附模型,活性染料比酸性染料具有更高的吸附平衡常数和覆盖率. 在TiO2对偶氮染料的光催化降解反应中,脱色率和反应速率常数随pH值的升高而降低,并且活性染料比酸性染料更易于发生光催化降解反应.     

The effect of perspiration on photo-induced chemical reaction of azo dyes and the determination of aromatic amine products

In order to investigate the impact of perspiration on photo-induced chemical reaction of azo dyes and the carcinogenic aromatic amine products produced from the reaction, we have carried out experimental studies on the photochemical reaction of C.I. Reactive Red 2 mixed with American Association of Textile Chemists and Colorists（AATCC）standard artificial perspiration. UV-vis spectroscopic technique was employed to monitor the reaction processes, and the reaction products were analyzed by hollow fiber protected liquid-liquid-liquid phase micro-extraction with capillary electrophoresis（HF-LLLME-CE). The results showed that perspiration had remarkable influence on the photochemical reaction of azo dyes. Aromtic amines formed during the photochemical process as a result of reduction of azo dyes by organic components in perspiration. The HF-LLLME-CE methodology was validated in analyzing aromatic amines produced from the photochemical degradation of azo dye C.I. Reactive Red 2 and C.I. Acid Red 35 mixed with artificial perspiration.     

Application of genetic algorithm to color recipe formulation using reactive and direct dyestuffs mixtures

Color reproduction is a science in constant development. In this article, a new model to solve the color recipe prediction problem using a genetic algorithm is proposed. The objective is to optimize the color recipe prediction stage by determining the dyes to use in a mixture and their respective proportions to reproduce the target color. Two ranges of dyes were used for dyeing 100% cotton woven fabrics: three reactive dyes (CI Reactive Red 238, CI Reactive Yellow 145, and CI Reactive Blue 235) and four direct dyes (CI Direct Orange 34, CI Direct Red 227, CI Direct Blue 85, and CI Direct Black 22). The criterion of optimization, in reproducing the desired shades, is to minimize the CMC color difference between the desired reference color and the color resulting of the predicted recipe. The proposed algorithm revealed good results with small CMC color differences between target and reproduced colors. The effectiveness of the algorithm was also evaluated and proven by calculating errors between the predicted concentrations in the proposed recipes and the actual concentrations.     

Kinetics of dye decolorization in an air–solid system

The photocatalytic decolorization of adsorbed organic dyes (Acid Blue 9, Acid Orange 7, Reactive Black 5 and Reactive Blue 19) in air was examined, applicable to self-cleaning surfaces and catalyst characterization. Dye-coated Degussa P25 titanium dioxide (TiO₂) and dye-coated photo-inert aluminum oxide (Al₂O₃) particles, both of sub-monolayer initial dye coverage, were illuminated with 1.3 mW cm⁻² of near-UV light. Visual evidence of color removal is reported with photographic images. Two methods, Indirect and Direct Analysis, were employed to quantitatively examine the decolorization kinetics of dyes using UV–visible transmission and diffuse reflectance spectroscopy, respectively. A decrease in dye concentration with time was observed with near-UV illumination of dye-coated TiO₂ powders for all dyes. Dyes did not photodegrade significantly on photo-inert Al₂O₃.

UV–visible spectroscopy data was used to model the kinetics of the photocatalytic degradation. Two first-order reactions in series provided the most convincing rate form for the photodegradation of dyes adsorbed to TiO₂, with a first step the conversion of colored dye to colored intermediate, and the second the conversion to colorless product(s). The first rate constant was of similar magnitude for all dyes, averaging k₁ = 0.13 min⁻¹. Similarly, for the second, k₂ = 0.0014 min⁻¹.     

九种致癌染料剥色工艺的优化

针对纺织品上可能存在的九种致癌染料(C.I.酸性红26、C.I.分散橙11、C.I.分散黄3、C.I.分散蓝1、C.I.直接蓝6、C.I.直接黑38、C.I.直接红28、C.I.碱性红9、C.I.碱性紫14),本文研究并比较了不同剥色工艺对不同致癌染料剥色效果的影响.并提出选用加入尿素的甲醇作为剥色剂,使用超声功率为100W的超声波在70℃处理30分钟可以获得比较理想的剥色效果.     

Electrochemical discolouration and degradation of reactive dichlorotriazine dyes: reaction pathways

Results of electrochemical oxidation of two reactive dichlorotriazine dyes: Reactive Red 2 and Reactive Blue 81, are presented in this paper. Two electrode materials: Ti/TiO₂(70%)–RuO₂(30%) and carbon felt, were applied in the investigations as anodes. Voltammetric measurements show that Reactive Blue 81 electrooxidation proceeds easier and with higher rate than electrooxidation of Reactive Red 2. Both dyes are oxidised irreversibly in at least one electrode step before oxygen evolution starts at the electrode. Effectiveness of electrochemical oxidation under potentiostatic conditions achieved for Reactive Blue 81 was higher than for Reactive Red 2, with application of a carbon felt anode. Pulse radiolysis measurements prove addition of ^•OH radical to the dye molecule and formation of cyclohexadienyl and naphthoxyl radicals. Results of voltammetric analysis, pulse radiolysis measurements and GC–MS identification of intermediate products suggest two possible pathways of the dyes electrochemical oxidation.     

Photocatalytic Discoloration of Dyes: Relation between Effect of Operating Parameters and Dye Structure

The process of TiO₂/UV photocatalytic discoloration of wastewaters containing organic dyes is influenced by a number of variables. In this paper, the effects of some of these parameters, i.e., mass of catalyst, initial dye concentration, and pH, were related to the structural nature of the dyes investigated, azo and anthraquinone dyes, two families that are representative of about 75 % of the dyes marketed nowadays. Both bibliographical and own experimental data were used to analyze and discuss the photocatalytic discoloration in terms of dye structure and degradation pathways. It is shown that azo dyes (Methyl Orange, Metanil Yellow, Acid Orange 7, and Reactive Red 120) are more easily discolored than Reactive Blue 19 (anthraquinone dye), due to the higher molecular stability of the latter. It is also shown that azo dye discoloration is more influenced by the initial dye concentration, whereas recalcitrant anthraquinone dyes (Reactive Blue 19) mainly demand for basic pH values to generate enough OH^• radicals. Concerning TiO₂ loading, both the bibliographical and current research data showed no effect of this variable in the experimental range analyzed.     

Enhanced adsorption of two azo dyes produced by carbon modification of TiO2

The process of removal of two azo dyes (Reactive Red 198 and Direct Green 99) from water was investigated. The adsorption of azo dyes onto surfaces of pristine TiO₂, P25 and carbon-modified TiO₂ (at 120 °C for 24 h) was presented. The Freundlich model of adsorption isotherm was found for pristine TiO₂ and TiO₂-P25. Modification of TiO₂ by carbon lead to the change from the Freundlich model to the Langmuir model of adsorption isotherm. For the TiO₂-C photocatalyst the adsorption capacity was determined, which was almost two times higher for Direct Green 99 than Reactive Red 198 dyes. As a result we observed the increase of photocatalytic activity of carbon-modified TiO₂ photocatalyst.     

Cathodic decolourisation of textile waste water containing reactive dyes using a multi‐cathode electrolyser

The reductive decolourisation of textile dyestuffs containing an azo group was investigated by direct cathodic electron transfer CI Acid Red 27 and CI Acid Yellow 9 were used as model compounds for azo dyes. Reactive dyes, eg CI Reactive Red 4, CI Reactive Orange 4, and CI Reactive Black 5, which are in technical use for cellulose dyeing were investigated as representatives of practical importance. A basic characterisation of the reduction–decolourisation behaviour of the dyes was achieved by redox titration with Fe(II)–triethanolamine as reducing agent and parallel spectrophotometric observation of changes in the chromogenic system. From the redox titration experiments basic data describing the experimental conditions for successful cathodic electron transfer can be derived. The electrochemical dyestuff reduction experiments were performed in batch trials using a multi‐cathode electrolyser with high cathode area. According to the typical composition of such dyebaths 0.12 mol dm^?3 NaOH was used as ground electrolyte. The absorbance of the investigated dyestuff solutions could be decreased to below 20% of the initial value. For a 50% decrease in absorbance, electrical energy of about 6 kWh m^?3 is consumed. The process is of particular interest for the treatment of concentrated dyestuff solutions as they are used in continuous dyeing processes. © 2001 Society of Chemical Industry     

Studies on mixture dyeing. IV. Equilibrium adsorption of direct dyes

Chrysophenine G (C.I. Direct Yellow 12), Benzopurpurine 4B (Red 2), Sirius Red 4B (Red 81), Sirius Supra Blue BRR (Blue 71) and Sky Blue 6B (Blue 1) were selected as typical direct dyes, and the equilibrium adsorptions on cellulose (Cellophane) from the 1:1 and 2:1 molar mixture dye baths were investigated at 90° and 70°C. The standard affinity in mixture dyeing was obtained by the equation derived from the assumption of monodispersed and diffusive adsorption. The standard affinity in mixture dyeing was nearly equal to that in single dyeing, except for the Chrysophenine G–Sky Blue 6B system. However, judging from the fiber and solution log sum plots, there was a definite difference between mixture and single dyeing. It was explained by the change of activity of dye and sodium ions on substrate followed by the marked change of the total adsorption. The adsorption behavior of direct dyes is discussed in detail from the viewpoint of concentration dependence of the activity coefficient of dye and sodium ions on the substrate.     

Chemically modified sunflower stalks as adsorbents for color removal from textile wastewater

Quaternary ammonium groups were chemically grafted onto sunflower stalks in order to improve their adsorption performance to anionic species in wastewater. The chemically modified sunflower stalks were evaluated as adsorbents for two basic dyes (Methylene Blue and Basic Red 9) and two direct dyes (Congo Red and Direct Blue 71) in aqueous solutions by using equilibrium isotherms and kinetic adsorption. Before the modification, sunflower stalks exhibited relatively low adsorption to the direct dyes but very high adsorption to the basic dyes. The modified sunflower stalks showed increased adsorption to the anionic dyes, but slightly reduced adsorption to the cationic dyes, due to the existence of quaternary ammonium ions on the surface of the residues. The maximum adsorption capacities of two direct dyes on the modified sunflower stalks are 191.0 and 216.0 mg g for Congo Red and Direct Blue 71 at 50°C, respectively, which were at least four times higher than that of the unmodified residues. The adsorption rates of two direct dyestuffs are much higher on the modified residues than on the unmodified ones. Within 30 min, about 80% of direct dyes were removed from the solutions by the residues. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1841–1850, 1999     

Crystal structure and surface species of CuFe2O4 spinel catalysts in steam reforming of dimethyl ether

The application of catalytic ozonation processes for the decolourisation and mineralisation of coloured aqueous solutions was studied. One acid azo dye, CI Acid Blue 113, and two reactive dyes, CI Reactive Yellow 3 and CI Reactive Blue 5, with azo and anthraquinone chromophores, respectively, were used as representative textile dyes. The catalytic activities of activated carbon, cerium oxide and a ceria-activated carbon composite were evaluated in the removal of the selected dyes. In all cases, with an initial dye concentration of 50 mg/L, a complete decolourisation was achieved by single ozonation in short reaction times (less than 10 min). The ceria-activated carbon composite allowed the highest removal of total organic carbon. For dye concentrations of 50 mg/L, mineralisation degrees of 100%, 98% and 97% were achieved with the composite after 2 h of reaction, respectively for CI Reactive Blue 5, CI Acid Blue 113 and CI Reactive Yellow 3. The activity of the catalyst containing cerium was affected by the presence of carbonate and bicarbonate ions due to their scavenging effect towards hydroxyl radicals; for example the mineralisation degree of CI Reactive Blue 5 (C₀ = 300 mg/L) after 120 min of reaction was only 63%, contrasting with the value of 85% obtained in the absence of carbonates. All the catalytic systems were evaluated in the treatment of textile effluents, collected before or after conventional biological treatment. Catalytic ozonation was proven to be effective when used as tertiary treatment for bio-treated effluents.     

活性蓝Turquoise Blue G的结构表征及性能研究

采用紫外—可见、红外光谱、热重分析和质谱对标题染料进行了表征,确定了活性基的数目。对染色性能和牢度性能进行了研究。并与同类产品进行了比较。     

Impact of Ozonation on Decolorization and Mineralization of Azo Dyes: Biodegradability Enhancement,By-Products Formation,Required Energy and Cost

In the present study ozonation process was implemented to analyze the effect of ozonation time on the rate of chemical oxygen demand (COD) removal, mineralization and rate of decolorization of azo dyes. Three types of azo dyes i.e. Acid Red 14, Direct Red 28 and Reactive Black 5 were selected. Decolorization and mineralization of samples were conducted in batch scale. The COD and color removal efficiency were found to be increasing at a certain time of ozonation. The results with Acid Red 14, Congo Red and Reactive Black 5 dyes solutions lead to maximum COD reduction of 75%, 67% & 50% respectively. 93%, 92% and 94% color removal were achieved after 25 min of ozonation time of the same dyes which highlighted that ozonation process was found to be more efficient for reactive dye decolorization. Ozonation by-products analyzed by ion chromatography resulted that it partially mineralized with the formation of chloride, fluoride, sulphate, nitrate and oxalate ions. During ozonation process a rapid decrease in pH value indicated the acidic nature of by-products. The effect of buffered dye solutions on the ozonoation process highlighted that the decolorization efficiency decreases in comparison to unbuffered dye solutions. Ozonation led to enhancement of biodegradability ratio (BOD₅/COD) and increased electrical conductivity of the dye solutions. Optimum ozonation time required for degradation of dye solutions reflected the evaluation of energy consumption and cost of the treatment after ozonation.     

Extraction of reactive dyes from aqueous solutions by halogen‐free ionic liquids

Dyes are commonly used in various industries and unfortunately many of them are discharged into water bodies, causing environmental problems. In the current study, three hydrophobic, halogen‐free ionic liquids were synthesised and their capability as extracting agents was evaluated using four reactive dyes (CI Reactive Blue 4, CI Reactive Black 5, CI Reactive Orange 16 and CI Reactive Red 2). The ionic liquids, immiscible with the aqueous phase, could extract the reactive dyes from aqueous solutions, withdrawing the same amount of weight. The effects of pH and temperature on the extraction process were also studied. Trioctylmethyl ammonium ethylenediaminetetraacetate displayed a high extraction efficiency (99%), where only 33 mg of ionic liquids extracted 50 mg of CI Reactive Blue 4. Fourier Transform–infrared spectroscopy was used to screen the interaction between the ionic liquid and CI Reactive Blue 4 during the extraction stage.     

Interaction of dis‐azo dyes with quaternized poly(dimethylaminoethyl methacrylate) as a function of the dye structure and polycation charge density

Interactions between some dis‐azo dyes, different by either the position of their sulfonic groups or their number (Ponceau SS, Crocein Scarlet MOO, Congo Red, and Direct Blue 1), and some strong polycations (PCs), with cationic centers in their side chains and dye removal from artificial wastewaters were systematically investigated in this study. PCs with variable charge densities (CDs) were prepared from poly(dimethylaminoethyl methacrylate) by controlled quaternization with benzyl chloride. Even when the main process in the dye removal was charge neutralization (coagulation) for all of the dyes, significant effects of the CD and dis‐azo dye structure on the metachromatic behavior of the dyes in dilute aqueous solutions and on the dye removal efficiency were observed. The stability of the PC/azo dye complex and, connected with this, the flocculation window were higher when the PC with the highest CD was used. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Photoreduction of Azo Dyes by Reducing Agents Formed upon Photo-excitation of some Simple Aliphatic and Aromatic Compounds

Many organic compounds that absorb ultraviolet radiation can act as powerful reducing agents when irradiated in the ultraviolet. Such irradiation in the presence of azo dyes can lead to the photoreduction of the dyes. It is shown that simple ketyl radicals have strong reducing properties and can reduce azo dyes. It is demonstrated that similar radicals produced from glucose also act as reducing agents. The structural relation between glucose and cellulose suggests that the photoreduction can also play a role in the photofading of azo dyes on cellulosic textile materials.     

Diffusion/adsorption model of cellulose dyeing. I. The diffusion through never-dry cellulose

The diffusion coefficients D₀, of C.I. Direct Yellow 12, Red 2, Blue 1, and Blue 15 in aqueous NaCl solution were measured at 90°C by the diaphagm cell method. The values of D₀ for Yellow 12 and Red 2 showed a salt concentration dependence and those for Blue 1 and Blue 15 were constant over the ionic strength range from 0.01 to 0.10. In the adsorption/diffusion models proposed so far for the direct dye–cellulose system, the Standing–Warwicker–Willis model was shown to be similar in principle to the Weisz–Zollinger model. The adsorption/diffusion behaviors in never-dry cellophane sheet for C.I. Direct Yellow 12 and Blue 15 were examined by the method of cylindrical film roll at 90°C. The concentration dependence of the apparent diffusion coefficient for these dyes showed an incomplete validity of both the models.     

Microwave-assisted solvent-free synthesis and spectral properties of some dimethine cyanine dyes as fluorescent dyes for DNA detection

A series of dimethine cyanine dyes were synthesized in a fast, efficient and high yield by the condensation of quaternary salts with 1H-indole-3-carbaldehyde in the presence of piperidine under solvent-free microwave irradiation. The products were identified by ¹H NMR, IR, UV–vis spectroscopy and elemental analysis. The absorption and fluorescence properties of the dyes in both the free state and DNA or BSA were investigated. Significant enhancement of the fluorescent quantum yield was observed for all the dyes in the presence of DNA, with one compound demonstrating excellent sensitivity as a fluorescent probe.     

Diffusion mechanism of direct dyes into a cellulose membrane: The structural effect of direct dyes on the adsorption rate

The transport of three typical direct dyes, C.I. Direct Yellow 12, C.I. Direct Red 2, and C. I. Direct Blue 15, into a cellulose membrane has been studied at 55°C. Sodium chloride was used as a stimulator for dyeing. The effects of the concentration of the stimulator on the adsorption isotherms, the adsorption rate, and the concentration profiles in the membrane were tested. The experimental adsorption rates of three dyes were quite different. The diffusion mechanism of the dyes into a cellulose membrane was analyzed on the basis of the parallel transport equation of surface and pore diffusion as developed in our previous paper. The experimental uptake curves showed good agreement with the theoretical curves for surface diffusion control. Experimental concentration profiles also agreed reasonably well with the theoretical lines for surface diffusion control rather than pore diffusion control. The surface diffusivities of three dyes were quite different and nearly independent of the adsorbed phase concentration of the dye.