Comments on "The effect of substituent groups on the reductive degradation of azo dyes by zerovalent iron" by M. Hou, et al. [J. Hazard. Mater. 145 (2007) 305

This letter discusses possible improvements in experimental conditions to enable a purposeful discussion on the effect of substituent groups on the reductive degradation of azo dyes by elemental iron (Fe(0)) in a recent article by Hou and his co-workers. Also recalled is the pH dependence of the iron corrosion mechanism which is usually overlooked in the iron technology literature.     

Influence of iron on degradation of organic dyes in corona

In this work application of AOPs such as Fenton process, aqueous phase high voltage electrical discharge (corona) and their combination have been studied for colored wastewater treatment. Experiments were conducted on water solutions of four different organic dyes, two azo dyes C.I. Mordant Yellow 10 (MY10) and C.I. Direct Orange 39 (DO39), and two reactive of azo type C.I. Reactive Red 45 (RR45) and C.I. Reactive Blue 137 (RB137). The efficiency of studied AOPs has been estimated on the bases of UV-vis spectrophotometric and TOC measurements. The rate constants in the kinetic model have been determined. Experimental data have been compared with the developed mathematical model.     

Immobilisation of bacteria onto magnetic nanoparticles for the decolorisation and degradation of azo dyes

Azo dyes are widely used in industries and their release in the environment contributes to the pollution of effluents. The authors aim to develop a new eco‐friendly water treatment method for the degradation of azo dyes based on in situ magnetic separation and immobilisation of bacterial cells. The immobilisation was achieved using superparamagnetic Fe₃ O₄ nanoparticles and offers the possibility of reusing bacteria by magnetic separation for several degradation cycles. The iron– oxide nanoparticles were synthesised by reverse co‐precipitation. The Gram‐positive bacteria Bacillus subtilis were immobilised using iron–oxide nanoparticles by adsorption and then separated with an external magnetic field. Transmission electron microscopy observation showed that the particles'' diameter was ∼20 nm with a narrow size distribution. Moreover, the iron–oxide nanoparticles were adsorbed onto the surface in order to coat the cells. B. subtilis has proved its ability to decolorise and degrade several azo dyes at different values of pH, with the highest decolorisation rate for Congo red. Furthermore, immobilised cells have a degradation activity similar to that of free cells. The system provided a degradation rate up to 80% and could be reused for seven batch cycles.Inspec keywords: biotechnology, microorganisms, pH, adsorption, iron compounds, superparamagnetism, transmission electron microscopy, ultraviolet spectra, chemical technology, wastewater treatment, effluents, dyes, magnetic separation, iron, magnetic particles, decontaminationOther keywords: degradation rate, immobilisation, magnetic nanoparticles, azo dyes, eco‐friendly water treatment method, degradation cycles, Gram‐positive bacteria, iron–oxide nanoparticles, external magnetic field, immobilised cells, degradation activity, magnetic separation, effluents, bacterial cells, Fe₃ O₄      

Study on the nonlinear optical properties of three azo dyes by Z-scan measurements

The nonlinear optical properties of p-aminoazobenzene (PAAB), methyl orange (MO) and p-dimethylamino benzene arsenic acid (PDBAA) were investigated by a single beam Z-scan technique, respectively. Their solution samples all exhibited large nonlinear refractive indices under the excitation of a 633 nm laser. Among the three azo dyes, PDBAA showed the largest value of nonlinear refractive index. Moreover, the process of nonlinear refraction induced by the laser thermal effect was also analyzed in this paper.     

Oxidative treatment of azo dyes in aqueous solution by potassium permanganate

This work was conducted to study the ability of permanganate (KMnO(4)) oxidative treatment as a method to decolourise the solutions containing azo dye C.I. Acid Orange 7, C.I. Acid Orange 8, C.I. Acid Red 14, or C.I. Acid Red 73, in a batch system. The results of the study demonstrated the complete removal of the colour and partial mineralization for each dye solution. The effect of the key operating variables such as initial dye concentration, permanganate amount, pH and temperature were studied. Decolourisation reactions were influenced by the acidity and temperature of the treated solutions. To avoid the overdose of KMnO(4), the stoichiometric amount of permanganate required for 1 mol of dye complete colour removal was determined. The reactions between permanganate and C.I. Acid Orange 7, C.I. Acid Orange 8, C.I. Acid Red 14 and C.I. Acid Red 73 dyes in acidic medium exhibit (2.05, 2.20, 2.42 and 2.79):1 stoichiometry (MnO(4)(-):dye). Dye degradation efficiency by potassium permanganate was studied, monitoring total organic carbon (TOC). The results indicated that the degradation efficiency of azo dyes increased with the increase of the potassium permanganate amount. Meanwhile, even in large excess of the oxidant, the dye mineralization was incomplete.     

Decolouration of industrial azo dyes by crude laccase from Trametes hirsuta

The decolouration of several azo dyes, commonly used in the leather industry, by crude laccase obtained from Trametes hirsuta cultivation was assessed. Among the six dyes studied four showed a decolouration percentage higher than 50% in 4h, whereas the other two showed more resistance to degradation. These results show the ability of laccase towards different dye structures as well as its enormous potential for the decolouration of recalcitrant azo dyes.     

Effects of ferrous ions on the reductive dechlorination of trichloroethylene by zero-valent iron

The surface characteristics of zero-valent iron (ZVI) and the efficiency of reductive dechlorination of trichloroethylene (TCE) in the presence of ferrous ions were studied. The experimental results indicated that the acid-washing of a metallic iron sample enhanced the efficiency of TCE degradation by ZVI. This occurred because acid-washing changed the conformation of oxides on the surface of iron from maghemite (gamma-Fe(2)O(3)) to the more hydrated goethite (alpha-FeOOH), as was confirmed by XPS analysis. However, when ferrous ions were simultaneous with TCE in water, the TCE degradation rate decreased as the concentration of ferrous ion increased. This was due to the formation of passive precipitates of ferrous hydroxide, including maghemite and magnetite (Fe(3)O(4)), that coated on the surface of acid-washed ZVI, which as a result inhibited the electron transfer and catalytic hydrogenation mechanisms. On the other hand, in an Fe(0)-TCE system without the acid-washing pretreatment of ZVI, ferrous ions were adsorbed into the maghemite lattice which was then converted to semiconductive magnetite. Thus, the electrons were transferred from the iron surface and passed through the precipitates, allowing for the reductive dechlorination of TCE.     

Degradation of azo dyes by sequential Fenton's oxidation and aerobic biological treatment

A two stage sequential Fenton's oxidation followed by aerobic biological treatment train was used to achieve decolorization and to enhance mineralization of azo dyes, viz. Reactive Black 5 (RB5), Reactive Blue 13 (RB13), and Acid Orange 7 (AO7). In the first stage, Fenton's oxidation process was used while in the second stage aerobic sequential batch reactors (SBRs) were used as biological process. Study was done to evaluate effect of pH on Fenton's oxidation process. Results reveal that pH 3 was optimum pH for achieving decolorization and dearomatization of dyes by Fenton's process. Degradation of dye was assessed by COD reduction and reduction in aromatic amines (naphthalene chromophores) which was measured by reduction in absorbance at 200 nm. More than 95% of color was removed with Fenton's oxidation process in all dyes. In overall treatment train 81.95, 85.57, and 77.83% of COD reduction was achieved in RB5, RB13, and AO7 dyes, respectively. In the Fenton's oxidation process 56, 24.5, and 80% reduction in naphthalene group was observed in RB5, RB13, and AO7, respectively, which further increased to 81.34, 68.73, and 92% after aerobic treatment. Fenton's oxidation process followed by aerobic SBRs treatment sequence seems to be viable method for achieving significant degradation of azo dye.     

Competitive biosorption of azo dyes from aqueous solution on the templated crosslinked-chitosan nanoparticles

The nanoparticles of templated crosslinked chitosan, ECH-RB5 and ECH-3R, were prepared through the imprinting process using Remazol Black 5 (RB5) and Remazol Brilliant Orange 3R (3R) dyes, respectively, as templates and ECH as a crosslinker. The nanoparticles exhibited significantly higher adsorption capacities of the dyes than other nanoparticles formed without a dye template and with three crosslinkers (ECH, GLA, and EGDE). The adsorption of the dyes on the nanoparticles was affected by the initial pH, dye concentration, and temperature. The results were in accordance with the second-order and the Langmuir adsorption models. Meanwhile, the E values of the dyes calculated using the Dubinnin-Radushkevich model revealed that the adsorption process may be due to the dual nature of the process, physisorption and chemisorption, and that adsorption was predominant in the chemisorption process. The adsorption processes in the nanoparticles were spontaneous and exothermic. Moreover, competition adsorption through analysis of the intraparticle diffusion model apparently favored the 3R dye more than the RB5 dye on the nanoparticles in mixture solution B. The nanoparticles for the adsorption of the dyes were regenerated efficiently through the alkaline solution and were then reused for dye removal.     

Kinetics and thermodynamics of cadmium ion removal by adsorption onto nano zerovalent iron particles

Nano zerovalent iron (nZVI) is an effective adsorbent for removing various organic and inorganic contaminants. In this study, nZVI particles were used to investigate the removal of Cd(2+) in the concentration range of 25-450 mg L(-1). The effect of temperature on kinetics and equilibrium of cadmium sorption on nZVI particles was thoroughly examined. Consistent with an endothermic reaction, an increase in the temperature resulted in increasing cadmium adsorption rate. The adsorption kinetics well fitted using a pseudo second-order kinetic model. The calculated activation energy for adsorption was 54.8 kJ mol(-1), indicating the adsorption process to be chemisorption. The intraparticle diffusion model described that the intraparticle diffusion was not the only rate-limiting step. The adsorption isotherm data could be well described by the Langmuir as well as Temkin equations. The maximum adsorption capacity of nZVI for Cd(2+) was found to be 769.2 mg g(-1) at 297 K. Thermodynamic parameters (i.e., change in the free energy (ΔG(o)), the enthalpy (ΔH(o)), and the entropy (ΔS(o))) were also evaluated. The overall adsorption process was endothermic and spontaneous in nature. EDX analysis indicated the presence of cadmium ions on the nZVI surface. These results suggest that nZVI could be employed as an efficient adsorbent for the removal of cadmium from contaminated water sources.     

Studies on degradation of reactive textile dyes solution by electrochemical method

The indirect electrochemical degradation of industrial effluents has become an attractive method in recent years. This paper deals with the electrochemical degradation of Novacron Deep Red C-D (NDRCD) and Novacron Orange C-RN (NOCRN) reactive azo dyes from aqueous solution using graphite carbon electrodes. The results indicated that initial pH, current density and supporting electrolytes were played an important role in the degradation of dyes. Electrochemical behavior of reactive azo dyes has been studied with cyclic voltammetry in acidic medium using pencil graphite as working electrode. The potentials selected for the two dyes were in the range +1.0 to -0.4V and +0.5 to -0.2V, respectively. The CV, UV-Vis and chemical oxygen demand (COD) studies were selected to evaluate the degradation efficiency. The maximum colour removal efficiency of 99% and 97% and chemical oxygen demand (COD) removal efficiency of 88% and 82% could be achieved for CDRCD and COCRN, respectively at 7 g L(-1) of NaCl concentration. The LC-MS study revealed the degradation of both the dyes and confirmed that the azo groups and aromatic rings were destroyed. The results revealed the suitability of the present process for the effective degradation of dye effluents.     

Development of a polyoxometallate-based photocatalyst assembled with cucurbit[6]uril via hydrogen bonds for azo dyes degradation

A water insoluble cucurbit[6]uril-polyoxometallates (CB[6]-POMs) composite assembled from α-Keggin type polysilicontungstate anions and macrocycle cucurbit[6]uril (CB[6]) via hydrogen bonding has been synthesized as visible light active photocatalyst. The physical and photocatalytic properties of such photocatalyst have been fully characterized by PXRD, FTIR, TG, XPS, and UV/vis diffuse reflectance spectra. The catalyst shows a good photocatalytic activity towards the degradation of methyl orange (MO) under visible light irradiation and displays good reproducibility of photocatalytic degradation by a simple recycled procedure without obvious loss in catalytic activity, which is of great significance for practical use of the photocatalyst. In the photodegradation process, the {Ni-CB[6]}(n) chain of the photocatalyst acts as sensitizer and can be induced by visible light, meanwhile the POMs chain of the photocatalyst acts as electron acceptor and deposits the electron in its LUMO. The effects of various experimental parameters and the proposed mechanisms are discussed in detail.     

Enhanced accumulation and visible light-assisted degradation of azo dyes in poly(allylamine hydrochloride)-modified mesoporous silica spheres

A new route for the economic and efficient treatment of azo dye pollutants is reported, in which surface-modified organic-inorganic hybrid mesoporous silica (MS) spheres were chosen as microreactors for the accumulation and subsequent photodegradation of pollutants in defined regions. The surface-modified silica materials were prepared by anchoring the polycationic species such as poly(allylamine hydrochloride) on MS spheres via a simple wet impregnation method. The as-synthesized spheres with well-defined porous structures exhibited 15 times of accumulating capacity for orange II and Congo red compared to that of the pure MS spheres. Diffuse reflectance UV-vis spectroscopy and confocal laser scanning microscopy demonstrated that the accumulated orange II and CR in defined MS spheres were rapidly degraded in the presence of Fenton reagent under visible radiation. Kinetics analysis in recycling degradation showed that the as-synthesized materials might be utilized as environment-friendly preconcentrators/microreactors for the remediation of dye wastewater.     

Photocatalytic degradation of organic dyes by mesoporous nanocrystalline anatase

Mesoporous nanocrystalline anatase was prepared via EISA employing P123 and CTAB as structure directing agents. The resultant mesoporous crystalline phases exhibited specific surface areas as high as ∼150 m² g⁻¹, average unimodal pore sizes of ∼3 nm and ∼6 nm, and average crystallite size of ∼10 nm; and were used as photocatalysts for the UV degradation of methylene blue, methyl orange, methyl red and rhodamine 6G. The mesoporous anatase phases photodegraded MB, MO and MR ∼2–3 times faster than conventional nanocrystalline anatase and showed limited photocatalytic activity for rhodamine 6G.     

Photo degradation of methyl orange an azo dye by advanced Fenton process using zero valent metallic iron: influence of various reaction parameters and its degradation mechanism

Advanced Fenton process (AFP) using zero valent metallic iron (ZVMI) is studied as a potential technique to degrade the azo dye in the aqueous medium. The influence of various reaction parameters like effect of iron dosage, concentration of H(2)O(2)/ammonium per sulfate (APS), initial dye concentration, effect of pH and the influence of radical scavenger are studied and optimum conditions are reported. The degradation rate decreased at higher iron dosages and also at higher oxidant concentrations due to the surface precipitation which deactivates the iron surface. The rate constant for the processes Fe(0)/UV and Fe(0)/APS/UV is twice compared to their respective Fe(0)/dark and Fe(0)/APS/dark processes. The rate constant for Fe(0)/H(2)O(2)/UV process is four times higher than Fe(0)/H(2)O(2)/dark process. The increase in the efficiency of Fe(0)/UV process is attributed to the cleavage of stable iron complexes which produces Fe(2+) ions that participates in cyclic Fenton mechanism for the generation of hydroxyl radicals. The increase in the efficiency of Fe(0)/APS/UV or H(2)O(2) compared to dark process is due to continuous generation of hydroxyl radicals and also due to the frequent photo reduction of Fe(3+) ions to Fe(2+) ions. Though H(2)O(2) is a better oxidant than APS in all respects, but it is more susceptible to deactivation by hydroxyl radical scavengers. The decrease in the rate constant in the presence of hydroxyl radical scavenger is more for H(2)O(2) than APS. Iron powder retains its recycling efficiency better in the presence of H(2)O(2) than APS. The decrease in the degradation rate in the presence of APS as an oxidant is due to the fact that generation of free radicals on iron surface is slower compared to H(2)O(2). Also, the excess acidity provided by APS retards the degradation rate as excess H(+) ions acts as hydroxyl radical scavenger. The degradation of Methyl Orange (MO) using Fe(0) is an acid driven process shows higher efficiency at pH 3. The efficiency of various processes for the de colorization of MO dye is of the following order: Fe(0)/H(2)O(2)/UV>Fe(0)/H(2)O(2)/dark>Fe(0)/APS/UV>Fe(0)/UV>Fe(0)/APS/dark>H(2)O(2)/UV approximately Fe(0)/dark>APS/UV. Dye resisted to degradation in the presence of oxidizing agent in dark. The degradation process was followed by UV-vis and GC-MS spectroscopic techniques. Based on the intermediates obtained probable degradation mechanism has been proposed. The result suggests that complete degradation of the dye was achieved in the presence of oxidizing agent when the system was amended with iron powder under UV light illumination. The concentration of Fe(2+) ions leached at the end of the optimized degradation experiment is found to be 2.78 x 10(-3)M. With optimization, the degradation using Fe(0) can be effective way to treat azo dyes in aqueous solution.     

Photocatalytic degradation of azo dyes using Au:TiO2, gamma-Fe2O3:TiO2 functional nanosystems

We report photocatalytic degradation studies on Navy Blue HE2R (NB) dye on significant details as a representative from the class of azo dyes using functional nanosystems specifically designed to allow a strong photocatalytic activity. A modified sol-gel route was employed to synthesize Au and gamma-Fe2O3 modified TiO2 nanoparticles (NPs) at low temperature. The attachment strategy is better because it allows clear surface of TiO2 to remain open for photo-catalysis. X-ray diffraction, Raman and UV-VIS spectroscopy studies showed the presence of gold and iron oxide phases along-with the anatase TiO2 phase. TEM studies showed TiO2 nanocomposite particles of size approximately 10-12 nm. A detailed investigation on heterogeneous photocatalytic performance for Navy Blue HE2R dye was done using the as-synthesized catalysts Au:TiO2 and gamma-Fe2O3:TiO2 in aqueous suspension under 8 W low-pressure mercury vapour lamp irradiation. Also, the photocatalytic degradation of Amranth and Orange G azo dyes were studied. The surface modified TiO2 NPs showed significantly improved photocatalytic activity as compared to pure TiO2. Exposure of the dye to the UV light in the presence of pure and gold NPs attached TiO2 catalysts caused dye degradation of about approximately 20% and approximately 80%, respectively, in the first couple of hours. In the presence of gamma-Fe2O3 NPs attached TiO2, a remarkable approximately 95% degradation of the azo dye was observed only in the first 15 min of UV exposure. The process parameters for the optimum catalytic activity are established which lead to a complete decoloration and substantial dye degradation, supported by the values of the Chemical Oxygen Demand (COD) approximately 93% and Total Organic Carbon (TOC) approximately 65% of the treated dye solution after 5 hours on the employment of the UV/Au:TiO2/H2O2 photocatalytic process.     

Photocatalytic degradation of three azo dyes using immobilized TiO2 nanoparticles on glass plates activated by UV light irradiation: Influence of dye molecular structure

In order to discuss the effect of chemical structure on photocatalysis efficiency, the photocatalytic degradation of three commercial textile dyes (C.I. Acid Orange 10 (AO10), C.I. Acid Orange 12 (AO12) and C.I. Acid Orange 8 (AO8)) with different structure and different substitute groups has been investigated using supported TiO₂ photocatalyst under UV light irradiation. All the experiments were performed in a circulation photochemical reactor equipped with a 15-W UV lamp emitted around 365 nm. The investigated photocatalyst was industrial Millennium PC-500 (crystallites mean size 5–10 nm) immobilized on glass plates by a heat attachment method. SEM images of the immobilized TiO₂ nanoparticles showed the good coating on the plates, after repeating the deposition procedure three times. Our results indicated that the photocatalytic decolorization kinetics of the dyes were in the order of AO10 > AO12 > AO8. Photocatalytic mineralization of the dyes was monitored by total organic carbon (TOC) decrease, changes in UV–vis spectra and ammonium ion formation. The dye solutions could be completely decolorized and effectively mineralized, with an average overall TOC removal larger than 94% for a photocatalytic reaction time of 6 h. The nitrogen-to-nitrogen double bond of the azo dyes was transformed predominantly into NH₄⁺ ion. The kinetic of photocatalytic decolorization of the dyes was found to follow a first-order rate law. The photocatalysis efficiency was evaluated by figure-of-merit electrical energy per order (E_EO).     

Synthesis,characterisation, and effect of pH on degradation of dyes of copper-doped TiO2

Copper-doped TiO₂ nanoparticles were synthesised using an ultrasonic-assisted sol–gel method with various doping concentrations from 0 to 2.5 at.%. The samples were characterised by X-ray diffraction, UV–vis diffuse reflectance spectroscopy (UV–vis), transmission electron microscopy (TEM), Brunauer–Emmett–Teller surface area determination, and zeta potential. The presence of copper in TiO₂ crystal structure was revealed by UV–vis spectra, and the TEM analysis showed that particles are mainly spherical around the size range of 15–20 nm. In addition, doping copper into TiO₂ lattice caused a decrease in the surface area due to the aggregation of nanoparticles and a shift of isoelectric point towards lower pH when the dopant concentration increased. The photocatalytic reactivity of these materials was evaluated by the degradation of methylene blue and methyl orange under the UV light. The effect of the initial solution pH on the adsorption capacity and the photocatalytic behaviour of the Cu-doped TiO₂ in the decolourisation of these dyes were also studied.     

Removal of acid orange II azo dyes using Fe-based metallic glass catalysts by Fenton-like process

Journal of Materials Science - The unique structural characteristics of metallic glasses make them highly qualified to be applied in the treatment of organic pollutants. In this work, the...