Effective removal of dyes from aqueous solution using ultrafine silk fibroin powder

Ultrafine silk fibroin powder was successfully produced using our developed machine and used as low-cost adsorbent to remove dyes in the printing and dyeing wastewater. The silk powder thus prepared was characterized by scanning electronic microscopy (SEM), laser particle analyzer and Fourier transform infrared (FTIR) spectrum. It showed that the silk powder with an average diameter of 3.8 μm was dominant in β-sheet structure. Dye adsorption experiments demonstrated that silk powder could effectively remove model dyes including direct orange (DO), disperse blue (DB) and methylene blue (MB) in particular. Factors influencing the adsorption of MB, e.g., solution pH, contact time, adsorption concentration and ionic strength were systematically investigated. Isotherm equilibrium studies demonstrated that MB adsorption process followed Langmuir model. The maximum adsorption capacity for MB dye was estimated to be 20.58 mg/g and the decoloration percentage could reach up to 95%. The batch experimental results suggested that silk fibroin powder could be used as an efficient sorbent to remove dyes in textile effluents.     

Removal of the hazardous dye—Tartrazine by photodegradation on titanium dioxide surface

The removal of the dye—tartrazine by photodegradation has been investigated using titanium dioxide surface as photocatalyst under UV light. The process was carried out at different pH, catalyst dose, dye concentration and effects of the electron acceptor H₂O₂. It was found that under the influence of TiO₂ as catalyst, the colored solution of the dye became colorless and the process followed a pseudo first order kinetics. The optimum conditions for the degradation of dye were 6 × 10^? 5 M dye concentration, pH of 11, and 0.18 mg/L of catalyst dose. In order to evaluate the effect of electron acceptor, the effect of H₂O₂ on the degradation process was also monitored and it was found that the hydroxyl radical formation and retardation of electron–hole recombination took place simultaneously. The adsorption studies of tartrazine at various dose of TiO₂ followed the Langmuir isotherm trend. In order to determine the quality of waste water, Chemical Oxygen Demand (COD) measurements were carried out both before and after the treatment and a significant decrease in the values was observed, implying good potential of this technique to remove tartrazine dye from aqueous solutions.     

Preparation of surface modified zinc oxide nanoparticle with high capacity dye removal ability

In this paper, the surface modification of zinc oxide nanoparticle (ZON) by amine functionalization was studied to prepare high capacity adsorbent. Dye removal ability of amine-functionalized zinc oxide nanoparticle (AFZON) and zinc oxide nanoparticle (ZON) was also investigated. The physical characteristics of AFZON were studied using Fourier transform infrared (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Acid Blue 25 (AB25), Direct Red 23 (DR23) and Direct Red 31 (DR31) were used as model compounds. The effect of operational parameters such as dye concentration, adsorbent dosage, pH and salt on dye removal was evaluated. The isotherm and kinetic of dye adsorption were studied. The maximum dye adsorption capacity (Q₀) was 20 mg/g AB25, 12 mg/g DR23 and 15 mg/g DR31 for ZON and 1250 mg/g AB25, 1000 mg/g DR23 and 1429 mg/g DR31 for AFZON. It was found that dye adsorption followed Langmuir isotherm. Adsorption kinetic of dyes was found to conform to pseudo-second order kinetics. Dye desorption tests (adsorbent regeneration) showed that the maximum dye release of 90% AB25, 86% for DR23 and 90% for DR31 were achieved in aqueous solution at pH 12. Based on the data of the present investigation, it can be concluded that the AFZON being an adsorbent with high dye adsorption capacity might be a suitable alternative to remove dyes from colored aqueous solutions.     

Equilibrium,kinetic and thermodynamic studies on the adsorption of phenol onto graphene

Graphene, a new member of carbon family, has been prepared, characterized and used as adsorbent to remove phenol from aqueous solution. The effect parameters including pH, dosage, contact time, and temperature on the adsorption properties of phenol onto graphene were investigated. The results showed that the maximum adsorption capacity can reach 28.26 mg/g at the conditions of initial phenol concentration of 50 mg/L, pH 6.3 and 285 K. Adsorption data were well described by both Freundlich and Langmuir models. The kinetic study illustrated that the adsorption of phenol onto graphene fit the pseudo second-order model. The thermodynamic parameters indicated that the adsorption of phenol onto graphene was endothermic and spontaneous.     

Removal of Pb(II) ions from aqueous solution by adsorption using bael leaves (Aegle marmelos)

Biosorption of Pb(II) on bael leaves (Aegle marmelos) was investigated for the removal of Pb(II) from aqueous solution using different doses of adsorbent, initial pH, and contact time. The maximum Pb loading capacity of the bael leaves was 104 mg g^?1 at 50 mg L^?1 initial Pb(II) concentration at pH 5.1. SEM and FT-IR studies indicated that the adsorption of Pb(II) occurs inside the wall of the hollow tubes present in the bael leaves and carboxylic acid, thioester and sulphonamide groups are involved in the process. The sorption process was best described by pseudo second order kinetics. Among Freundlich and Langmuir isotherms, the latter had a better fit with the experimental data. The activation energy E_a confirmed that the nature of adsorption was physisorption. Bael leaves can selectively remove Pb(II) in the presence of other metal ions. This was demonstrated by removing Pb from the effluent of exhausted batteries.     

Chitosan beads as barriers to the transport of azo dye in soil column

The development of chitosan-based materials as useful adsorbent polymeric matrices is an expanding field in the area of adsorption science. Although chitosan has been successfully used for the removal of dyes from aqueous solutions, no consideration is given to the removal of dyes from contaminated soils. Therefore this study focuses on the potential use of chitosan as an in situ remediation technology. The chitosan beads were used as barriers to the transport of a reactive dye (Reactive Black 5, RB5) in soil column experiments. Batch sorption experiments, kinetic and equilibrium, were performed to estimate the sorption behavior of both chitosan and soil. The chitosan beads were prepared in accordance with published literature and a synthetic soil was prepared by mixing quantities of sand, silt and clay. The synthetic soil was classified according to British Standards. Calcium chloride was used as tracer to define transport rates and other physical experimental parameters. Dye transport reaction parameters were determined by fitting dye breakthrough curves (BTCs) to the HYDRUS-1D version 4.xx software. Fourier Transform-Infra Red (FT-IR) spectroscopy was used to reveal the sorption mechanism. The study showed that chitosan exhibited a high sorption capacity (S_max = 238 mg/g) and pseudo-first sorption rate (k₁ = 1.02 h^?1) coupled with low swelling and increased retardation for the azo dye tested. Thus it has potential as a Permeable Reactive Barrier (PRB) for containment and remediation of contaminated sites.     

Preparation,characterization and photocatalytic properties of terbium orthoferrite nanopowder

Perovskite-type terbium orthoferrite (TbFeO₃) nanopowder was synthesized through a polyacrylamide gel route. The as-synthesized particles were characterized by XRD, TEM, BET surface area, UV–visible absorption spectroscopy, and XPS. It is shown that the particles are uniformly and regularly shaped like spheres with an average size of ～50 nm, and have a BET specific surface area of 15.4 m² g^?1. The optical energy bandgap of the nanosized TbFeO₃ is obtained to be 1.98 eV. The photocatalytic activity of the TbFeO₃ particles was evaluated by the photodegradation of various organic dyes including methyl orange (MO), rhodamine B (RhB), methylene blue (MB), acid fuchsine (AF), and congo red (CR). It is demonstrated that the product exhibits a pronounced photocatalytic degradation of the dyes under visible-light irradiation. The photocatalytic efficiency is observed to depend on the dye type, and under the present experimental conditions it follows the sequence: CR > AF > MB > RhB > MO.     

As(V) removal from aqueous media using α-MnO2 nanorods-impregnated laterite composite adsorbents

We present a novel way of enhancing the utility of low cost readily available laterite by impregnating it with the α-MnO₂ nanorods, thus making a composite material suitable for the removal of As(V) from aqueous media. The composites were synthesized by two methods: (i) ball-milling of a physical blend of laterite with pre-synthesized MnO₂; and (ii) in situ formation of MnO₂ in the presence of laterite. The BET surface area of composites prepared by both methods was markedly higher compared to un-modified laterite, and the presence of MnO₂ in the composite was also confirmed by XRD analysis and TEM microscopy. The adsorption capacity for As(V) was found to be highly pH dependent and the adsorption kinetics followed a pseudo second-order kinetic model. The Langmuir adsorption isotherm was found to be the best model to describe the adsorption equilibrium of As(V) onto un-modified laterite as well both ball-milled and in situ formed composite. The adsorption capacities at room temperature and pH 7.0 were found to be 1.50 mg g^?1, 8.93 mg g^?1 and 9.70 mg g^?1, for un-modified laterite, ball-milled and in situ formed composite, respectively.     

Spectroscopic properties and amplified spontaneous emission of fluorescein laser dye in ionic liquids as green media

The use of ionic liquids (ILs) as milieu materials for laser dyes is a promising field and quite competitive with volatile organic solvents and solid state-dye laser systems. This paper investigates some photo-physical parameters of fluorescein dye incorporated into ionic liquids; 1-Butyl-3-methylimidazolium chloride (BMIM Cl), 1-Butyl-3-methylimidazolium tetrachloroaluminate (BMIM AlCl₄) and 1-Butyl-3-methylimidazolium tetrafluoroborate (BMIM BF₄) as promising host matrix in addition to ethanol as reference. These parameters are: absorption and emission cross-sections, fluorescence lifetime and quantum yield, in addition to the transition dipole moment, the attenuation length and oscillator strength were also investigated. Lasing characteristics such as amplified spontaneous emission (ASE), the gain, and the photostability of fluorescein laser dye dissolved in different host materials were assessed. The composition and properties of the matrix of ILs were found that it has great interest in optimizing the laser performance and photostability of the investigated laser dye. Under transverse pumping of fluorescein dye by blue laser diode (450 nm) of (400 mW), the initial ASE for dye dissolved in BMIM AlCl₄ and ethanol were decreased to 39% and 36% respectively as time progressed 132 min. Relatively high efficiency and high fluorescence quantum yield (11.8% and 0.82% respectively) were obtained with good photostability in case of fluorescein in BMIM BF₄ that was decreased to ∼56% of the initial ASE after continuously pumping with 400 mW for 132 min.     

Selective adsorption and release of cationic organic dye molecules on mesoporous borosilicates

Mesoporous materials can play a pivotal role as a host material for delivery application to a specific part of a system. In this work we explore the selective adsorption and release of cationic organic dye molecules such as safranine T (ST) and malachite green (MG) on mesoporous borosilicate materials. The mesoporous silica SBA-15 and borosilicate materials (MBS) were prepared using non-ionic surfactant Pluronic P123 as template via evaporation induced self-assembly (EISA) method. After template removal the materials show high surface areas and in some cases ordered mesopores of dimensions ca. 6–7 nm. High surface area, mesoporosity and the presence of heteroatom (boron) help this mesoporous borosilicate material to adsorb high amount of cationic dye molecules at its surface from the respective aqueous solutions. Furthermore, the mesoporous borosilicate samples containing higher percentage adsorbed dyes show excellent release of ST or MG dye in simulated body fluid (SBF) solution at physiological pH = 7.4 and temperature 310 K. The adsorption and release efficiency of mesoporous borosilicate samples are compared with reference boron-free mesoporous pure silica material to understand the nature of adsorbate–adsorbent interaction at the surfaces.     

Photoluminescence spectra of bisphenol A based pyrazoloquinoline dimers in different solvents: Experiment and quantum chemical calculations

Paper presents measured optical absorption and photoluminescent spectra for several derivatives of bisphenol A based pyrazoloquinoline dimers (BAPQD). BAPQD dyes exhibit the first absorption band in the region of 400–415 nm, whereas their photoluminescence maxima are centered in the spectral region of 430–480 nm depending on solvent polarity. Several phenyl containing BAPQD dyes reveal rather strong solvatochromism of their photoluminescence spectra which is assumed to be related with intramolecular charge transfer. The experimental results are compared with quantum chemical calculations performed by means of semiempirical methods AM1 and PM3 in combination with molecular dynamics simulations at T = 300 K. Both methods well reproduce the overall shape of the measured spectra, however the semiempirical PM3 method exhibits much better agreement with experimental data, especially in predicting spectral position of the first absorption band (absorption threshold) and photoluminescence maxima. The obtained results may be of substantial interest for chemical engineering which deals with a designing of new efficient organic luminophores for electroluminescent applications. BAPQD dyes may be considered as potential dopants for polymer based organic diodes that emit light with different shades of blue color.     

Na0.5Li0.5CoO2 nanopowders: Facile synthesis,characterization and their application for the removal of methylene blue dye from aqueous solution

In this paper, delafossite-type Na_0.5Li_0.5CoO₂ nanoparticles (NPs) with an average particle size of 50 nm were successfully synthesized by sol–gel method. Prepared NPs were characterized by differential thermal analysis, powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, and scanning tunneling microscopy. The nanoparticles showed the excellent adsorption properties towards methylene blue dye (MBD) as a reactive dye. The kinetics of removal of MBD in aqueous solutions was studied in a series of experiments which were varied in the amount of NPs, contact time, pH, and temperature. The experimental data were fitted very well in the pseudo-second order kinetic model and the Freundlich adsorption isotherm model. 92% of dye was successfully removed in 10 min using 0.02 g Na_0.5Li_0.5CoO₂ NPs in a pH = 11. Thermodynamic study indicates that the adsorption of MBD is feasible, and spontaneous in nature.     

Removal of Congo Red from aqueous solution by cattail root

In this study, cattail root was used to remove Congo Red (CR) from aqueous solution. The effects of operation variables, such as cattail root dosage, contact time, initial pH, ionic strength and temperature on the removal of CR were investigated using batch adsorption technique. Removal efficiency increased with increase of cattail root dosage and ionic strength, but decreased with increase of temperature. The equilibrium data fitted well to the Langmuir model (R² > 0.98) and the adsorption kinetic followed the pseudo-second-order equation (R² > 0.99). Thermodynamics parameters such as standard free energy change (ΔG°), standard enthalpy change (ΔH°), and standard entropy change (ΔS°) were analyzed. The values of ΔG° were between ?7.871 and ?4.702 kJ mol^?1, of ΔH° was ?54.116 kJ mol^?1, and of ΔS° was ?0.157 kJ mol^?1 K^?1, revealing that the removal of CR from aqueous solution by cattail root was a spontaneous and exothermic adsorption process. The maximum adsorption capacities of CR on cattail root were 38.79, 34.59 and 30.61 mg g^?1 at 20, 30 and 40 °C, respectively. These results suggest that cattail root is a potential low-cost adsorbent for the dye removal from industrial wastewater.     

Effect of chondroitin sulfate on osteogenetic differentiation of human mesenchymal stem cells

Chondroitin sulfate (CS) has anti-inflammatory properties and increases the regeneration ability of injured bone. In different in vivo investigations on bone defects the addition of CS to calcium phosphate bone cement has lead to an enhanced bone remodeling and increased new bone formation. The goal of this study was to evaluate the cellular effects of CS on human mesenchymal stem cells (hMSCs). In cell culture experiments hMSCs were incubated on calcium phosphate bone cements with and without CS and cultivated in a proliferation and an osteogenetic differentiation media. Alkaline phosphatase and the proliferation rate were determined on days 1, 7 and 14. Concerning the proliferation rates, no significant differences were detected. On days 1, 7 and 14 a significantly higher activity of alkaline phosphatase, an early marker of osteogenesis, was detected around CS modified cements in both types of media. The addition of CS leads to a significant increase of osteogenetic differentiation of hMSCs. To evaluate the influence of the osteoconductive potency of CS in twelve adult male Wistar rats, the interface reaction of cancellous bone to a nanocrystalline hydroxyapatite cement containing type I collagen (CDHA/Coll) without and with CS (CDHA/Coll/CS) was evaluated. Cylindrical implants were inserted press-fit into a defect of the tibial head. 28 days after the operation the direct bone contact and the percentage of newly formed bone were significantly higher on CDHA/Coll/CS-implants (p < 0.05). The addition of CS appears to enhance new bone formation on CDHA/Coll-composites in the early stages of bone healing. Possible mechanisms are discussed.     

Interaction of cationic dye/surfactants with Klebsiella K18 capsular polysaccharides: Physico-chemical studies

Physico-chemical studies on the interaction of capsular polysaccharide (SPS) isolated from Klebsiella K18, with cationic dyes and surfactants have been reported. SPS is an integral component of gram-negative bacteria and having glucuronic acid as the potential anionic site, induced strong metachromasy (blue shift ～ 110 nm) in the cationic dye pinacyanol chloride (PCYN). Reversal of metachromasy was observed upon addition of co-solvents which provides a qualitative measurement of stability and nature of metachromatic compound associated with PCYN–SPS interaction. Thermodynamic parameters such as association constant, changes in free energy, enthalpy and entropy of dye–polymer interaction, were evaluated which revealed the nature of interaction. Studies on fluorescence quenching of acridine orange (AO) was also performed. The interaction of SPS with cationic and cationic–non-ionic mixed surfactant systems have been studied by turbidimetry, spectrophotometry, spectrofluorometry and viscosity measurements. The studies could provide an understanding on the effects of the surfactants on binding with the polymer. The binding was found to be electrostatic in origin and also hydrophobic in nature to a certain extent.     

Copper remediation by Eichhornia spp. and sulphate-reducing bacteria

Eichhornia spp. biomass was collected from Chandola Lake, Ahmedabad, Gujarat, India. Point of zero charge of the biomass was pH 7.3. Flask study showed pH 5 and 2–3 h contact time as optimum conditions for copper sorption with 67.25% copper removal. At the end of 24 h of contact time, copper removal reached to 85.0%, from 100 ppm copper containing solution. Copper loading capacity of the biomass ranged between 9.9 and 28.5 mg g^?1 of biomass. To understand the interaction among pH, temperature, presence of nickel and zinc in the system, 2⁴ factorial experiment was performed. Under the experimental conditions pH and interactions between pH–nickel, temperature–pH and temperature–pH–nickel–zinc were found to be significant with 60–74.7% copper removal. Langmuir isotherm was better fit as compared to Freundlich isotherm and pseudo-second order equation gave R² of 0.999 for biosorption kinetic of Eichhornia biomass. Reactor study showed 90% overall copper removal from 24 L of copper containing waste studied and sulphate-reducing bacteria played a significant role. SEMquant element analysis showed increase from 41.66% to 53.93%, 1.02–19.73% and 0.0–12.39% of chloride, aluminium and copper respectively in the loaded biomass as compare to unexposed biomass.     

Characterization of sodium dodecyl sulfate modified iron pillared montmorillonite and its application for the removal of aqueous Cu(II) and Co(II)

Anionic surfactant modified Fe-pillared montmorillonites were prepared by Fe-hydrate solution and sodium dodecyl sulfate (SDS) solution. These organo–inorgano complex montmorillonites were divided into three types (CM1, CM2 and CM3) depending on different intercalation processes. X-ray diffraction spectra, the Fourier transform infrared (FTIR) spectra were used to analyze the structure of the raw and modified montmorillonites. X-ray photoelectron spectra of the simples have been studied to determine spectral characteristics to allow the identification of Fe(III) hydroxide. The specific surface area of the host montmorillonite (M0) is 73.2 m²/g, while for the modified montmorillonites it is 114.0 m²/g, 117.2 m²/g, and 115.8 m²/g, respectively. The mesopore volumes of the montmorillonites decrease after modification. Ions of copper and cobalt were selected as adsorbates to evaluate the adsorption performance of each montmorillonite. The adsorption data was analyzed by both Freundlich and Langmuir isotherm models and the data was well fit by the Langmuir isotherm model. The adsorption was efficient and significantly influenced by metal speciation, metal concentration, contact time, and pH. Higher adsorption capacity of the modified montmorillonites were obtained at pH 5–6. The results of desorption indicated that the metal ions were covalently bound to the modified montmorillonites.     

Luminescence properties of nanocrystalline YVO4:Eu3+ under UV and VUV excitation

Single phase of Eu³⁺-doped YVO₄ nanophosphors at different pH values were synthesized by a mild hydrothermal method. Their photoluminescence were evaluated under UV and VUV region, respectively. Monitoring by 619 nm emission, broad bands at around 143 nm, 200 nm, 260 nm were observed in the excitation spectrum of YVO₄:5 mol%Eu³⁺. These peaks could be assigned to host absorption, the overlap of the VO₄³⁻ host absorption and charge transfer transition between Eu³⁺ and O²⁻, respectively. Both 254 nm and 147 nm excitations, the emission spectra were identical, they were all composed of Eu³⁺ emission transitions arising mainly from the ⁵D₀ level to the ⁷F_J (J = 1, 2, 3, 4) manifolds. With the pH values ranging from 7 to 11, the relative intensity of the emission spectra were decreasing, and the position of the predominant peak (⁵D₀ → ⁷F₂) was changed from 619 nm to 615 nm when the pH values changed from 7 to 11.     

Surface-functionalized pomelo peel-derived biochar with mercapto-1,2,4-triazloe for selective elimination of toxic Pb (II) in aqueous solutions

A novel biochar adsorbent (GP-AMT) is prepared by functionalizing biochar derived from pomelo peel to eliminate Pb (II) from water. GP-AMT was characterized by FTIR, SEM, BET, TGA and XPS. GP-AMT has a large specific area and is multiaperture. The adsorption performance was studied. At the pH = 5, the maximum uptake amount of Pb(II) on GP-AMT reached 420 mg/g. The sorption behavior of GP-AMT obeys with Langmuir and pseudo second-order formula, which shows that the adsorbing property of GP-AMT is uniform chemical sorption. Thermodynamic studies attested that the sorption was an irreversible endothermic course. GP-AMT demonstrated excellent selectivity and reproducibility. After 5 cycles, it still has an excellent sorption property. XPS and zeta potential analysis revealed that the adsorbing nature of GP-AMT for heavy metal ions was coordination and ion exchange. In conclusion, surface modification of biochar can significantly improve its sorption capacity, selectivity and regenerative ability for Pb(II), and reduce the pomelo peel waste pollution.     

Photobleaching of metal phthalocyanine sulfonates under UV and visible light irradiation over TiO2 semiconductor

The stability of eleven metal phthalocyanine sulfonates against UV (λ > 320 nm) or visible light (λ > 450 nm) in the presence of TiO₂ semiconductor was studied in an aqueous medium. Although all the dyes were quite photostable in a homogeneous solution, they underwent notably photobleaching in the presence of TiO₂. The degree of dye bleaching was strongly dependent on the central metal in the complex, whereas for each complex the bleaching rate under UV irradiation was much faster than that under visible light irradiation. The spectral analysis showed that the dye photobleaching led to complete destruction of the phthalocyanine ring. In addition, the visible light stability of the dye was greatly affected by physical properties of TiO₂ semiconductor, and the dye photostability could be improved by addition of electron sacrifice such as 4-chlorophenol.