Sonocatalytic rapid degradation of Congo red dye from aqueous solution using magnetic Fe0/polyaniline nanofibers

Nano-sized magnetic Fe⁰/polyaniline (Fe⁰/PANI) nanofibers were used as an effective material for sonocatalytic degradation of organic anionic Congo red (CR) dye. Fe⁰/PANI_, was synthesized via reductive deposition of nano-Fe⁰ onto the PANI nanofibers at room temperature. Prepared catalyst was characterized using HR-TEM, FE-SEM, XRD, FTIR instruments. The efficacy of catalyst in removing CR was assessed colorimetrically using UV–visible spectroscopy under different experimental conditions such as % of Fe⁰ loading into the composite material, solution pH, initial concentration of dye, catalyst dosage, temperature and ultrasonic power. The optimum conditions for sonocatalytic degradation of CR were obtained at catalyst concentrations = 500 mg.L⁻¹, concentration of CR = 200 ppm, solution pH = neutral (7.0), temperature = 30 °C, % of Fe⁰ loading = 30% and 500 W ultrasonic power. The experimental results showed that ultrasonic process could remove 98% of Congo red within 30 min with higher Q_max value (Q_max = 446.4 at 25 °C). The rate of degradation of CR dye was much faster in this ultrasonic technique rather than conventional adsorption process. The degradation efficiency declined with the addition of common inorganic salts (NaCl, Na₂CO₃, Na₂SO₄ and Na₃PO₄). The rate of degradation suppressed more with increasing salt concentration. Kinetic and isotherm studies indicated that the degradation of CR provides pseudo-second order rate kinetic and Langmuir isotherm model compared to all other models tested. The excellent high degradation capacity of Fe⁰/PANI under ultrasonic irradiation can be explained on the basis of the formation of active hydroxyl radicals (OH) and subsequently a series of free radical reactions.     

Removal of Congo red dye from aqueous solution with nickel-based metal-organic framework/graphene oxide composites prepared by ultrasonic wave-assisted ball milling

Metal-organic frameworks (MOFs) were successfully synthesized by ultrasonic wave-assisted ball milling. In the absence of organic solvent, the coupling effect of ultrasonic wave and mechanical force played an significant role in the synthesis of MOFs. Adsorption of Congo red (CR) was studied in view of adsorption kinetic, isotherm and thermodynamics. The adsorbent was carried out using X-ray diffraction (XRD), thermogravimetric analysis (TGA), N₂ adsorption-desorption isotherms, Raman spectroscopy and scanning electron microscope (SEM) methods. It was found that pseudo-second-order kinetic model and Freundlich adsorption isotherm matched well for the adsorption of CR onto nickel-based metal-organic framework/graphene oxide composites (Ni-MOF/GO). The results of the adsorption thermodynamics indicated that the adsorption process was a spontaneous and endothermic process. The adsorption capacity of graphene oxide/metal-organic frameworks (GO/MOFs) for CR reached 2489 mg/g, much higher than previous reports. It was demonstrated that an increase in the number of active metal sites can dramatically improve the adsorption capacity of dye. A suitable dry temperature is beneficial for the improvement of adsorption capacity for dye. In this paper, the adsorption results indicated that ultrasonic wave-assisted ball milling has a good prospect for synthesis of MOFs with excellent adsorption performance.     

Preparation of activated carbon from Enteromorpha prolifera and its use on cationic red X-GRL removal

Enteromorpha prolifera was pyrolyzed to prepare activated carbon using chemical activation by zinc chloride. The effect of activation parameters such as activation temperature, weight ratio (Enteromorpha prolifera to ZnCl₂), and activation time was investigated. The BET results showed that the surface area and pore volume of activated carbons were achieved as high as 1722 m²/g and 1.11 cm³/g, respectively, in the optimal activation conditions. Batch adsorption studies were carried out to study the adsorption properties of cationic red X-GRL onto activated carbon by varying the parameters like initial solution pH, contact time, and temperature. The kinetic studies showed that the adsorption data followed a pseudo second-order model. The isotherm analysis indicated that the adsorption data could be represented by the Langmuir isotherm model. The Langmuir monolayer adsorption capacity of cationic red X-GRL was estimated as 263.16 mg/g at pH 6.0.     

Ultrasound wave assisted adsorption of congo red using gold-magnetic nanocomposite loaded on activated carbon: Optimization of process parameters

In this study, gold-magnetic nanocomposite in the presence of ultrasound wave assisted was synthesized and loaded on activated carbon (Au-Fe₃O₄-NCs-AC) by simple, fast and low-cost process. This novel material was applied for ultrasound assisted adsorption of congo red (CR) as model of toxic and even carcinogenic substance from aqueous solution. The detail of morphology and identity of Au-Fe₃O₄-AC was characterized by SEM and TEM techniques and correlation among response to variables such as pH (2–10), adsorbent mass (0.005–0.025 g), initial CR concentration (10–30 mg L⁻¹) and ultrasound time (2–6 min) was investigated by response surface methodology (RSM) under central composite design (CCD). Analysis of variance (ANOVA) exhibit a high R² value of 0.999 and confirm suitability of constructed second-order regression model for excellent evaluation and prediction of the experimental data. The interaction and main factor and optimum conditions of the under study process were determined from response surface plots based on desirability function. The maximum CR adsorption were achieved at pH of 4, 15 mg L⁻¹ of CR, 0.017 g of Au-Fe₃O₄-AC and 5 min sonication which owing to 99.49% removal efficiency is highly recommended for future CR removal from different matrixes. Adsorption kinetic follow second-order rate expression in combination to inter particle diffusion and equilibrium adsorption data best represented by the Langmuir isotherm with maximum mono-layer adsorption capacity of 43.88 mg g⁻¹.     

Adsorptive removal and kinetics of methylene blue from aqueous solution using NiO/MCM-41 composite

Highly ordered mesoporous material MCM-41 was synthesized from tetraethylorthosilicate (TEOS) as Si source and cetyltrimethylammonium bromide (CTAB) as template. Well-dispersed NiO nanoparticles were introduced into the highly ordered mesoporous MCM-41 by chemical precipitation method to prepare the highly ordered mesoporous NiO/MCM-41 composite. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), and nitrogen adsorption–desorption measurement were used to examine the morphology and the microstructure of the obtained composite. The morphological study clearly revealed that the synthesized NiO/MCM-41 composite has a highly ordered mesoporous structure with a specific surface area of 435.9 m² g⁻¹. A possible formation mechanism is preliminary proposed for the formation of the nanostructure. The adsorption performance of NiO/MCM-41 composite as an adsorbent was further demonstrated in the removal azo dyes of methyl orange (MO), Congo red (CR), methylene blue (MB) and rhodaming B (RB) under visible light irradiation and dark, respectively. The kinetics and mechanism of removal methylene blue were studied. The results show that NiO/MCM-41 composite has a good removal capacity for organic pollutant MB from the wastewater under the room temperature. Compared with MCM-41 and NiO nanoparticles, 54.2% and 100% higher removal rate were obtained by the NiO/MCM-41 composite.     

Adsorption and solid phase extraction of 8-hydroxyquinoline from aqueous solutions by using natural bentonite

The nitrogen-heterocyclic compound 8-hydroxyquinoline (8HQ) is one of the components of coal tar and has a wide variety of uses in industry. Because of its toxicity for aquatic organisms and harmful effects for human health, the removal of 8HQ from aqueous solutions by adsorption onto natural bentonite was investigated in the present work. The experimental results show that the optimum pH value of 2.5 is favourable for the 8HQ adsorption. The experimental data were fitted well with the pseudo-second-order kinetic and Langmuir adsorption isotherm models at all studied temperatures. The maximum adsorption capacity obtained from the Langmuir isotherm model at 20 °C was 120.6 mg g⁻¹. The calculated thermodynamic results such as ΔG° (−24.3 kJ mol⁻¹) and ΔH° (−9.56 kJ mol⁻¹) indicate that the adsorption process is spontaneous and exothermic in nature. Solid phase extraction of 8HQ was also performed. The X-ray diffractometry (XRD), Fourier Transform Infrared (FTIR) and thermogravimetric (TG) analyses were carried out in order to confirm the 8HQ adsorption onto bentonite. According to the obtained results, natural bentonite can be a reusable and effective adsorbent for the removal of 8HQ.     

Enhanced adsorption of Congo red using chitin suspension after sonoenzymolysis

In the present work, chitin suspensions after enzymolysis and sonoenzymolysis were taken as adsorbents to evaluate the adsorption properties of Congo red (CR) dyes. Compared with untreated chitin suspension, the CR adsorption performance was significantly improved after enzymolysis and even more after sonoenzymolysis. According to different adsorption kinetic and isotherm models, Langmuir isotherm and the pseudo-second order model were more reliable to describe the adsorption process of CR onto different chitin samples and demonstrated a monolayer and favorable physisorption process. What’s more, negative values of ΔG (Gibbs free energy change) and the shifts to higher negative values with the temperature increasing from adsorption thermodynamic study proved a spontaneous CR adsorption process. The structural characterization before and after adsorption further verified the physical adsorption between chitin and CR, and a larger specific area and higher porosity of chitin suspension was obtained after sonoenzymolysis with more available active sites.     

Ultrasonic-assisted synthesis of polyacrylamide/bentonite hydrogel nanocomposite for the sequestration of lead and cadmium from aqueous phase: Equilibrium,kinetics and thermodynamic studies

Clay-hydrogel nanocomposites are suitable material for mitigating the pollution/environmental impact because of their high adsorption capacity. In this study, the synthesis of polyacrylamide/bentonite hydrogel nanocomposite was assisted by ultrasound through successful incorporation of nanobentonite as filler and cross-linker into polyacrylamide framework. The adsorbent was characterized by FTIR, XRD, BET, SEM-EDX, and TEM in order to observe structural changes and sorption interactions. The effect of adsorbent dose, contact time, initial metal ion concentration and pH on the sequestration of Pb²⁺ and Cd²⁺ was analyzed. The adsorbent removed more than 95% Pb²⁺ and Cd²⁺ within first 20 min, which corresponds to relatively high pseudo-first order rate constant, k₁ (0.240 for Pb²⁺ and 0.253 1/min for Cd²⁺) and pseudo-second order rate constant, k₂ (0.031 for Pb²⁺ and 0.033 g/mg/min for Cd²⁺). The isotherm and kinetics modeling data were best described by Freundlich isotherm over the entire concentration range and pseudo-second order rate equation, respectively. The thermodynamic studies implied spontaneous and endothermic nature of adsorption process. The maximum adsorption capacity (138.33 for Pb²⁺ and 200.41 mg/g for Cd²⁺) determined using Langmuir model along with a good regeneration potential depicts that polyacrylamide/bentonite hydrogel nanocomposite could be used effectively for Pb²⁺ and Cd²⁺ uptake from aqueous solution.     

Thermodynamic and kinetic parameters of ciprofloxacin adsorption onto modified coal fly ash from aqueous solution

Batch adsorption experiments were carried out for the removal of ciprofloxacin from aqueous solution using modified coal fly ash as adsorbent. The effects of various parameters such as contact time, initial solution concentration and temperature on the adsorption system were investigated. The optimum contact time was found to be 100 min. The isotherm adsorption data fit well with the Langmuir model, and the kinetic data fit well with the pseudo-second order and the intra-particle diffusion model. Intra-particle diffusion analysis demonstrates that ciprofloxacin diffuses quickly among the particles at the beginning of the adsorption process, and then the diffusion slows down and stabilizes. Thermodynamic parameters such as ΔG, ΔH and ΔS were also calculated. The negative Gibbs free energy change and the positive enthalpy change indicated the spontaneous and endothermic nature of the adsorption, and the positive entropy change indicated that the adsorption process was aided by increased randomness.     

Photocatalytic activity of multielement doped TiO2 in the degradation of congo red

TiO₂ although considered a promising photocatalyst for the degradation of aqueous pollutants, it suffers from poor absorption in the visible region and hence requires ultraviolet (UV) light for activation. To make TiO₂ a visible active photocatalyst, multielement (C, N, B, and F) doping has been done. The synthesised CNBF/TiO₂ catalysts were calcined at different temperatures and characterized by XRD, BET surface area, UV DRS, XPS, HRSEM-EDAX, and TEM techniques. These catalysts found to show less band gap values when compared to bare TiO₂. These catalysts were tested for their catalytic activity towards the degradation of a textile dye - congo red (CR) under different reaction conditions. It was found that the photocatalytic activity was dependent on both doping of multielement and the calcination temperature of CNBF/TiO₂. The co-doped catalysts which were calcined at 400 °C and 600 °C (100% intensity in anatase phase) were found to be the best catalysts (100% decolourisation of CR in 21/2 h and 2 h respectively). TOC analysis carried out for the samples at the reaction time of 5 h showed very high percentage (83%) degradation of CR over CNBF/TiO₂ catalysts calcined at 600 °C when compared to the other catalysts calcined at different temperatures. CNBF/TiO₂ (1000 °C) showed very less photocatalytic activity due to the formation of rutile phase.     

Adsorption behavior of a textile dye of Reactive Blue 19 from aqueous solutions onto modified bentonite

The aim of this study is to evaluate adsorption kinetics, isotherms and thermodynamic parameters of Reactive Blue 19 (RB19) onto modified bentonite from aqueous solutions. The effects of pH, contact time, initial dye concentration and temperature were investigated in the experimentally. Natural bentonite was modified by using 1,6-diamino hexane (DAH) as a modifying agent. The characterization of modified bentonite (DAH-bentonite) was accomplished by using FTIR, TGA, BET and elemental analysis techniques. The optimum pH value for the adsorption experiments was found to be 1.5 and all the experiments were carried out at this pH value. The pseudo-second-order kinetic model agrees very well with the experimental results. Equilibrium data were also fitted well to the Langmuir isotherm model in the studied concentration range of RB19 at 20 °C. The results indicate that DAH-modified bentonite is a suitable adsorbent for the adsorption of textile dyes.     

Surface heterogeneity effects of activated carbons on the kinetics of paracetamol removal from aqueous solution

The removal of a compound with therapeutic activity (paracetamol) from aqueous solutions using chemically modified activated carbons has been investigated. The chemical nature of the activated carbon material was modified by wet oxidation, so as to study the effect of the carbon surface chemistry and composition on the removal of paracetamol. The surface heterogeneity of the carbon created upon oxidation was found to be a determinant in the adsorption capability of the modified adsorbents, as well as in the rate of paracetamol removal. The experimental kinetic data were fitted to the pseudo-second order and intraparticle diffusion models. The parameters obtained were linked to the textural and chemical features of the activated carbons. After oxidation the wettability of the carbon is enhanced, which favors the transfer of paracetamol molecules to the carbon pores (smaller boundary layer thickness). At the same time the overall adsorption rate and removal efficiency are reduced in the oxidized carbon due to the competitive effect of water molecules.     

Adsorption of methylene blue onto sonicated sepiolite from aqueous solutions

The aim of the present study is to enhance the methylene blue (MB) adsorption of sepiolite by ultrasonic treatment. The natural sepiolite was pretreated by sonication to improve the surface characteristics and enhance the dye uptake capacity. Sonication process resulted in a significant increase in the specific surface area (SSA) of sepiolite. The FTIR spectrum of the sonicated sepiolite indicates that the tetrahedral sheet is probably distorted after sonication process. The effect of various parameters such as sonication, pH, initial dye concentration and temperature on dye adsorption has been investigated. The adsorbed amount of MB on sepiolite increased after sonication as well as with increasing pH and temperature. The experimental data were evaluated by applying the pseudo-first- and second-order, and the intraparticle diffusion adsorption kinetic models. Adsorption process of MB onto sepiolite followed the pseudo-second-order rate expression. The experimental data were analyzed by Langmuir and Freundlich isotherms, and found that the isotherm data were reasonably well correlated by Langmuir isotherm. Maximum monolayer adsorption capacity of sepiolite for MB increased from 79.37 to 128.21 mg/g after the sonication. Various thermodynamic parameters, such as ΔG⁰, ΔH⁰ and ΔS⁰ were calculated. The thermodynamics of MB/sepiolite system indicated spontaneous and endothermic nature of the process. Adsorption measurements showed that the process was very fast and physical in nature.     

磁性碳纳米管吸附去除水中甲基橙的研究

采用高温催化裂解法制备碳纳米管,对其用浓硝酸氧化法进行纯化处理,并用化学共沉淀方法制备了磁性碳纳米管(简称磁性管)。利用场发射扫描电子显微镜对磁性管进行了表征。将磁分离技术应用于碳纳米管吸附性能研究,探索碳纳米管负载磁性颗粒后对甲基橙的吸附性能,寻找最佳实验条件,对吸附质溶液进行紫外-可见吸收光谱分析。同时,进行了磁性管的脱附和再吸附性能研究。     

Cobalt-nickel mixed oxide surface: A promising adsorbent for the removal of PR dye from water

A mixed oxide of cobalt (Co) and nickel (Ni) with an approximate composition of Co_0.4Ni_0.4O_0.2 was prepared chemically by precipitating from the corresponding metal carbonates and heating the mixture of carbonates at 650 °C under ambient atmosphere. The mixed (Co-Ni) oxide thus prepared was characterized by IR, SEM and XRD methods. The composition of the mixed metal oxide was obtained by EDX analysis. The surface behavior of the Co-Ni mixed oxide matrix was tested by adsorption studies and pH_pzc measurement. The Co-Ni mixed oxide matrix behaves as a charged adsorbent at the pH media higher and lower than its pH_pzc value (9.50) and thus found to be capable of anchoring the oppositely charged species onto its surface. Removal of cationic and anionic dyestuffs, viz., methylene blue (MB) and procion red (PR), respectively, was attempted using the mixed oxide surface as adsorbent. Although both the dyes can be removed by the mixed oxide, the extent of PR removal (∼70%) seems to be much higher than that of MB (∼20%) demonstrating the superior performance of the Co-Ni mixed oxide for its use as adsorbent in removing the anionic PR dyestuff from water.     

Adsorptive removal of anionic dyes by modified nanoporous silica SBA-3

Batch sorption experiments were carried out to remove dyes, methyl orange (MO), orange G (OG) and brilliant red X-3B (X-3B), from their aqueous solutions using a mesoporous silica SBA-3 as an adsorbent. The effect of surfactant template in SBA-3 on the removal of OG, MO and X-3B was investigated. Experiments were carried out to investigate the influence of contact time, initial concentration, pH, and adsorbent dosage on the adsorption performance. The adsorption results of anionic dyes on the uncalcined SBA-3 (noted as SBA-3) were compared with those of the calcined SBA-3 (noted as C-SBA-3). The uncalcined SBA-3 adsorbent has a large adsorption capacity and a strong affinity for the anionic dyes. Langmuir, Freundlich and Temkin isotherms were employed to model the experimental results, from which the Freundlich isotherm exhibited the most appropriate to predict the same. Freundlich isotherm exhibited the most appropriate to predict the experimental results. The kinetic data were also analyzed through pseudo-first-order and pseudo-second-order models. The pseudo-second-order kinetic model well depicted the kinetics of dyes adsorption on mesoporous SBA-3.     

Study on the toxic interactions of Ni with DNA using neutral red dye as a fluorescence probe

The interaction between Ni²⁺ and calf thymus DNA (ctDNA) was investigated in simulated physiological buffer (pH 7.4) using the Neutral Red (NR) dye as a spectral probe by UV-vis absorption and fluorescence spectroscopy, as well as CD spectra. The experimental results showed that the conformational changes in DNA helix induced by Ni²⁺ are the reason for the fluorescence quenching of the DNA-NR system. From the experimental results, conclusion can be drawn that Ni²⁺ can cause structural changes of ctDNA and bind with DNA by electrostatic interaction. At the same time, the paper proved that conformation changes of DNA can also lead to the fluorescence decrease of DNA-probe systems.     

Enhancement of saccharin removal from aqueous solution by activated carbon adsorption with ultrasonic treatment

This study investigates the use of ultrasonication as a pretreatment process and its effect on the adsorption characteristics of saccharin onto activated carbon (AC). Ultrasonic decomposition of saccharin was performed at a frequency of 500 kHz under argon and O2/N2 (20/80 vol%) atmospheres. Adsorption was carried out using a commercial activated carbon. The behavior of total organic carbon (TOC) during ultrasonication was investigated. Saccharin removal after 180 min of ultrasonication under Ar and O2/N2 atmospheres are 38% and 26%, respectively, while the amount of saccharin removed by activated carbon adsorption without US pretreatment is 40% after 16 h. After 16 h of AC adsorption with 180 min of ultrasonic pretreatment under Ar and O2/N2 atmospheres, both removal ratios increased to 75%. These results indicated that the pretreatment of sonication under O2/N2 leads to the increase in the amount of saccharin adsorbed on AC. On the other hand, the TOC removal by decomposition by ultrasound is not more than 5% in both Ar and O2/N2 atmospheres after 180 min ultrasonication. However, the TOC removal increased to 54% and 69% after 16 h of adsorption of saccharin pretreated by ultrasonication for 180 min under Ar and O2/N2 atmospheres, respectively. About 13% and 16% TOC removal in Ar and in O2/N2, respectively, were achieved due to adsorption of the by-products. It is considered that the improvement in TOC removal is also brought about by the formation of the by-products that were adsorbed onto AC.     

Mercury removal from aqueous solution and flue gas by adsorption on activated carbon fibres

The use of two activated carbon fibres, one laboratorial sample prepared from a commercial acrylic textile fibre and one commercial sample of Kynol^®, as prepared/received and modified by reaction with powdered sulfur and H₂S gas in order to increase the sulfur content were studied for the removal of mercury from aqueous solution and from flue gases from a fluidized bed combustor. The sulfur introduced ranged from 1 to 6 wt.% depending on the method used. The most important parameter for the mercury uptake is the type of sulfur introduced rather than the total amount and it was found that the H₂S treatment of ACF leads to samples with the highest mercury uptake, despite the lower sulfur amount introduced. The modified samples by both methods can remove HgCl₂ from aqueous solutions at pH 6 within the range 290-710 mg/g (ACF) which can be favourably compared with other studies already published. The use of a filter made with an activated carbon fibre modified by powdered sulfur totally removed the mercury species present in the flue gases produced by combustion of fossil fuel.