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.     

Catalytic reduction of organic dyes at gold nanoparticles impregnated silica materials: influence of functional groups and surfactants

Gold nanoparticles (Au NPs) in three different silica based sol–gel matrixes with and without surfactants are prepared. They are characterized by UV–vis absorbance and transmission electron microscopic (TEM) studies. The size and shape of Au NPs varied with the organo-functional group present in the sol–gel matrix. In the presence of mercaptopropyl functionalized organo-silica, large sized (200–280 nm) spherical Au NPs are formed whereas in the presence of aminopropyl functionalized organo-silica small sized (5–15 nm) Au NPs are formed inside the tube like organo-silica. Further, it is found that Au NPs act as efficient catalyst for the reduction of organic dyes. The catalytic rate constant is evaluated from the decrease in absorbance of the dye molecules. Presence of cationic or anionic surfactants greatly influences the catalytic reaction. The other factors like hydrophobicity of the organic dyes, complex formation of the dyes with anionic surfactants, repulsion between dyes and cationic surfactant, adsorption of dyes on the Au NPs also play important role on the reaction rate.     

TiO2 nanoparticles with high ability for selective adsorption and photodegradation of textile dyes under visible light by feasible preparation

Particular TiO₂ nanoparticles with high selective photocatalytic oxidation of anionic dyes are prepared by a feasible hydrothermal method. Moreover, its photocatalytic selectivity can be easily switched to cationic dyes by a simple post-treatment in ammonia solution, which makes the prepared TiO₂ have bi-directional selectivity in dye photodegradation. Based on the photocatalytic performances and the structure and surface characteristics of the catalyst, the bi-directional selectivity of the catalysts is found to be closely related to the adsorption selectivity. The adsorption selectivity originates from surface charge groups, which are introduced during the preparation and post-treatment progresses. This study provides a facile and economical approach towards selective degradation of dyes with high efficiency by the special TiO₂ nanoparticles synthesized through a simple hydrothermal method, which may be used practically in the future.     

Sonochemical preparation of polyaniline@TiO2 and polyaniline@SiO2 for the removal of anionic and cationic dyes

Polyaniline (PANI) synthesized by simple CDs (carbon dots) initiated polymerization has formed a composite with TiO₂ and SiO₂, respectively via a sonochemical method. These PANI@TiO₂ and PANI@SiO₂ composites were proven as effective adsorbent materials to rapidly adsorb the anionic and cationic dyes from wastewater at neutral pH and ambient temperature. Selected popular cationic and anionic organic dyes consisted of methylene blue (MB), brilliant blue (BB), Evans blue (EB), crystal violet (CV), Congo red (CR), rhodamine B (RB), and rhodamine 6G (R6G). The adsorption equilibria were governed by Langmuir and Freundlich isotherms. The kinetic results revealed that the PANI@TiO₂ and PANI@SiO₂ composite materials synthesized via the sonochemical method are efficient adsorbents compared to other adsorbent materials for the removal of organic dyes from the water. The adsorbed dyes were effectively desorbed from the composites, rendering the reusability of PANI@TiO₂ and PANI@SiO₂. The estimated adsorption capacities of PANI@TiO₂ and PANI@SiO₂ composites were 89, 93, 80, 94 and 74, 71, 61, 61 mg/g for MB, CR, CV, and R6G, respectively.     

Electrospun Fibrous Membranes of Modified Polystyrene and its Copolymer With Butyl Acrylate and Their Respective Adsorption Capabilities for Cationic Blue and Copper Ions

Cationic dyes and metal ions in wastewater are considered as environmental pollutants. In order to treat these pollutants individually polystyrene (PS) and poly (styrene-co-butyl acrylate) (P(St-co-BA)) were first electrospun into fibrous membranes with a porous structure and then two simple modification methods were adopted to introduce -SO₃H and -COO^? groups into the PS fibrous membranes' and the P(St-co-BA) fibrous membranes' surfaces, respectively; finally the modified samples were used individually to adsorb either cationic blue dyes or copper ions, respectively. The results showed that the PS fibrous membranes were hydrophobic before modification but they became hydrophilic after modification due to the introduction of -SO₃H. Then the modified PS fibrous membranes had the capability to adsorb cationic blue dyes from water, and their adsorption efficiency, with an adsorption time of 300 min, reached 68.1%. For the P(St-co-BA) fibrous membranes, the -COO^? groups were introduced into their surfaces after hydrolysis in alkali lye; however, they showed very weak adsorption capability for copper ions due to the loss of the fiber-web structure. In addition, the thermal properties of the fibrous membranes before and after modification were analyzed, and the morphology was also observed by field emission scanning electron microscopy.     

Absorption spectra of associates of heterogeneous dye molecules in polymer matrices

The formation processes for heterogeneous associates of cationic dyes in polyvinyl alcohol films are investigated. The influence of colorless anions on the heterogeneous association efficiency is established. The structures of heterogeneous dimers of various dyes in polymer matrixes are defined.     

Influence of Solvent on Dye-Sensitized Solar Cell Efficiency: What is so Special About Acetonitrile? (Part. Part. Syst. Charact. 5/2021)

The selection of solvent for preparing a working electrode (and to act as the electrolyte) is known to influence the efficiency of dye-sensitized solar cells. In this topical review, results taken from a systematic study are presented from the authors’ own lab examining how protic and aprotic solvents, as well as solvent polarity, affect adsorption of carboxylic dyes on the titanium dioxide nanoparticle surface and electron injection from the dye to the semiconductor. Adsorption of dye molecules on nanoparticle surfaces is measured through second harmonic light scattering and electron injection through ultrafast transient mid-infrared absorption. It is revealed that protic solvents do not allow direct adsorption of the dye onto the semiconductor surface, due to hydrogen bonding with the dye and competitive binding to the semiconductor surface. Aprotic solvents, on the other hand, support solvation of the dye molecules but also facilitate dye adsorption on the semiconductor nanoparticle. Among aprotic solvents, it is found that solvents with higher polarity result in larger adsorption free energy for the dye and faster electron injection. Overall, these studies reveal that aprotic solvents with high solvent polarity (such as acetonitrile) yield more efficient solar cell devices.     

The adsorption of caesium—137 on bentonites from the Carpathian basin

The adsorption of cesium was studied on the surface of bentonite rocks from the Carpathian basin. The adsorbed quantity at carrier-free concentration was measured using ¹³⁷Cs, the adsorption capacity of bentonites for cesium ions was determined by X-ray fluorescence analysis. The relation of the cesium adsorption and mineral composition as well as the structural modifications of crystal structure was studied by X-ray diffraction spectrometry and thermoanalysis. The results show that the adsorbed quantity of cesium primarily depends on the montmorillonite content of bentonites.     

Specific features of the radiative relaxation of excited states of polymethine dyes of different ionicity in films of photoconductive and nonphotoconductive polymers

The spectral and luminescent properties of film composites based on photoconductive poly-N-epoxipropylcarbazole and nonphotoconductive polyvinylbutyral with admixtures of cationic and anionic polymethine dyes, as well as the effect of an external magnetic field on these properties, are studied. It is found that the magnetic field affects the intensity and kinetics of the delayed fluorescence and recombination luminescence of the cationic dye in photoconductive films. This is explained by specific features of photogeneration of charge pairs, namely, by the participation of the singlet and triplet excited states of dye molecules in this process, as well as by the singlet-triplet conversion in dye molecules and photogenerated charge pairs.     

Ultrasonic enhancement of the simultaneous removal of quaternary toxic organic dyes by CuO nanoparticles loaded on activated carbon: Central composite design,kinetic and isotherm study

Copper oxide nanoparticles loaded on activated carbon (CuO-NPs-AC) were prepared and fully analyzed and characterized with FE-SEM, XRD and FT-IR. Subsequently, this novel material was used for simultaneous ultrasound-assisted adsorption of brilliant green (BG), auramine O (AO), methylene blue (MB) and eosin yellow (EY) dyes. Problems regard to dyes spectra overlap in quaternary solution of this dyes were omitted by derivative spectrophotometric method. The best pH in quaternary system was studied by using one at a time method to achieved maximum dyes removal percentage. Subsequently, sonication time, adsorbent dosage and initial dyes concentrations influence on dyes removal was optimized by central composite design (CCD) combined with desirability function approach (DFA). Desirability score of 0.978 show optimum conditions set at sonication time (4.2 min), adsorbent mass (0.029 g), initial dyes concentration (4.5 mg L⁻¹). Under this optimum condition the removal percentage for MB, AO, EY and BG dyes 97.58, 94.66, 96.22 and 94.93, respectively. The adsorption rate well fitted by pseudo second-order while adsorption capacity according to the Langmuir model as best equilibrium isotherm model for BG, MB, AO and EY was 20.48, 21.26, 22.34 and 21.29 mg g⁻¹, respectively.     

阴阳离子菁染料在溴碘化银乳剂颗粒上J-聚体反射光谱

本文对两种阴阳离子菁染料在碘溴化银立方体颗粒表面的聚集行为进行了研究。用紫外-可见分光光度计测定了菁染料J-聚集的反射光谱曲线。与对应的阴离子、阳离子菁染料各自在碘溴化银立方体颗粒表面的聚集进行了实验对比。结果表明:阴阳离子菁染料吸附在碘溴化银立方体颗料表面形成的J-聚集态的反射光谱具有单个阴离子、阳离子菁染料形成J-聚体反射光谱的峰值波长。表明阴阳离子菁染料具有两个感色区域,既有阴离子菁染料的感色区又有阳离子菁染料的感色区。     

季铵型纤维素的红外光谱及对持久性有机污染物的吸附特征

文章研究了季铵型阳离子纤维素(QACC)的红外光谱和对持久性有机污染物的吸附及循环利用问题。研究了吸附工艺参数对QACC吸附容量的影响。研究了QACC对染料的吸附等温式,测定了QACC吸附染料过程的热力学参数(ΔH, ΔS, ΔG)、吸附速率常数和吸附活化能,探讨了QACC吸附机理。在近中性水溶液中,QACC对含磺酸基、羧基、羟基的水溶性芳香族有机污染物具有较大的饱和吸附容量,常见共存离子对吸附不产生影响。QACC对上述污染物的吸附既有化学吸附,也有物理吸附,而以化学吸附为主。吸附符合Langmuir等温式和一级动力学方程,吸附速率随温度升高而增大。水溶性有机污染物用0.5 mol·L-1氢氧化钠水溶液洗脱,再生后QACC可以循环利用。QACC是一种性能优良的新型功能材料,可应用于环境中持久性有机污染物的治理。     

Degradation of organic water pollutants through sonophotocatalysis in the presence of TiO(2)

The degradation of 2-chlorophenol and of the two azo dyes acid orange 8 and acid red 1 in aqueous solution was investigated kinetically under sonolysis at 20 kHz and under photocatalysis in the presence of titanium dioxide particles, as well as under simultaneous sonolysis and photocatalysis, i.e. sonophotocatalysis. The influence on the degradation and mineralisation rates of the initial substrate concentration and of the photocatalyst amount was systematically investigated to ascertain the origin of the synergistic effect observed between the two degradation techniques. The evolution of hydrogen peroxide during kinetic runs was also monitored. Small amounts of Fe(III) were found to affect both the adsorption equilibria on the semiconductor and the degradation paths. Ultrasound may modify the rate of photocatalytic degradation by promoting the deaggregation of the photocatalyst, by inducing the desorption of organic substrates and degradation intermediates from the photocatalyst surface and, mainly, by favouring the scission of the photocatalytically and sonolytically produced H(2)O(2), with a consequent increase of oxidising species in the aqueous phase.     

Adsorption of hexavalent chromium onto montmorillonite modified with hydroxyaluminum and cetyltrimethylammonium bromide

Aluminum hydroxypolycation and cetyltrimethylammonium bromide (CTMAB) were chosen to synthesize inorganic-organic pillared montmorillonite. Three different methods were employed for the intercalation. The characteristics of natural and modified montmorillonite were determined with X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), X-ray photoelectron spectrum (XPS), and zeta potential. It was found that aluminum hydroxypolycation and CTMAB had either entered the interlayer or sorbed on the external surface of the clay. Different intercalation orders can result in different structures. Batch adsorption of hexavalent chromium (Cr⁶⁺) onto modified montmorillonite was also investigated. The experimental data revealed that if aluminum hydroxypolycation was intercalated before CTMAB, the adsorption capacity was better than that of intercalated simultaneously or CTMAB pre-intercalated. The pH of the solution and environmental temperature had significant influences on the adsorption of Cr⁶⁺. The optimal pH for the removal was about 4, and the temperature of 298 K was best suitable. All adsorption processes were rapid during the first 5 min and reached equilibrium in 20 min. The adsorption kinetics can be described quite well by pseudo-second-order model. The adsorption rates of ACM, CAM and ACCOM were 3.814, 0.915, and 3.143 mg/g/min, respectively. The adsorption capacities of Cr⁶⁺ at 298 K on ACM, CAM, and ACCOM inferred from the Langmuir model were 11.970, 6.541, and 9.090 mg/g, respectively. The adsorption of Cr⁶⁺ on modified montmorillonite was mainly induced by the surface charge and the complexation reaction between CTMA⁺ and hexavalent chromium species at the edge of the clay particle.     

Effect of electrostatic interaction on the methylene blue and methyl orange adsorption by the pristine and functionalized carbon nanotubes

Multi-walled carbon nanotubes (MWCNTs) were functionalized with cysteamine groups by several percentage of mass as adsorbents, then kinetics adsorption capacity was investigated for methylene blue (MB) and methyl orange (MO) as anionic and cationic dyes adsorbate molecules, respectively. The effect of temperature (from 283 to 303 K), contact time and initial concentration of the MB and MO dyes in a solution (10 to 40 ppm) was considered. The optimal contact time was found to be about 60 min. Some kinetics model such as pseudo-first-order, pseudo-second-order, intra-particle diffusion and the Elovich were tested. The adsorptions of MB dye on the pristine and functionalized MWCNT surfaces were found to be the intra-particle diffusion and the pseudo-second-order kinetic model, respectively and for adsorption of MO dye by the pristine and low functionalized MWCNTs and highly functionalized tubes, found to be the pseudo-second-order and intra-particle diffusion kinetic model, respectively, based on the chi-square statistic (X²) and also high correlation coefficient (R²) values.     

Computational study of new azo dyes with different anchoring groups for dye-sensitised solar cells

Some of new azo dyes with different anchoring groups, such as biscarbodithiolic acid, hydroxamic acid, phosphonic acid, carboxcylic acid and sulfonic acid have been investigated theoretically to evaluate the effects of various anchoring groups on the optical and electronic properties of the dyes in dye-sensitised solar cells. Optical and electronic properties, UV–Vis absorption spectra, light-harvesting efficiency, lifetime of the excited state, chemical hardness and lowest unoccupied molecular orbital (LUMO) orbital weight of the dyes on the anchoring groups, have been studied to shed light on how the various anchoring groups influence the properties of the dyes. The biscarbodithiolic acid-based dye shows the longest maximum absorption wavelength and the widest absorption spectra together with the highest light-harvesting efficiency, the longest lifetime of the excited state and the highest the LUMO orbital weight of the dye on the atoms of the anchoring group, suggesting the good ability in electron injection. Theoretical calculations have been also performed on the adsorption of these dyes on the TiO₂ anatase (101) surface. These results show that the biscarbodithiolic acid-based dye has the highest adsorption energy and the largest negative shift of the conduction band of TiO₂ due to the adsorption of the dye onto the TiO₂.     

胶束体系中荧光素与四溴荧光素间能量转移条件及模型研究

研究了阳离子表面活性剂(CSAA)在水溶液中与阴离子酸性染料四溴荧光素(TBF)的荧光反应,发现当CSAA单体与TBF形成离子缔合物时,TBF的荧光发生猝灭,而CSAA胶束与TBF作用又会产生一个新的、更强的荧光。进而研究了阳离子表面活性剂CTMAB及CPB胶束体系中酸性阴离子荧光染料荧光素与四溴荧光素间的能量转移条件。表明只有在带相反电荷的CSAA形成的胶束中,阴离子染料间的能量转移才可能发生,在2/3临界胶束浓度(CMC)时能量转移效率达到最大。并推测了胶束体系中染料间能量转移模型及染料间能量转移的一般规律。     

Simultaneous adsorption of dyes and heavy metals from multicomponent solutions using fly ash

In wastewaters originating from dye industry there are amounts of dyes (very common methyl orange, methylene blue—MB) and heavy metals (cadmium, copper, nickel mainly from the organo-metallic dyes). They tend to adsorb in a competitive process and modify the substrate. Advanced removal is usually proposed via adsorption and the use of modified fly ash as a substrate is sustainable solution. The main constituents of fly ash (silica, alumina, iron oxide and un-burned carbon), are the priority compounds which favour the heavy metal adsorption and are active sites in dyes’ adsorption processes. The paper studies the effect of MB adsorbed on the fly ash surface on the removal efficiency of cadmium, copper and nickel ionic species from complex, multi-cationic dye solutions. The adsorption efficiency and kinetics are evaluated from the complex, multicomponent systems and possible influences are discussed. High efficiencies are obtained at low heavy metal concentrations (as it is the real case for the dyes industry) whereas at medium values, competitive processes lower the individual efficiencies of copper, nickel or cadmium from mixtures.     

The electronic properties of the Cs/GaAs(100) interface and the formation of metastable Cs clusters

The method of threshold photoemission spectroscopy is used to investigate the electronic properties of the ultrafine gallium-enriched Cs/GaAs(100) interface. The rearrangement of the spectrum of surface photo-emission as a function of Cs coating, as well as the temperature dependence of the spectrum, enable one to identify two phases of adsorption with strong (Cs-Ga) and weak (Cs-Cs) bonds. In the first phase of adsorption with the coating of approximately 0.3 monolayers, two surface bands are detected which are due to the local interaction of cesium adatoms with gallium dimers. It is found that the transition from the first to the second phase of adsorption occurs with the Cs coating of approximately 0.7 monolayers, which corresponds to the saturation of all dangling bonds of gallium on the gallium-enriched GaAs(100) surface. In the second phase of adsorption with the coating of more than 0.7 monolayers, a number of additional photoemission singularities are observed in the spectra, whose emergence is associated with the formation of metastable Cs formations. Photoemission peaks at 1.9 and 2.17 eV may be associated with the excitation of quasi-two-and/or quasi-three-dimensional Cs clusters, and the peaks at 2.05, 2.4, and 2.78 eV may be associated with the excitation of an interface plasmon and of surface and bulk Cs plasmons, respectively.