Functionalization effect of Fe-type MOF for methylene blue adsorption

Water pollutant such as dyes had danger the water quality. Todays, porous materials are great potential for dye adsorption from water bodies. In this study, the iron-based metal–organic framework (MOF-Fe) of MIL-101 is synthesized through a facile solvothermal method. The amine-functionalization effect of the MOF-Fe (amine-MOF-Fe) is evaluated for the adsorptive removal of methylene blue (MB) from aqueous solution. The adsorption behaviour had shown a rapid MB adsorption within the first hour of the process due to the pore-filling mechanism of the porous MOF-Fe structure. The electrostatic interaction between the amino group of amine-MOF-Fe and MB had contributed to the high adsorption capacity. The amine-functionalization effect also found the amine-MOF-Fe is having two times higher adsorption capacity when used with the loading two times lower than non-functionalized MOF-Fe. The maximum equilibrium adsorption capacities were measured at 149.25 and 312.5 mg/g with optimum MOFs loading of 0.8 and 0.4 g/L for MOF-Fe and amine-MOF-Fe, respectively. The adsorption mechanism proposed includes the electrostatic interaction, pore filling, hydrogen bonding, and π–π stacking. The regeneration study showed the MOFs could be recycled without interfering with the removal efficiency. Hence, the results indicate that the MOFs had desirable reusability for the practical adsorption of cationic dyes with its features of fast adsorption and high capacity.     

Electrochemical study of methylene blue/titanate nanotubes nanocomposite and its layer-by-layer assembly multilayer films

Titanate nanotubes (TNT) were proven to be efficient support for the immobilization of methylene blue (MB). UV–vis absorption and Fourier transform infrared spectra showed that the effect of MB absorbed on TNT was better than nanocrystalline anatase TiO₂ (TNP). The quantity of MB absorbed onto TNT was found to be greater than that of TNP and the electrode modified with the MB–TNT film was more stable due to the strong interaction between TNT and MB as well. The absorption of MB on TNT was impacted by the pH value of the reaction solution for the change of surface charge. Electrochemical oxidation of dopamine (DA) at different electrodes was studied. The result showed that the MB–TNT composite film exhibited excellent catalytic activities to DA compared to those of pure TNT, which is a result of the great promotion of the electron-transfer rate between DA and the electrode surface by the MB–TNT film. Furthermore, the layer-by-layer self-assembly behavior of the electrochemically functional MB–TNT nanocomposite was also discussed after obtaining the stable colloid suspension of MB–TNT. The excellent electrochemical ability and the easy fabrication of layered nanocomposite make the MB–TNT nanocomposite very promising in electrochemistry study and new nanotube-based devices.     

Mechanism of methylene blue dye adsorption on siliceous minerals

Summary The present experiments were undertaken to establish the mechanism of methylene blue dye adsorption from aqueous solution on common siliceous minerals found in petroleum reservoir formations. Three minerals (a montmorillonite, a kaolinite, and a silica-sand flour) were prepared so that all thecec sites on the mineral surfaces were occupied by sodium (²³Na +²²Na). Methylene blue (Cl^–) dye adsorption isotherms were measured on these three minerals prepared in the sodium form. Measurement of the transmittance of the equilibrium solutions and measurement of the gamma-counting activity (²²Na) of the equilibrium solutions permitted a quantitative determination of dye cation adsorption and of sodium cation displacement.In the case of the clays (montmorillonite and kaolinite) the saturation dye adsorption capacity must be attributed to two mechanisms: first, to cation exchange resulting from isomorphous substitution in the alumino-silicate lattice and, second, to an adsorption mechanism which might be either physical (van der Waals) adsorption or chemisorption (hydrogen bonding) with the surface SiOH and AlOH of the aluminosilicate lattice.Dye adsorption on silica is due to the physical or chemisorption mechanisms alone. It was demonstrated that the distribution of this type of adsorption site on the two clays after correction for the distribution of thecec sites ranged from 4.9 to 6.1×10^–8 me/cm² and was in good agreement with the value 5.1×10^–8 me/cm² for the total adsorption sites on silica.In spite of the existence of mechanisms other than cation exchange, methylene blue dye adsorption can nonetheless be used as a rapid, approximate method for estimation ofcec of siliceous sediments owing to the fortuitous circumstance that in a saturated monomolecular layer of dye adsorbate the effective coverage area of the dye molecule approximates the area available per exchange site on the common clay minerals, e. g., montmorillonite and kaolinite.

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Zusammenfassung Die beschriebenen Untersuchungen wurden durchgeführt, um den Mechanismus der Adsorption von Methylenblau aus wäßriger Lösung an bekannten Silikaten, wie sie in erdölführenden Schichten gefunden werden, aufzuklären. Drei Minerale, ein Montmorillonit, ein Kaolinit und ein mehliger Silicium-Sand, wurden so behandelt, daß alle Kation-Austauschstellen (Cation Exchange Capacity) auf den Oberflächen des Minerales von Natrium besetzt waren (²³Na +²²Na). Isothermen der Adsorption des Farbstoffes Methylenblau-Chlorid wurden an den Natrium-Formen dieser Minerale aufgenommen. Die Messung der Lichtdurchlässigkeit der Lösung im Gleichgewicht und die Messung der Gamma-Aktivität (²²Na) dieser Gleichgewichtslösung erlaubten es, quantitativ die Adsorption von Farbstoff-Kation und den Ersatz von Natrium-Kation festzustellen.Im Falle der Tone, Montmorillonit und Kaolinit, muß die Sättigungsfähigkeit der Farbstoffadsorption zwei Mechanismen zugeschrieben werden: in erster Linie dem Kationenaustausch, der sich aus der isomorphen Substitution im Gitter des Aluminiumsilikates herleitet, in zweiter Linie einem Adsorptionsmechanismus, der entweder aus physikalischer Adsorption (van der Waals) oder Chemisorption (Wasserstoffbindung) mit den Oberflächengruppen SiOH und AlOH des Aluminosilikatgitters besteht.Farbstoffadsorption an Siliciumdioxid kann nur der physikalischen oder der aktivierten Adsorption zugeschrieben werden. Es wurde gezeigt, daß die Verteilung dieser Art von Adsorptionsstellen an den beiden Tonen von 4,9–6,1×10^–8 Milliäquivalenten pro cm² reichte (nach Korrekturen für die Verteilung der Kationen-Austauschstellen). Das stimmt sehr gut mit dem Wert 5,1×10^–8 Milliäquivalenten pro cm² für alle Adsorptionsstellen an Siliciumdioxid überein.Obwohl es einen anderen Mechanismus als den Kationenaustausch gibt, kann doch die Adsorption von Methylenblau als schnelle Feldmethode dazu dienen, die Kationen-Austauschstellen (cec) von Silikatsedimenten abzuschätzen. Und zwar, einmolekulare Bedeckung mit adsorbiertem Farbstoff vorausgesetzt, weil die vom Farbstoffmolekül effektiv bedeckte Fläche der zugänglichen Fläche pro Austauschstelle entspricht; jedenfalls bei gewöhnlichen Tonmineralen wie Montmorillonit und Kaolinit.

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Publication No. 358, Exploration and Production Research Laboratory, Shell Development Company (a Division of the Shell Oil Company), Houston, Texas.     

Study of adsorption of methylene blue and new methylene blue in liquid-solid interface by slab optical waveguide spectroscopy

A slab optical waveguide (SOWG) has been used for study of adsorption of both methylene blue (MB) and new methylene blue (NMB) in liquid–solid interface. Adsorption characteristics of MB and NMB on both bare SOWG and silanized SOWG by octadecyltrichlorosilane (ODS) were compared. Effect of pH on adsorption on MB and NMB was investigated. Binding rate constant analysis showed that both MB and NMB on bare SOWG demonstrates larger association constants than those on ODS-SOWG. Interactions of MB and NMB on bare SOWG and ODS-SOWG were analyzed by molecular mechanics calculation method. The binding energy change was in the following order: E_NMB–bare > E_MB–bare > E_NMB–ODS > E_MB–ODS.     

Thermodynamic studies of methylene blue adsorption onto Fe-doped sulfated titania

Adsorption equilibrium of methylene blue onto Fe-doped sulfated titania (FST) samples was studied at different temperatures (298, 303, and 308 K). Based on the wavelength scanning from 580 to 760 nm, the wavelength of maximum absorbance of methylene blue was determined to be 666 nm and the corresponding calibration curve can be described by the equation of A = 0.0068 + 0.1514C. The adsorption of methylene blue onto FST samples was conformed to the Langmuir isotherms. The absorption capacity of each FST sample for methylene blue increases with increasing temperature. The increase in the adsorption parameters (q _m, b, and K ₀) and the positive ΔH ^θ reveal the endothermic feature of this adsorption process. The negative ΔG ^θ shows the adsorption of methylene blue onto FST samples can be carried out spontaneously at the examined temperatures. Furthermore, with the calcination temperature increases, the variation in crystallization degree, the surface and the sulfur species will obviously influence the adsorption properties of FST samples and the thermodynamic parameters of this adsorption process.     

Enthalpies of adsorption of methylene blue and crystal violet to montmorillonite

Calorimetric measurements of the enthalpy of adsorption on montmorillonite indicate different patterns for methylene blue (MB) and crystal violet (CV). The enthalpy of adsorption of MB is endothermic up to 73% of the cation exchange capacity (CEC) (i.e., about 0.6 mmol g^-1 clay), whereas at higher adsorption ratios the adsorption reaction becomes exothermic. The enthalpy of adsorption of CV is exothermic for all amounts adsorbed. These results were confirmed with adsorption experiments that prove that adsorption of MB increase with temperature, whereas CV adsorption decreases. This behavior indicates changes in the equilibrium coefficient according to Van't Hoff's equation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Amino modified mesostructured silica nanoparticles for efficient adsorption of methylene blue

In this work, mesostructured silica nanoparticles (MSN(AP)) with high adsorptivity were prepared by a modification with 3-aminopropyl triethoxysilane (APTES) as a pore expander. The performance of the MSN(AP) was tested by the adsorption of MB in a batch system under varying pH (2-11), adsorbent dosage (0.1-0.5gL(-1)), and initial MB concentration (5-60mgL(-1)). The best conditions were achieved at pH 7 when using 0.1gL(-1) MSN(AP) and 60mgL(-1)MB to give a maximum monolayer adsorption capacity of 500.1mgg(-1) at 303K. The equilibrium data were evaluated using the Langmuir, Freundlich, Temkin, and Harkins-Jura isotherms and fit well to the Freundlich isotherm model. The adsorption kinetics was best described by the pseudo-second order model. The results indicate the potential for a new use of mesostructured materials as an effective adsorbent for MB.     

A new decavanadate polyoxovanadate nanocluster: synthesis,characterization and rapid adsorption of methylene blue

A new decavanadate polyoxovanadate nanocluster, [2-ampH]₆[V₁₀O₂₈]?2H₂O (1), was synthesized through reaction between ammonium vanadate and 2-aminopyridine at pH = 2. Nanocluster 1 was characterized by IR, elemental analysis, and X-ray crystallography. 1 was found to adsorb and desorb dyes and may have widespread application in wastewater treatment. The utility of 1 for adsorption of methylene blue was studied. The adsorbed dyes can be easily desorbed, and 1 has full efficiency after five cycles.     

Porous graphene oxide-based carbon artefact with high capacity for methylene blue adsorption

A three-dimensional porous graphene oxide (PGO) material prepared by hydrothermal method was selected to adsorb methylene blue (MB), which demonstrates a high MB adsorption capacity, up to 1100 mg g^?1 in alkaline solution at room temperature. The influences of different pore structures and different contents of oxygen-containing functional groups on MB adsorption behaviors were studied in detail, which indicated that the high MB adsorption capacity is mainly ascribed to the synergistic effect of the large number of oxygen-containing functional groups and the interconnected 3D porous network. Moreover, based on the investigation on the adsorption kinetics and the effect of pH value on MB adsorption, we propose a two-step adsorption kinetics for PGO, which involved in two interactions between MB molecular and porous graphene oxide-based carbon: electrostatic force and π-π stacking. Besides, the calculation of the activation energies indicates that chemisorption dominates the adsorption for PGO in comparison with physisorption for three-dimensional porous graphene materials which has low adsorption capacity because of the removal of functional groups. The results are of great significance for the design and environmental applications of PGO as a promising adsorbent material for water purification.     

Synthesis,characterization and the electrocatalytic application of prussian blue/titanate nanotubes nanocomposite

A novel kind of nanocomposite, titanate nanotubes (TNTs) decorated by electroactive Prussian blue (PB), was fabricated by a simple chemical method. The as-prepared nanocomposite was characterized by XRD, XPS, TEM, FT-IR and Cyclic voltammetry (CV). Experimental results revealed that PB was adsorbed on the surface of TNTs, and the adsorption capacity of TNTs was stronger than that of anatase-type TiO₂ powder (TNP). The PB-TNTs nanocomposite was modified onto a glassy carbon electrode and the electrode showed excellent electroactivity. The modified electrode also exhibited outstanding electrocatalytic activity towards the reduction of hydrogen peroxide and can serve as an amperometric sensor for H₂O₂ detection. The sensor fabricated by casting Nafion (NF) above the PB-TNTs composite film (NF/PB-TNTs/GCE) showed two linear ranges of 2 × 10^?5–5 × 10^?4 M and 2 × 10^?3–7 × 10^?3 M, with a detection limit of 1 × 10^?6 M. Furthermore, PB-TNTs modified electrode with Nafion (NF/PB-TNTs/GCE) showed wider linear range and better stability compared with PB-TNTs modified electrode without Nafion (PB-TNTs/GCE) and PB modified electrode with Nafion (NF/PB/GCE).     

Comparative study for the removal of methylene blue via adsorption and photocatalytic degradation

Physically and chemically activated carbons were prepared from date pits and olive stones. Titania and WO(x)-TiO(2)/MCM-41 were prepared as photoactive catalysts. Surface characterizations were investigated from ash content, pH, base neutralization capacities and FT-IR techniques. The textural characteristics, namely specific surface area (S(BET)) and pore texture, were determined from low temperature adsorption of N(2) at 77 K. The decolorization of aqueous solution of methylene blue was performed by means of two alternative methods. Steam-activated carbons own higher surface area compared with ZnCl(2)-activated carbons, and the micropore surface area represents the major contribution of the total area. Steam-activated carbons were the most efficient decolorizing adsorbents owing to its higher surface area, total pore volume and the basic nature of the surface. The calculated values of DeltaG(0), DeltaH(0) and DeltaS(0) indicate the spontaneous behavior of adsorption. The photocatalytic degradation is more convenient method in decolorizing of methylene blue compared with the adsorption process onto activated carbons.     

Surface characterization of dead microalgae‐based biomass using methylene blue adsorption

To examine the surface characterization of dead chlorella biomass, the chlorella‐manufacturing residue was used as an adsorbent for removal of cationic dye (i.e. methylene blue) from aqueous solutions at low concentrations (less than 5 mg dm^?3). It could be elucidated by considering the ion‐exchange adsorption phenomena on the negative‐charged surface of the adsorbent based on the characterization of functional groups by the Fourier transform infrared (FTIR) analysis. On the basis of monolayer dye adsorption capacity, the specific surface area of this spherical biomass powder was estimated as 11.8 m² g^?1, which was consistent with the rigid cell wall structure of the dead chlorella particles as shown in the SEM observation. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of Ag nanoparticles decorated on TiO2 nanotubes for surface adsorption and photo-decomposition of methylene blue under dark and visible light irradiation

Research on Chemical Intermediates - TiO2 nanotubes and Ag/TiO2 nanotubes (TNT) have been synthesized by simple hydrothermal and solvothermal method and were characterized by XRD, UV, ICP, TEM,...     

Ionic polyacrylamide hydrogel improved by graphene oxide for efficient adsorption of methylene blue

Research on Chemical Intermediates - The ionic polyacrylamide/graphene oxide (PAM/GO) hydrogel as an excellent methylene blue (MB) adsorbent was prepared by an improved one-step radical...     

A novel study on synthesis of egg shell based activated carbon for degradation of methylene blue via photocatalysis

Egg shell-based activated carbon was successfully synthesized by the simple chemical activation process. Orthophosphoric acid and sodium hydroxide used as an activation agent. XRD pattern reveals the hexagonal structure of activated carbon. The functional group presents in activated carbon was identified using FT-IR spectroscopy. SEM images show irregular shapes of carbon. The photocatalytic performance of investigated activated carbon by illuminating methylene blue dye under UV–Visible irradiations. Photocatalytic activity of activated carbon results maximum degradation efficiency of 83%. Adsorption efficiency have been increased with respect of time for degradation of dye. Free radicals and superoxide’s play a significant role is decolourization of methylene blue. Photocatalytic activity of activated carbon synthesized by Orthophosphoric acid results shows the high degradation efficiency when compared to NaOH.     

Effect of CO2 activation of carbon xerogels on the adsorption of methylene blue

The effect of physical activation with CO₂ of carbon xerogels, synthesized by pyrolysis of a resorcinol-formaldehyde aqueous gel, on the adsorption capacities of Methylene Blue (MB) was studied. The activation with CO₂ lead?to carbon materials with micropore volumes ranging from $0.28\ \mathrm{to}\ 0.98~\mathrm{cm}^{3}\,\mathrm{g}_{\mathrm{C}}^{-1}$ . MB-adsorption isotherm studies showed that the increase of micropore volume and corresponding surface area led to: (i) a significant improvement in the capacity of MB-adsorption at monolayer coverage, from $212\ \mathrm{to}\ 714~\mathrm{mg}\,\mathrm{g}_{\mathrm{C}}^{-1}$ , and (ii) an increase of the binding energy related to Langmuir isotherm constant up to 45 times greater than those of commercial microporous activated carbons used as reference (NORIT R2030, CALGON BPL and CALGON NC35). It is proposed that the increase of the binding energy results from chemical cleaning of the O-groups onto carbon surface as a consequence of CO₂-activation, increasing the π–π interaction between MB and graphene layers of the carbon xerogels. Finally, a series of batch kinetics were performed to investigate the effect of CO₂-activation conditions on the mechanism of MB-adsorption. Experimental data were fitted using pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models. From pseudo-second-order kinetic model, one observes an increase in the initial rate of MB-adsorption from 0.019 to 0.0565 min^?1, by increasing the specific surface area from $630\ \mathrm{to}\ 2180~\mathrm{m}^{2}\,\mathrm{g}_{\mathrm{C}}^{-1}$ via CO₂-activation. Depending on the activation degree of the carbons, two different mechanisms control the MB-adsorption rate: (i) at low activation degree, the intraparticle diffusion is the rate-limiting phenomenon, whereas (ii) at high activation degree, the reactions occurring at the solid/liquid interface are the rate-limiting steps.     

Phosphorylated cellulose for water purification: a promising material with outstanding adsorption capacity towards methylene blue

Cellulose - Enhancing the sorption properties of cellulose is a prerequisite for its efficient use in water purification as an alternative to costly activated carbon. Here, solvent-free...     

基于静电喷射法活性多孔磁性炭球的制备及其对亚甲基蓝的吸附

在利用静电喷射一步法获得壳聚糖(CS)磁性微球(Fe₃O₄/CS)的基础上,对Fe₃O₄/CS进行高温炭化和碱活化处理获得活性磁性多孔炭球(A-Fe₃O₄/C),并对A-Fe₃O₄/C吸附水中亚甲基蓝(MB)分子的性能进行了研究。在利用扫描电子显微镜、红外吸收光谱仪、比表面分析仪对制备微球的形貌和结构进行分析的基础上,深入研究溶液pH、吸附时间、温度以及活化剂种类等因素对A-Fe₃O₄/C吸附性能的影响。研究结果表明,A-Fe₃O₄/C对MB的吸附量随着pH值的增加而增大,且经KOH活化后的A-Fe₃O₄/C对MB表现出较优的吸附性能。A-Fe₃O₄/C对MB的吸附过程符合伪二级动力学方程和Langmuir等温线模型,理论最大吸附容量可达300.6 mg·g^-1。此外,A-Fe₃O₄/C表现出良好的重复利用性能,6次循环后对MB的去除率没有明显下降。     

基于静电喷射法活性多孔磁性炭球的制备及其对亚甲基蓝的吸附

在利用静电喷射一步法获得壳聚糖(CS)磁性微球(Fe₃O4/CS)的基础上,对Fe₃O4/CS进行高温炭化和碱活化处理获得活性磁性多孔炭球(A-Fe₃O4/C),并对A-Fe₃O4/C吸附水中亚甲基蓝(MB)分子的性能进行了研究。在利用扫描电子显微镜、红外吸收光谱仪、比表面分析仪对制备微球的形貌和结构进行分析的基础上,深入研究溶液pH、吸附时间、温度以及活化剂种类等因素对A-Fe₃O4/C吸附性能的影响。研究结果表明,A-Fe₃O4/C对MB的吸附量随着pH值的增加而增大,且经KOH活化后的A-Fe₃O4/C对MB表现出较优的吸附性能。A-Fe₃O4/C对MB的吸附过程符合伪二级动力学方程和Langmuir等温线模型,理论最大吸附容量可达300.6 mg·g^-1。此外,A-Fe₃O4/C表现出良好的重复利用性能,6次循环后对MB的去除率没有明显下降。