Adsorption site analysis of impurity embedded single-walled carbon nanotube bundles

Bundle morphology and adsorptive contributions from nanotubes and impurities are studied both experimentally and by simulation using a computer-aided methodology, which employs a small physisorbed probe molecule to explore the porosity of nanotube samples. Grand canonical Monte Carlo simulation of nitrogen adsorption on localized sites of a bundle is carried out to predict adsorption in its accessible internal pore volume and on its external surface as a function of tube diameter. External adsorption is split into the contributions from the clean surface of the outermost nanotubes of the bundle and from the surface of the impurities. The site-specific isotherms are then combined into a global isotherm for a given sample using knowledge of its tube-diameter distribution obtained by Raman spectroscopy. The structural parameters of the sample, such as the fraction of open-ended nanotubes and the contributions from impurities and nanotube bundles to total external surface area, are determined by fitting the experimental nitrogen adsorption data to the simulated isotherm. The degree of closure between experimental and calculated adsorption isotherms for samples manufactured by two different methods, to provide different nanotube morphology and contamination level, further strengthens the validity and resulting interpretations based on the proposed approach. The average number of nanotubes per bundle and average bundle size, within a sample, are also quantified. The proposed method allows for extrapolation of adsorption properties to conditions where the purification process is 100% effective at removing all impurities and opening access to all intrabundle adsorption sites.     

Characterization of copper-silica catalysts by means ofin Situ diffuse reflectance infrared Fourier transform spectroscopy

Copper silica catalyst precursors have been characterized by diffuse reflectance infrared Fourier transform spectroscopy. The measurements were performed both under atmospheric conditions and under controlled gasatmospheres at elevated temperatures. Two reflection bands at 3615 and 690 cm^–1 have been attributed to hydroxyl vibrations associated with the presence of copper ions highly dispersed over the silica surface. Calcination of a catalyst precursor at 800 K led to the disappearance of the copper-related surface hydroxyl groups.     

Surface functionalized carbon microspheres for the recovery of copper ion from refinery wastewater

Micro-sized carbon spheres (CNS) were synthesized by hydrothermal process from glucose solution at 443.15 K and two different reaction times. The synthesized CNS samples were surface functionalized with hydroxyl (-OH) functional groups using NaOH treatment, and were tested in batch adsorption to remove heavy metal ion (Cu²⁺) from aqueous solutions. Experimental results revealed that CNS contains mostly amorphous carbon. NaOH functionalized CNS had significantly higher adsorption capacity of copper ～170×10^?3 Kg Cu²⁺/Kg-CNS as compared to the untreated CNS. The adsorption isotherms were well fitted by the Langmuir isotherm equation. The surface morphology of the native and functionalized CNS samples was characterized by a number of techniques and based on which the adsorption of copper ion was discussed.     

Adsorption of Cu(II) onto silica gel-immobilized Schiff base derivative

4-chloroisonitroacetophenone 4-aminobenzylhydrazone (CAAH) chemically anchored on a silica gel surface, has been used for Cu(II) sorption from aqueous solution. The surface modification processes was performed after silanization of silica, then analyzed by elemental analysis, infrared spectroscopy, and thermogravimetry. The sorption behavior of copper(II) was evaluated by the use of batch and column methods. The influences of the concentration, temperature and pH for sorption on the immobilized silica gel with Schiff base were investigated. The obtained dynamic data were fitted to Freundlich, Langmuir and Dubinin-Raduskevich (D-R) isotherms. The mean sorption energy (E) of copper sorption onto silica gel was calculated from D-R isotherm indicating a chemical ion-exchange. The thermodynamic parameters such as Gibbs free energy change, enthalpy change and entropy change were calculated from the adsorption isotherms which were used to explain the mechanism of the adsorption.     

Study of the Porous Solids Obtained by Acid Treatment of a High Surface Area Saponite

A new deposit of saponite, Vicálvaro (Madrid, Spain), has recently been described in the Madrid Basin (provinces of Madrid and Toledo, Central Spain). The acid treatment of such material and the characterization of the solids obtained are reported in the present paper. The surface area of the natural saponite is rather high, 197 m²/g, related to the very small size of the clay particles due to the sedimentary origin of the deposit. The treatment of the saponitic material at room temperature with 0.62 wt% HCl for times of between 2 and 48 h or with 1.25 wt% HCl solutions for times of up to 6 h produces a partial dissolution of the saponite structure, resulting in the formation of mixtures of unattacked saponite and free silica, with a high development of the textural properties of the solids. The treatment with 1.25 wt% HCl solutions for times of over 6 h results in an almost total dissolution of the structure of the clay, the obtained solids being mainly formed by some delaminated saponite sheets, free silica and insoluble impurities. Solids with a maximum surface area of 462 m²/g and a maximum number of acid centres of 0.98 mmol H⁺/g are obtained.     

Effects of fluoride ion on the formation of earthworm‐like mesoporous silica

In a strong acidic environment, ordered earthworm‐like mesoporous silica has been synthesized with CTAB templating and fluoride ion (F^?) as a counterion. The synthesized products were characterized by small‐angle X‐ray diffraction (SXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N₂ adsorption‐desorption isotherms, and Fourier‐transform infrared spectroscopy (FTIR). The effects of F/Si mole ratio on the morphology, surface area, and the pore size of the sample were discussed. It was found that a F/Si mole ratio at 0.083 induced the formation of 3D hexagonal mesophase, whereas higher F/Si mole ratios led to the formation of 2D hexagonal mesoporous silica, the optimum molar ratio of F/Si for the formation of delicate earthworm‐like mesoporous silica was observed at 0.250. The effects of the F/Si mole ratio, surfactant chain length, acid concentration, and shear flow on morphology were also studied.     

Surface properties of cement hydration products. I. Pore structure of calcium silicate hydrates prepared in a suspension form

Adsorption–desorption isotherms of water vapour at 30° were determined on preparations of calcium silicate hydrates of different molar ratios of lime/silica before and after free lime and free silica extractions. From these isotherms specific surface areas were measured and total pore structure analysis was evaluated. A surface layer thickness (t) curve for the adsorption of water vapour on calcium silicate hydrates was constructed, based on experimental curves previously published for the number of layers adsorbed on a variety of non-porous solids with the same heat of adsorption as the calcium silicate hydrates. The existence of both wide pores and micropores was detected in the calcium silicate hydrates. When the samples were free from uncombined lime and silica the micropores were estimated to have an average hydraulic radius of 4–5 Å, whereas the wide pores had an average size of 10 Å. Wide pores up to 200 Å also exist. The pores were predominantly parallel plates.     

Synthesis of graphene-like nanosheets and their hydrogen adsorption capacity

Graphene-like nanosheets have been synthesized by the reduction of a colloidal suspension of exfoliated graphite oxide. The morphology and structure of the graphene powder sample was studied using scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Raman spectroscopy. The graphene sheets are found to be in a highly agglomerated state, with many wrinkles. The sample has a BET surface area of 640 m²/g as measured by nitrogen adsorption at 77 K. Hydrogen adsorption-desorption isotherms were measured in the temperature range 77-298 K and at pressures of up to 10 bar. This gives hydrogen adsorption capacities of about 1.2 wt.% and 0.1 wt.% at 77 K and 298 K, respectively. The isosteric heat of adsorption is in the range of 5.9-4 kJ/mol, indicating a favourable interaction between hydrogen and surface of the graphene sheets. The estimated room temperature H₂ uptake capacity of 0.72 wt.% at 100 bar and the isosteric heat of adsorption of our sample are comparable to those of high surface area activated carbons, however significantly better than the recently reported values for graphene and a range of other carbon and nanoporous materials; single and multi walled carbon nanotubes, nanofibers, graphites and zeolites.     

Improved analytical flowfactors for mass-flow hoppers

A significant proportion of the U.S. hematitic ores contain silica and other impurities in a very finely dispersed form. The mineralogical heterogeneity of the particle surface and sub-surface regions of such natural hematite and the effect of desliming treatments, are examined in this work using scanning electron microscopy, energy dispersive analysis of X-rays and Auger spectroscopy techniques. The implications of the observed mineralogical heterogeneity on interfacial properties such as zeta potential and adsorption, and on the validity of prior interpretations of results obtained for such properties are discussed. Specifically, the reasons for a lower isoelectric point of natural hematites than that of the synthetic hematite, and for the adsorption of anionic collectors on natural hematite above their isoelectric point, are explained on the basis of the concentration of impurities, as in this case silica and clay, in the surface region.     

Functionalization of Tailored Porous Carbon Monolith for Decontamination of Radioactive Substances

As the control over radioactive species becomes critical for the contemporary human life, the development of functional materials for decontamination of radioactive substances has also become important. In this work, a three-dimensional (3D) porous carbon monolith functionalized with Prussian blue particles was prepared through removal of colloidal silica particles from exfoliated graphene/silica composite precursors. The colloidal silica particles with a narrow size distribution were used to act a role of hard template and provide a sufficient surface area that could accommodate potentially hazardous radioactive substances by adsorption. The unique surface and pore structure of the functionalized porous carbon monolith was examined using electron microscopy and energy-dispersive X-ray analysis (EDS). The effective incorporation of PB nanoparticles was confirmed using diverse instrumentations such as X-ray diffraction (XRD), Fourier-transform infrared (FT-IR), and X-ray photoelectron spectroscopy (XPS). A nitrogen adsorption/desorption study showed that surface area and pore volume increased significantly compared with the starting precursor. Adsorption tests were performed with ¹³³Cs ions to examine adsorption isotherms using both Langmuir and Freundlich isotherms. In addition, adsorption kinetics were also investigated and parameters were calculated. The functionalized porous carbon monolith showed a relatively higher adsorption capacity than that of pristine porous carbon monolith and the bulk PB to most radioactive ions such as ¹³³Cs, ⁸⁵Rb, ¹³⁸Ba, ⁸⁸Sr, ¹⁴⁰Ce, and ²⁰⁵Tl. This material can be used for decontamination in expanded application fields.     

Uses of Ozone in a Three-Phase System for Water Treatment: Ozone Adsorption

A new technique of using ozone for water treatment is presented. This new technique consists of using a three-step-process composed firstly of ozone adsorption on an appropriate adsorbent, secondly water treatment, and thirdly regeneration of the adsorbent. Results regarding ozone adsorption (the first step) are presented in this paper. Different types of silica gel and a type of TiO₂ have been tested for ozone adsorption. It was found that the physical characteristics of the silica gel affect its capacity for ozone. Titanium dioxide has shown ozone decomposition instead of adsorption as it contains Lewis acid sites. An exponential decrease of the silica gel capacity with its moisture content has been found. Linear isotherms in the range of ozone concentrations less than 100?g/m³ NTP have been found. A particle diffusion model with linear equilibrium isotherm has been used to model the breakthrough curves in fixed bed columns.     

焙烧态Ca-Mg-Al类水滑石的制备及其吸附As(V)的研究

实验合成了一种焙烧态Ca-Mg-Al类水滑石,通过吸附动力学、吸附热力学及pH值的影响实验研究其对As (V)的吸附性能;并通过X射线衍射(XRD)、比表面积及孔径(BET)、场发射扫面电子显微镜(FESEM)、傅里叶红外光谱(FTIR)和X射线光电子能谱(XPS)等测试对合成材料进行表征并分析其吸附机理.实验结果表明,焙烧态Ca-Mg-Al 类水滑石对As(V)具有较强的吸附能力,其最大吸附量为71.86 mg/g,其吸附行为较符合Freundlich吸附等温方程和准一级动力学方程,且在不同的pH值下均能保持较好的吸附能力.焙烧态Ca-Mg-Al 类水滑石吸附As(V)的吸附机理主要包括类水滑石晶体结构的重建以及其表面羟基官能团的络合作用.     

天然石英中气液杂质的热动力解吸

高纯天然石英是生产透明石英玻璃、石英坩埚的原料,其中气-液杂质的含量是影响石英玻璃许多性能的决定性因素。用配有离子源和无油真空泵系统的质谱仪对天然石英中的10种主要气-液杂质进行研究。结果表明：水是天然石英中的主要气-液杂质。熔制实验证明：高温水的含量是影响天然石英质量的最主要因素。根据测试数据可以计算出不同温度阶段水在石英中的扩散系数,推荐脱除天然石英中气-液杂质的工艺条件。     

Synthesis and characterisation of organo-silica hydrophobic clay heterostructures for volatile organic compounds removal

Mesostructured materials belonging to a new class of solid acids known as porous clay heterostructures (PCHs) have been prepared by chemical modification of a natural clay, by using a cationic surfactant, a neutral amine, and an equimolar mixture of bis(triethoxysilyl)benzene (BTEB) and tetraethyl orthosilicate (TEOS). The effect of different polymerisation times of the silica sources and of the hydrocarbon chain length of the neutral amine was studied. The materials retained their layered structure after the formation of stable pillars by the polymerisation of hydrolysed TEOS and BTEB. All materials were characterised by low temperature nitrogen adsorption isotherms, ¹³C CP MAS, ²⁹Si MAS and CP MAS NMR spectroscopy, thermal analyses and infrared spectroscopy. The specific surface BET areas of the materials were in the range 550–800 m² g⁻¹ and the corresponding microporous volume were near 0.2–0.3 cm³ g⁻¹. The reduction of the reaction time from 12 to 4 h avoids the extra-gallery polymerisation, contributing for a larger specific surface area. The increase of two carbon atoms in the neutral amine chain does not show much effect on the available surface area.

These materials were very effective as adsorbents of volatile organic compounds (VOCs), according to tests on methanol, methyl ethyl ketone, toluene and trichloroethylene. The water adsorption isotherms proved the hydrophobicity of the materials, suggesting their capabilities for VOC adsorption in the presence of water.     

Preparative scale isocratic chromatographic purification of a polyethylene mono-alcohol accompanied by high resolution evaluation of molecular weight distribution

A simple preparative-scale adsorption chromatographic method for separating a commercially available polyethylene mono-alcohol from its non-functional polyethylene impurities has been established using silica as the stationary phase and toluene at 75°C as the isocratic eluant. Characterization of the chromatographic fractions by ¹H-NMR spectroscopy also provided unexpected comprehensive information on the molecular structure and molar mass distribution of the polyethylene mono-alcohol. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Adsorption of thiram from aqueous solution on activated carbon and sepiolite

Adsorption of thiram on activated carbon and acid-heat treated sepiolite from aqueous solution at 10° C, 20° C, 30° C and 40° C has been studied. The adsorption isotherms may be classified as L type of the Giles classification which suggests that there is no strong competition from the solvent for adsorption sites. The experimental data points have been fitted to the Langmuir equation in order to calculate the adsorption capacities of the solids as well as their surface areas available to the thiram molecules. The removal efficiency (P) has been calculated for both adsorbents resulting that activated carbon is more effective (P = 98–100%) in removing thiram from aqueous solution than acid-heat treated sepiolite (P = 14–52%).     

Kinetic behaviour of adsorption of gelatin at solid–liquid interface

The kinetics of adsorption of gelatin from its aqueous solution on to silica has been studied at room temperature. The adsorption isotherms were found to be of the Langmuir type. From the adsorption isotherms, the adsorption coefficient, surface coverage and rate constants for adsorption and desorption were evaluated. The rate of adsorption was found to be maximum at the isoelectric point of gelatin and decreased with increase in pH of the adsorption medium. The increased ionic strength of the medium also caused an increase in the rate and amount of adsorption.     

Phenol adsorption on porous and non-porous carbons

Phenol physisorption on a series of porous and non-porous amorphous carbons was studied at 298 K. Grand Canonical Monte Carlo computer simulations were performed to simulate phenol adsorption from the gas phase. Phenol is adsorbed in a solid-like state within the pores and there is no well-developed multilayer regime. The ‘t’ plot method was adapted to phenol adsorption and the results obtained are in agreement with the model solids employed. The simulated adsorption isotherms were compared with experimental results obtained for adsorption from aqueous solutions of phenol. BET surface areas were calculated. Other characteristics of the adsorption system analyzed were: adsorption energy distribution functions, density profiles, distribution of molecules according to gas-solid energy, and local isotherms.     

X-ray Photoelectron Spectroscopy Analysis of Potassium Adsorption onto v-SiO2: Observation of Reactive Surface Defect Sites

The adsorption of potassium onto a clean silica surface has been studied by X-ray photoelectron spectroscopy (XPS). The fracture surface of silica was cleaned by Ar⁺ sputtering and exposed to potassium metal vapor for 10-s intervals up to 50 s, resulting in 0.2 to 2 monolayer coverage. High-resolution XPS spectra were recorded for the K 2p, O 1s, and Si 2p photoelectrons at each potassium exposure. Potassium uptake curves were generated from peak areas which suggest the mechanism of adsorption. Curve synthesis techniques were employed on the O 1s spectra to identify the various chemical states present. A decrease in a reactive state is observed as the number of nonbridging oxygen states increases. Angleresolved XPS was also used to determine the relative position, with respect to depth, of these reactive sites, showing that they are at a higher concentration near the surface.