Enhancement of the Sorption Ability of Aluminum Oxide Desiccants by Alkaline Modification

The influence of impregnation of aluminum oxide desiccants prepared by centrifugal thermal activation of hydrargillite with alkali (KОН and NaOH) and carbonate (Na₂CO₃ and K₂СО₃) solutions on the physicochemical properties of the products was studied. Impregnation with alkali solutions increases the dynamic capacity of the desiccants by a factor of 2 and more, whereas impregnation with carbonate solutions decreases the sorption characteristics of the desiccants at similar texture characteristics. Introduction of alkaline modifiers leads to a considerable decrease in the concentration of Lewis acid sites on the surface and to an increase in the concentration of strong base sites. Linear correlation was revealed between the concentration of strong base sites on the surface of the desiccants and their dynamic capacity in drying of humid air. The desiccants modified by impregnation exhibit not only high static and dynamic capacity, allowing improvement of the drying efficiency, but also considerably enhanced mechanical strength.     

Effect of modifying alumina desiccants with sulfuric acid on their physicochemical properties

In the production of alumina desiccants by extrusion, the introduction of sulfuric acid at the stage of preparing a mouldable paste based on hydroxides containing bayerite or pseudoboehmite increases the sorption capacity of the product. This effect is most pronounced for the pseudoboehmite-based materials. The dynamic capacity of these desiccants increases to the level characteristic of the bayerite-containing hydroxide (>5 g H₂O/100 cm³) for a dew point of ?40°C and a contact time of 1.5 s), and their static capacity exceeds this value (increasing from 21.13 to 23.1 g H₂O/100 cm³). This procedure changes the phase composition and textural characteristics of the pseudoboehmite-based desiccants and increases Brønsted acidity and generates strong Lewis acid sites on the surface of all oxides. The dynamic capacity of desiccants with similar textural characteristics depends on the acid-base properties of their surface.     

Fabrication of highly porous starch monoliths and their application as green desiccants

Starch monoliths with oriented porous structures were developed from starches and glycerin as a plasticizer using unidirectional freeze‐drying technology. The morphology of the porous starch monoliths made from different starches was determined by scanning electron microscopy (SEM), and the porosity, mechanical properties and moisture absorption of the porous materials were evaluated. The results show that porous starch monoliths made from oxidized starch with 15% glycerin had good mechanical strength with the best moisture absorption. Increasing the starch concentration significantly improved their strength and increased the moisture absorption rate as well. The moisture absorption of the porous monolith made from oxidized starch is comparable with commonly used desiccants. The porous starch monoliths can successfully remove water from 95% ethanol to produce absolute ethanol due to their selective absorption for water. Copyright © 2011 John Wiley & Sons, Ltd.     

水滑石改性二氧化硅新材料去除养殖用水中的孔雀石绿及结晶紫

合成了水滑石改性的系列硅胶新材料HTS-n(s),该新材料同时包含有酸性位与碱性位,并通过碱腐蚀获得了3～4 nm的小孔和大的比表面积。该类材料可选择性吸附去除水产养殖用水中的工业染料类污染物孔雀石绿和结晶紫。吸附后水中剩余的染料浓度通过高效液相色谱-质谱/质谱联用仪进行检测,结果显示新材料的吸附性能超过常用的工业吸附剂NaY沸石和活性炭。     

Kinetic Aspects of the Adsorption on Aluminum Oxide Drying Agents Doped with Alkali Metal Ions

Fundamental dynamic (kinetic) aspects of the process in which water vapor interacts with the surface of drying agents that are synthesized on the basis of low-temperature modification of aluminum oxide produced from a pseudoboehmite-containing hydroxide and are modified (doped) with alkali atoms (K, Na). It is shown that the kinetics of adsorption on the samples under study, formed from the fine fraction (0.5–1.0 mm) of aluminum oxide adsorbents, can be described with the Glueckauf equation, which rather well describes the dynamics of water vapor absorption in the course of time. The equation parameters were determined: adsorption rate constants and the equilibrium adsorption capacities (a*). It was found that the alkaline modification of the surface of aluminum oxide adsorbents results in that a* increases (by ~40%) as compared with the unmodified drying agent. A correlation is observed between the equilibrium adsorption capacity of the samples under study and the acid-base properties of the surface.     

Control of buckling in colloidal droplets during evaporation-induced assembly of nanoparticles

Micrometric grains of anisotropic morphology have been achieved by evaporation-induced self-assembly of silica nanoparticles. The roles of polymer concentration and its molecular weight in controlling the buckling behavior of drying droplets during assembly have been investigated. Buckled doughnut grains have been observed in the case of only silica colloid. Such buckling of the drying droplet could be arrested by attaching poly(ethylene glycol) on the silica surface. The nature of buckling in the case of only silica as well as modified silica colloids has been explained in terms of theory of homogeneous elastic shell under capillary pressure. However, it has been observed that colloids, modified by polymer with relatively large molecular weight, gives rise to buckyball-type grains at higher concentration and could not be explained by the above theory. It has been demonstrated that the shell formed during drying of colloidal droplet in the presence of polymer becomes inhomogeneous due to the presence of soft polymer rich zones on the shell that act as buckling centers, resulting in buckyball-type grains.     

Preparation and characterization of modified aluminum oxide catalysts

The formation of individual and modified high-purity aluminum oxides (γ-Al₂O₃) prepared from aluminum alcoholates was studied. In the study of the hydrolysis of aluminum alcoholates and modified (Zr, Ti, and Si) aluminum alcoholates, it was found that an increase in the chain length of the alkoxy group and an increase in the aging temperature or aging time in mother liquor resulted in a decrease in the concentration of an amorphous phase, an increase in the concentration of a pseudoboehmite phase, and an improvement in its crystal structure. Hydrolysis in alkaline (a 0.5 wt % solution of ammonia) or neutral solutions made it possible to obtain samples with an almost 100% pseudoboehmite content. At the same time, the samples prepared by hydrolysis in an acidic solution (a 0.1 M solution of HCl) contained a considerable amount of an amorphous phase. It was found that the specific rate of dehydration of n-butanol on the modified aluminum oxide samples linearly decreased with the concentration of donor sites and linearly increased with the concentration of acceptor sites, whose concentration was measured using the spin probe method.     

Polysaccharide-modified iron oxide nanoparticles as an effective magnetic affinity adsorbent for bovine serum albumin

The magnetic separation technique based on magnetic iron oxide nanoparticles (MNPs) has potential applications in protein adsorption and purification, enzyme immobilization, cell sorting, nucleic acid detachment, and drug release. However, the naked MNPs are often insufficient for their hydrophilicity, colloidal stability, and further functionalization. To overcome these limitations, chitosan was firstly carboxymethylated and then covalently conjugated on the surface of the MNPs ranging in size from about 5 to 15 nm, which were prepared by co-precipitating iron (II) and iron (III) in alkaline solution and then treating under hydrothermal conditions. It was found that such modification did not result in the phase change of the MNPs, and the resultant modified nanoparticles were still superparamagnetic. In particular, the colloidal stability of MNPs in aqueous suspension was improved after the surface modification. By investigating the adsorption of bovine serum albumin (BSA) on the modified MNPs, it was observed that the adsorption capacity of the BSA on the modified MNPs increased rapidly within several minutes and then reached the maximum value at about 10 min. The adsorption equilibrium isotherm could be fitted well by the Langmuir model. The medium pH affected greatly the adsorption of the BSA. The maximum adsorption of the BSA occurred at the pH value close to the isoelectric point of the BSA, with a saturation adsorption amount of 94.45 mg/g (25 °C). For the BSA feed concentration of 1.017 mg/ml, a high desorption percentage of 91.5% could be achieved under an alkaline condition (pH 9.4).     

Modification of a montmorillonite-illite clay using alkaline hydrothermal treatment and its application for the removal of aqueous Cs+ ions

A montmorillonite-illite clay was modified using alkaline hydrothermal treatment (reflux method) and applied to the removal of aqueous Cs+ ions. The alkaline solutions were prepared by dissolving NaOH in seawater and in distilled water, and the effect of the two alkaline media on the sorption capacities of the modified clay was discussed. The modified materials were characterized using XRD, SEM/EDS, and FTIR. As a result of the modification, the original mineral was partially transformed into a zeolitic material with spherical morphology. The results showed that the modification improved the Cs+ uptake capacity of the starting clay, with the clay modified in distilled water medium demonstrating higher sorption capacity. The sorption data were adequately described using the Freundlich and Dubinin-Radushkevich isotherm models.     

Sorption of methylene blue on an organoclay bearing thiol groups and application to electrochemical sensing of the dye

In this work, a thiol functionalized-clay was prepared by the covalent grafting of 3-mercaptopropyltrimethoxysilane (MPTMS) onto the surface of a natural smectite clay mineral originating from Cameroon. Effectiveness of the grafting process and properties of the resulting hybrid material were studied by various physico-chemical techniques, such as Fourier transform infrared (FTIR) spectroscopy, N(2) adsorption-desorption experiments (surface area measurements by the BET method) and thermal gravimetric analysis (TGA) coupled with mass spectrometry (MS). Sorption of methylene blue (MB), an electroactive cationic dye, was investigated for both the raw clay and its modified counterpart, as a function of shaking time, adsorbate concentration and pH, through batch experiments. A significant enhancement of the adsorption capacity towards MB was observed with the clay bearing thiol groups in comparison with the pristine one. The obtained sorption data matched the Langmuir isotherm model, from which it appeared that the organoclay adsorbed MB at a maximal loading of 1.04mmolg(-1), while the natural clay displayed a significantly poorer performance (0.31mmolg(-1)). The uptake of MB by the modified clay was found to be highly affected by pH, the cationic dye being more effectively adsorbed in alkaline medium. The possible use of the thiol functionalized-clay as electrode modifier for MB sensing purposes was then evaluated by means of carbon paste electrodes, using cyclic voltammetry. A calibration curve was obtained in the concentration range from 1x10(-6) to 1.4x10(-5)molL(-1), with a detection limit of 4x10(-7)molL(-1)(signal/noise=3).     

应用于全氟辛烷磺酸萃取富集的全氟癸基修饰毛细管硅胶整体柱的制备及应用

利用溶胶-凝胶法,经过烷氧基硅烷的水解、硅羟基的缩聚、凝胶化、陈化、中孔制备、干燥和表面修饰等步骤制备了全氟癸基修饰的毛细管硅胶整体柱。采用该整体柱对全氟辛烷磺酸(PFOS)进行萃取富集,考察其富集特性和效率,并与传统的C18毛细管硅胶整体柱进行对比。结果表明,全氟癸基修饰毛细管硅胶整体柱(15 cm×75 μm)对PFOS具有更高的吸附量和更好的富集选择性,其平均吸附量可以达到75 ng;样品中PFOS的质量浓度为0.25 mg/L时,富集倍数平均可以达到29倍。此全氟癸基修饰毛细管硅胶整体柱对PFOS具有良好的萃取富集性能,可用于水质中痕量PFOS的萃取富集。     

Studying of phenol adsorption on modified forms of bentonite

The modified forms of bentonite are formed by treating it with salts of various metals. Their nature, force and molecule number per 1 cm² are investigated. Also quantity of basic centers on their surface was determined by phenol adsorption.     

Low-cost and effective phenol and basic dyes trapper derived from the porous silica coated with hydrotalcite gel

Novel low-cost and effective adsorbents of phenol and basic dyes were made by coating amorphous silica with hydrotalcite (HT) gel followed by soaking in alkaline solution, and the surface basic-acidic properties of resulting composites were evaluated by CO(2)-TPD, Hammett indicator method and NH(3)-TPD, respectively. Both BET surface area and microporous surface area of the composites were increased after they were soaked with alkaline solution; meanwhile the center of pore size distribution was changed from 9 to 3-4 nm. These composites efficiently captured phenol in gaseous and liquid phases, superior to mesoporous silica such as MCM-48 or SBA-15 and zeolite NaY, and the equilibrium data of gaseous adsorption could be well fitted to Freundlich model. These modified silicas also exhibited high adsorption capacity forward basic dyes such as crystal violet (CV) and leuco-crystal violet (LCV), reaching the adsorption equilibrium within 1 h and offering a new material for environment protection.     

Preparation and morphology of SiO2/PMMA nanohybrids by microemulsion polymerization

Polymethylmethacrylate/SiO2 nanocomposite particles were prepared through microemulsion polymerization by using the silica particles coated with 3-(trimethoxysilyl) propyl methacrylate (MSMA) in both acidic and alkaline conditions. Core-shell and other interesting morphology nanocomposite particles were obtained depending on the pH of the microemulsion, the amount of silanol, and the coupling agent concentration employed. Then, by combining a modified microemulsion polymerization process, i.e., an additional monomer-adding process, the solid contents of the polymer/inorganic nanocomposite microemulsion could greatly increase. Thus, by adjusting these parameters and polymerization process, it was possible to control the morphology and size of the nanocomposites.     

Sorption of Co(II), Ni(II), Ag(I) and Au(III) on pyrazolone-containing inorganic sorbents

The sorption capacity of 3-methyl-1-phenyl-pyrazolone-5 (HMPP)- modified inorganic sorbents has been investigated. The new sorbents are suitable for simultaneous concentration of the 3d elements being investigated over a wide pH range. Choosing appropriate pH values for the corresponding elements, it is possible to achieve their separate extraction.     

Adsorptive removal of tannin from aqueous solutions by cationic surfactant-modified bentonite clay

The removal of tannin from aqueous media by cationic surfactant-modified bentonite clay was studied in a batch system. The surfactant used was hexadecyltrimethylammonium chloride. Adsorbent characterizations were investigated using X-ray diffraction, infrared spectroscopy, surface area analysis, and potentiometric titration. The effects of pH, contact time, initial solute concentration, adsorbent dose, ionic strength, and temperature on the adsorption of tannin onto modified clay were investigated. The adsorbent exhibited higher tannin removal efficiency (>99.0%) from an initial concentration of 10.0 micromol/L at pH 3.0. Adsorption capacity decreased from 90.1 to 51.8% with an increase in temperature from 10 to 40 degrees C at an initial concentration of 25.0 micromol/L. The adsorption process was found to follow pseudo-first-order kinetics. Film diffusion was found to be the rate-limiting step. Tannin adsorption was found to decrease with increase in ionic strength. The tannin equilibrium adsorption data were fitted to Langmuir and Freundlich isotherm models, the former being found to provide the best fit of the experimental data. The maximum monolayer adsorption capacity for tannin was 69.80 micromol/g at 30 degrees C. Comparison of adsorption capacity of the modified clay with reported adsorbents in the literature was also presented. Adsorbed tannin on modified clay can be recovered by treatment with 0.1 M NaOH solution. Regeneration experiments were tried for four cycles and results indicate a capacity loss of <10.0%. From the results it can be concluded that the surfactant-modified clay could be a good adsorbent for treating tannin-contaminated waters.     

The formation of ultralow-density microcellular diane-formaldehyde gels and aerogels

A diane–formaldehyde aerogel is synthesized via a new two-step approach consisting of the sol–gel polycondensation of diane and formaldehyde. The first stage affords individual polymethylol phenols; at the second stage, these are cured in an alkaline solution at 225°С via the introduction of an additional amount of formaldehyde. The diane–formaldehyde gel is isolated for the first time from the initial solution at a minimum possible concentration of gel formation of 1 mg/mL. The aerogel is obtained during supercritical drying of the diane–formaldehyde gel. The density of the ultralow-density microcellular aerogels reaches 10.9 mg/cm³, and their specific surface area amounts to 340–716 m²/g. The features, structures, and properties of the resulting diane–formaldehyde gels are studied.     

Thermodynamic characterization of separations on alkaline-stable silica-based C18 columns: why basic solutes may have better capacity and peak performance at higher pH

A systematic study was made to explain the large improvements in separation performance and capacity of basic compounds at alkaline conditions. The adsorption of three probe components was investigated on four alkaline-stable silica-based C18 columns at three different pH-levels: 3, 7 and 11. The probes were 3-phenyl-1-propanol (neutral), 2-phenylbutyric acid (acidic) and metoprolol (basic). Adsorption isotherms were acquired over a broad concentration range, in order to detect both high and low energy sites. Before the choice of the proper adsorption isotherm model, the adsorption energy distribution (AED) was calculated yielding the number of different kinds of interaction sites between the solute and the stationary phase. The neutral probe was entirely unaffected by pH and its AED was unimodal (one site) indicating homogenous adsorption. For the acidic probe the interactions were unimodal at pH 3 where the probe is uncharged and at least bimodal (two sites) at pH 7 and 11 where the probe is charged. For the basic probe, the interactions were heterogeneous at both pH 3 and 11. The equilibrium constants of the high and low energy sites were different by a factor of 55-100 at pH 3 and only 6-7 at pH 11. The difference in saturation capacities between the two sites was much smaller at pH 11 where 20% of the total capacity is from the high energy site, as compared to pH 3 where the high energy site was only 2-5% of the total capacity. This explains why peaks of amines (basic solutes) tail at low pH while their peaks are symmetrical at alkaline pH. The Langmuir model fit the unimodal data and the bi-Langmuir model fit the bimodal AED data. The calculated band profiles based on these parameters agreed excellently with the experimental data. The electrostatic-modified Langmuir, on the other hand, did not describe this adsorption process well.     

Modified carrageenan. 5. Preparation,swelling behavior,salt‐ and pH‐sensitivity of partially hydrolyzed crosslinked carrageenan‐graft‐polymethacrylamide superabsorbent hydrogel

The polysaccharide, kappa‐carrageenan (κC) was chemically modified to achieve a novel superabsorbent hydrogel via graft copolymerization of methacrylamide (MAM) onto the substrate followed by alkaline hydrolysis. Ammonium persulfate (APS) and N,N′‐methylene bisacrylamide (MBA) were used as a free‐radical initiator and a crosslinker, respectively. The saponification reaction was carried out using sodium hydroxide aqueous solution. Either κC‐g‐PMAM or hydrolyzed κC‐g‐PMAM (PMAM: polymethacrylamide) was characterized by FT‐IR spectroscopy. The effect of grafting variables (i.e. concentration of MBA, MAM, and APS) and alkaline hydrolysis conditions (i.e. NaOH concentration, hydrolysis time and temperature) were systematically optimized to achieve a hydrogel with swelling capacity as high as possible. The swelling capacity of these hydrogels was also measured in various salt solutions. Results indicated that the swelling ratios decreased with an increase in the ionic strength of the salt solutions. This behavior can be attributed to charge screening effect for monovalent cations, as well as ionic crosslinking for multivalent cations. Absorbency of superabsorbing hydrogels was examined in buffer solutions with pH range 1–13. Also, the pH reversibility and on–off switching behavior, at pH values 3.0 and 8.0, makes the synthesized hydrogels good candidates for controlled delivery of bioactive agents. Finally, swelling kinetics in distilled water and various salt solutions was preliminary investigated. Results showed that the swelling in water was faster than in saline solutions. Copyright © 2004 John Wiley & Sons, Ltd.     

Effect of the nature of the additives of metal cations (Sr,Ba, and La) on the properties of Co-Mo hydrodesulfurization catalysts

The effect of the nature of the support modified with the ions of alkaline earth and rare earth elements (Sr, Ba, and La) on the properties of Co-Mo catalysts for the hydrodesulfurization of dibenzothiophene (DBT), 4-methyldibenzothiophene (4-MDBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) was studied using a set of physicochemical and catalytic techniques. It was found that the introduction of modifying additives decreased the surface concentration of Lewis acid sites (LASs) and increased the concentration of basic sites (BSs) in aluminum-containing supports; these changes were more significant upon modification with lanthanum and strontium. The modification affected the distribution and degree of dispersion of Co-Mo-S sulfide packets. It was found that the rate constants of DBT and 4-MDBT conversion increased with decreasing total surface concentration of both LASs and BSs on the support. The highest rate constant of 4,6-DMDBT conversion was reached at an optimum concentration of weak Lewis sites on Co-Mo catalysts, whose support was modified with strontium or barium.