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1.
Ide A Drisko GL Scales N Luca V Schiesser CH Caruso RA 《Langmuir : the ACS journal of surfaces and colloids》2011,27(21):12985-12995
To take advantage of the full potential of functionalized transition metal oxides, a well-understood nonsilane based grafting technique is required. The functionalization of mixed titanium zirconium oxides was studied in detail using a bisphosphonic acid, featuring two phosphonic acid groups with high surface affinity. The bisphosphonic acid employed was coupled to a UV active benzamide moiety in order to track the progress of the surface functionalization in situ. Using different material compositions, altering the pH environment, and looking at various annealing conditions, key features of the functionalization process were identified that consequently will allow for intelligent material design. Loading with bisphosphonic acid was highest on supports calcined at 650 °C compared to lower calcination temperatures: A maximum capacity of 0.13 mmol g(-1) was obtained and the adsorption process could be modeled with a pseudo-second-order rate relationship. Heating at 650 °C resulted in a phase transition of the mixed binary oxide to a ternary oxide, titanium zirconium oxide in the srilankite phase. This phase transition was crucial in order to achieve high loading of the bisphosphonic acid and enhanced chemical stability in highly acidic solutions. Due to the inert nature of phosphorus-oxygen-metal bonds, materials functionalized by bisphosphonic acids showed increased chemical stability compared to their nonfunctionalized counterparts in harshly acidic solutions. Leaching studies showed that the acid stability of the functionalized material was improved with a partially crystalline srilankite phase. The materials were characterized using nitrogen sorption, X-ray powder diffraction, and UV-vis spectroscopy; X-ray photoelectron spectroscopy was used to study surface coverage with the bisphosphonic acid molecules. 相似文献
2.
Sizgek GD Sizgek E Griffith CS Luca V 《Langmuir : the ACS journal of surfaces and colloids》2008,24(21):12323-12330
Mesoporous zirconium titanium mixed-oxide beads having disordered wormhole textures and mole fractions of Zr (x) ranging from x=0.25 to 0.67 have been prepared. The bead preparation method combined the forced hydrolysis of mixtures of zirconium-titanium alkoxides in the presence of long-chain carboxylates with external gelation. Uniformly sized beads could be produced in the size range 0.5-1.1 mm by varying the droplet size and viscosity of the mixed-oxide sol, thus making them suitable for large-scale column chromatographic applications. The beads exhibited narrow pore size distributions with similar mean pore diameters of around 3.7 nm. The specific surface areas of the beads were linked to the Zr mole fraction in the precursor solution and were generally greater than 350 m2/g for x=0.5. A combination of scanning transmission electron microscopy and X-ray absorption fine structure analysis indicated that the pore walls of the beads were composed of atomically dispersed Zr and Ti to form a continuous network of Zr-O-Ti bonds. Mass transport in the beads was evaluated by monitoring the kinetics of vanadate and vanadyl adsorption at pH 10.5 and 0.87, respectively. 相似文献
3.
Dong LiuPeng Yuan Daoyong Tan Hongmei Liu Tong WangMingde Fan Jianxi ZhuHongping He 《Journal of colloid and interface science》2012,388(1):176-184
Hierarchically porous carbons were prepared using a facile preparation method in which diatomite was utilized as both template and catalyst. The porous structures of the carbon products and their formation mechanisms were investigated. The macroporosity and microporosity of the diatomite-templated carbons were derived from replication of diatom shell and structure-reconfiguration of the carbon film, respectively. The macroporosity of carbons was strongly dependent on the original morphology of the diatomite template. The macroporous structure composed of carbon plates connected by the pillar- and tube-like macropores resulted from the replication of the central and edge pores of the diatom shells with disk-shaped morphology, respectively. And another macroporous carbon tubes were also replicated from canoe-shaped diatom shells. The acidity of diatomite dramatically affected the porosity of the carbons, more acid sites of diatomite template resulted in higher surface area and pore volume of the carbon products. The diatomite-templated carbons exhibited higher adsorption capacity for methylene blue than the commercial activated carbon (CAC), although the specific surface area was much smaller than that of CAC, due to the hierarchical porosity of diatomite-templated carbons. And the carbons were readily reclaimed and regenerated. 相似文献
4.
Griffith CS Sizgek GD Sizgek E Scales N Yee PJ Luca V 《Langmuir : the ACS journal of surfaces and colloids》2008,24(21):12312-12322
A series of zirconium titanium oxide mesophases containing 33 atom % Zr have been prepared using carboxylic acids of different alkyl chain lengths (Cy ) from y=4-18 through organic-inorganic polymer phase segregation as the gel transition is approached. Thermal treatment of these transparent gels up to 450 degrees C eliminated the organic template, and domain coarsening occurred affording stable worm-hole mesoporous materials of homogeneous composition and pore diameters varying from about 3 to 4 nm in fine increments. With such materials, it was subsequently possible to precisely study the adsorption of vanadium oxo-anions and cations from aqueous solutions and, more particularly, probe the kinetics of intraparticle mass transport as a function of the associated pore dimension. The kinetics of mass transport through the pore systems was investigated using aqueous vanadyl (VO2+) and orthovanadate (VO3(OH)2-) probe species at concentrations ranging from 10 to 200 ppm (0.2 to 4 mmol/L) and pH values of 0 and 10.5, respectively. In the case of both of these vanadium species, the zirconium titanate mesophases displayed relatively slow kinetics, taking in excess of about 500 min to achieve maximum uptake. By using a pseudo-second-order rate law, it was possible to extract the instantaneous and overall rate of the adsorption processes and then relate these to the pore diameters. Both the instantaneous and overall rates of adsorption increased with increasing surface area and pore diameter over the studied pore size range. However, the equilibrium adsorption capacity increased linearly with pore diameter only for the higher concentrations and was independent of pore diameter for the lower concentration. These results have been interpreted using a model in which discrete adsorption occurs at low concentrations and is then followed by multilayer adsorption at higher concentration. 相似文献
5.
6.
A. A. Shutilov G. A. Zenkovets V. Yu. Gavrilov S. V. Tsybulya 《Kinetics and Catalysis》2011,52(1):111-118
The formation of the structure of TiO2 (anatase) doped with 1–5 mol % Y2O3 is reported. The dopant changes the anatase structure from regular to nanocrystalline. The nanocruystalline structure consists
of incoherently intergrown 5- to 7-nm anatase crystallites (500°C) separated by interblock boundaries accommodating yttrium
ions. The formation of the nanocrystalline anatase structure stabilizes small anatase crystallites and raises the anatase-to-rutile
phase transition temperature above 900°C. Owing to this structure, the developed specific surface area and fine porous texture
of yttrium oxide-doped titanium dioxide survive up to higher temperatures than those of undoped titanium dioxide. 相似文献
7.
The intercalations of melamine into α- and γ-zirconium phosphates (α- and γ-ZrP) were investigated. Melamine-intercalated α-ZrP afforded two phases with different interlayer distances (d = 1.30 and 1.55 nm). The phase with d = 1.30 nm was obtained as the mixture with original α-ZrP at 30 min reaction by batch method, whereas the single phase with d = 1.55 nm was obtained by decantation method in saturated melamine aqueous solution. Contrary to this, for γ-ZrP a phase with d = 1.78 nm was obtained by both batch and decantation methods in saturated melamine aqueous solution. And new phase with d = 1.48 nm was formed in batch method at low pH or lower concentration of melamine aqueous solution. In these phases the arrangement of melamine changed from a monolayer structure to a bilayer structure with the increase of interlayer distance. Furthermore, melamine-intercalated α- and γ-ZrP adsorbed formaldehyde gas and formaldehyde in formalin solution by interacting with melamine molecule in the interlayer region. In melamine-intercalated γ-ZrP with d = 1.48 nm, the expansion of interlayer distance to around 1.6 nm was observed after the adsorption of formaldehyde gas and formaldehyde in formalin solution. The adsorption of formaldehyde in formalin solution was accompanied with the release of melamine in the interlayer region with increasing the concentration of formaldehyde at 65 °C. 相似文献
8.
JS Ni CY Hung KY Liu YH Chang KC Ho KF Lin 《Journal of colloid and interface science》2012,386(1):359-365
Ruthenium (II) complex dye, Ru(4,4'-dicarboxyl-2,2'-bipyridine)(4-nonyl-2,2'-bipyridine) (NCS)(2), (denoted as RuC9) tethering single alkyl chain was synthesized and well characterized. Its adsorption behavior onto the mesoporous TiO(2) and photovoltaic properties were compared with Z907 which has similar chemical structure but tethers two alkyl chains. RuC9 dyes tend to aggregate into vesicles in the acetonitrile/t-butanol co-solvent as a result of the amphiphilic structure, whereas Z907 dyes aggregate into lamellae. The dye-sensitized solar cell (DSSC) with RuC9 dye showed higher short-circuit photocurrent than that with Z907, attributing to its higher molar optical extinction coefficient and more adsorption amount onto the mesoporous TiO(2). However, the DSSC with Z907 dye has higher open-circuit photovoltage and power conversion efficiency, presumably due to the fact that Z907 with more alkyl chains formed a molecular layer with higher hydrophobicity. It reduced the charge recombination in the interface between the dye-sensitized mesoporous TiO(2) and electrolyte as verified by the electrochemical impedance spectroscopy and intensity modulated photocurrent and photovoltage spectroscopies. 相似文献
9.
10.
Hongngee Lim Anuar Kassim Nayming Huang Mohd. Ambar Yarmo Shootkian Yeong Poisim Khiew Weesiong Chiu 《Colloid Journal》2009,71(5):660-667
In the present study, olive and olein oils had been used for the preparation of three-component high internal phase emulsions
with oil volume fraction of more than 0.77 stabilized by palm-based laureth surfactants for the first time, respectively.
These emulsions were easily prepared by one-pot homogenization. The critical micelle concentration and Gibbs energy of the
as-synthesized surfactants were determined and discussed. Likewise, the morphology, structural properties, stability and hydration
efficacy of the as-prepared emulsions were investigated. Droplet size distribution observed from the optical micrographs was
in agreement with the light scattering results which suggested that droplet size increased with increasing ethylene oxide
chain length. The rheological measurements of the emulsions at room (25°C) and elevated (40°C) temperatures were interpreted
to give clear and direct explanation on the structure and stability of the emulsions. The hydration efficacy of the emulsions
was examined in vivo using a corneometer. Both the emulsions containing olive and olein oils, respectively exhibited high
stability as indicated by the rheological measurements and the structural properties did not differ from one another. However,
olein oil’s hydration efficacy was higher than olive oil’s, suggesting that olein oil could well be a potential moisturizing
lipid which might interest the dermatologists. 相似文献
11.
The applicability of an eluotropic scale pertaining to the desorption of low molecular weight Lewis base solutes from zirconium oxide is examined for its ability to rationalize the retention of proteins on this substrate. The strongest Lewis base eluents (phosphate and fluoride) are able to bring about elution of nearly all proteins provided that their initial mobile phase concentration almost saturates the eluent's adsorption isotherm. In contrast, weaker Lewis bases such as borate, sulfate and bromide are able to elute only those proteins which are retained primarily by ionic interactions. In weak eluents, proteins that contain a large number of accessible Lewis base sites are not eluted from the support. The effect of ionic strength and a variety of Lewis base eluents were also examined. 相似文献
12.
Non-solvent induced phase separation (NIPS) method was employed to fabricate biodegradable poly(lactic acid) (PLA) nanocomposite membranes. Morphological studies using scanning electron microscopy revealed that all the membranes prepared display asymmetric structures comprising finger-like macropores. The incorporation of modified polyhedral oligomeric silsesquioxane (POSS) particles into the PLA matrix resulted in enhanced crystallinity, mechanical, and thermal properties. Annealing of the membranes was performed to explore the influence of temperature on the morphology and properties. After annealing, membranes become more thin and compact, and drastic enhancement in crystallinity is also observed. Consequently, Young's modulus experiences a significant improvement. The reduction in oil absorption capacity after annealing can be attributed to the higher level of crystallinity, reduced porosity, and smaller pore diameter observed in the annealed membranes. Additionally, the unannealed PLA nanocomposite membranes demonstrated exceptional oil absorption capacity, reaching approximately 88%. It is foreseeable that these PLA/POSS nanocomposite membranes possess the potential to be utilized as effective tools for oil–water separation, offering the advantage of mitigating secondary pollution. 相似文献
13.
Q. Ching Wang Frantiek vec Jean M. J. Frchet 《Journal of polymer science. Part A, Polymer chemistry》1994,32(13):2577-2588
The porous structure of monodisperse macroporous beads can be controlled by using soluble polymers with well-defined structural characteristics as part of the porogenic mixture. In general, the use of linear polystyrene as a porogen in the preparation of poly (styrene-co-divinylbenzene) beads shifts the pore size distribution towards larger pores. While a direct correlation between pore size and molecular weight of the porogen has been established, the chemical composition of the polymer porogen has no effect on the porous and chromatographic properties of the beads. These findings suggest that the average molar volume of the porogenic system is important while the miscibility of the polymer porogen with the crosslinked polymer that is formed is of little relevance. © 1994 John Wiley & Sons, Inc. 相似文献
14.
Yu. G. Elistratova A. R. Mustafina D. A. Tatarinov V. F. Mironov V. A. Burilov I. G. Tananaev A. I. Konovalov 《Russian Chemical Bulletin》2011,60(5):790-796
A composite for the extraction of lanthanide ions from strongly acidic media by temperature-induced phase separation was designed
based on the nonionic surfactant Triton X-100 and new phosphine oxide derivatives. The dependence of the efficiency and selectivity
of micellar extraction on the length of the hydrophobic substituent at the P=O group is determined by both the influence of
hydrophobic substituents on the electron-donor capacity of the P=O group and the solubility of phosphine oxides in aqueous
and micellar phases. The nitric acid concentration was found to influence the efficiency of extraction of lanthanide ions
by phosphine oxides with different structures. An increase in the concentration of nitric acid in an aqueous medium from 0.1
to 1 mol L−1 leads to a decrease in the degree of extraction by water-soluble derivatives and a substantial increase in the degree of
extraction by phosphine oxides, which are soluble only in the micellar phase of Triton X-100. 相似文献
15.
Gillich T Benetti EM Rakhmatullina E Konradi R Li W Zhang A Schlüter AD Textor M 《Journal of the American Chemical Society》2011,133(28):10940-10950
This work covers the synthesis of second-generation, ethylene glycol dendrons covalently linked to a surface anchor that contains two, three, or four catechol groups, the molecular assembly in aqueous buffer on titanium oxide surfaces, and the evaluation of the resistance of the monomolecular adlayers against nonspecific protein adsorption in contact with full blood serum. The results were compared to those of a linear poly(ethylene glycol) (PEG) analogue with the same molecular weight. The adsorption kinetics as well as resulting surface coverages were monitored by ex situ spectroscopic ellipsometry (VASE), in situ optical waveguide lightmode spectroscopy (OWLS), and quartz crystal microbalance with dissipation (QCM-D) investigations. The expected compositions of the macromolecular films were verified by X-ray photoelectron spectroscopy (XPS). The results of the adsorption study, performed in a high ionic strength ("cloud-point") buffer at room temperature, demonstrate that the adsorption kinetics increase with increasing number of catechol binding moieties and exceed the values found for the linear PEG analogue. This is attributed to the comparatively smaller and more confined molecular volume of the dendritic macromolecules in solution, the improved presentation of the catechol anchor, and/or their much lower cloud-point in the chosen buffer (close to room temperature). Interestingly, in terms of mechanistic aspects of "nonfouling" surface properties, the dendron films were found to be much stiffer and considerably less hydrated in comparison to the linear PEG brush surface, closer in their physicochemical properties to oligo(ethylene glycol) alkanethiol self-assembled monolayers than to conventional brush surfaces. Despite these differences, both types of polymer architectures at saturation coverage proved to be highly resistant toward protein adsorption. Although associated with higher synthesis costs, dendritic macromolecules are considered to be an attractive alternative to linear polymers for surface (bio)functionalization in view of their spontaneous formation of ultrathin, confluent, and nonfouling monolayers at room temperature and their outstanding ability to present functional ligands (coupled to the termini of the dendritic structure) at high surface densities. 相似文献
16.
Dalibor Šatínský Ivana Brabcová Alena Maroušková Petr Chocholouš Petr Solich 《Analytical and bioanalytical chemistry》2013,405(18):6105-6115
A simple, rapid, and environmentally friendly HPLC method was developed and validated for the separation of four compounds (4-aminophenol, caffeine, paracetamol, and propyphenazone) with different chemical properties. A “green” mobile phase, employing water as the major eluent, was proposed and applied to the separation of analytes with different polarity on polyethylene glycol (PEG) stationary phase. The chromatography separation of all compounds and internal standard benzoic acid was performed using isocratic elution with a low-toxicity mobile phase consisting of 0.04 % (v/v) triethylamine and water. HPLC separation was carried out using a PEG reversed-phase stationary phase Supelco Discovery HS PEG column (15?×?4 mm; particle size 3 μm) at a temperature of 30 °C and flow rate at 1.0 mL min?1. The UV detector was set at 210 nm. In this study, a PEG stationary phase was shown to be suitable for the efficient isocratic separation of compounds that differ widely in hydrophobicity and acid–base properties, particularly 4-aminophenol (log P, 0.30), caffeine (log P, ?0.25), and propyphenazone (log P, 2.27). A polar PEG stationary phase provided specific selectivity which allowed traditional chromatographic problems related to the separation of analytes with different polarities to be solved. The retention properties of the group of structurally similar substances (aromatic amines, phenolic compounds, and xanthine derivatives) were tested with different mobile phases. The proposed green chromatography method was successfully applied to the analysis of active substances and one degradation impurity (4-aminophenol) in commercial preparation. Under the optimum chromatographic conditions, standard calibration was carried out with good linearity correlation coefficients for all compounds in the range (0.99914–0.99997, n?=?6) between the peak areas and concentration of compounds. Recovery of the sample preparation was in the range 100?±?5 % for all compounds. The intraday method precision was determined as RSD, and the values were lower than 1.00 %.
Green chromatography approach – advantages of the technique 相似文献
17.
Moreira MA Santos JC Ferreira AF Loureiro JM Ragon F Horcajada P Yot PG Serre C Rodrigues AE 《Langmuir : the ACS journal of surfaces and colloids》2012,28(7):3494-3502
The potential of the porous crystalline titanium dicarboxylate MIL-125(Ti) in powder form was studied for the separation in liquid phase of xylene isomers and ethylbenzene (MIL stands for Materials from Institut Lavoisier). We report here a detailed experimental study consisting of binary and multi-component adsorption equilibrium of xylene isomers in MIL-125(Ti) powder at low (≤0.8 M) and bulk (≥0.8 M) concentrations. A series of multi-component breakthrough experiments was first performed using n-heptane as the eluent at 313 K, and the obtained selectivities were compared, followed by binary breakthrough experiments to determine the adsorption isotherms at 313 K, using n-heptane as the eluent. MIL-125(Ti) is a para-selective material suitable at low concentrations to separate p-xylene from the other xylene isomers. Pulse experiments indicate a separation factor of 1.3 for p-xylene over o-xylene and m-xylene, while breakthrough experiments using a diluted ternary mixture lead to selectivity values of 1.5 and 1.6 for p-xylene over m-xylene and o-xylene, respectively. Introduction of ethylbenzene in the mixture results however in a decrease of the selectivity. 相似文献
18.
Ke Chen Zhihao Bao Ai Du Xiurong Zhu Jun Shen Guangming Wu Zhihua Zhang Bin Zhou 《Journal of Sol-Gel Science and Technology》2012,62(3):294-303
A rapid and facile synthesis of resorcinol/formaldehyde cross-linked silica (RF/SiO2) aerogels was carried out in one pot based on an acid-catalyzed route, instead of the previously reported base-catalyzed
ones. The gelation time was reduced to several hours at room temperature while it took several days even under heating conditions
in the base-catalyzed ones. The interpenetrating network of RF/SiO2 aerogels showed similar porous structures with those of silica aerogels or RF aerogels. Their thermal conductivity was as
low as that of the typical glass wool materials. The mechanical properties are characterized by dynamic mechanical analysis
and compression testing. At room temperature, the results of compression testing show that the compressive Young’s modulus
or ultimate failure strength of RF/SiO2 aerogel specimen is higher than that of native SiO2 aerogels with a similar density. The one-pot method improves the efficiency and reduces the cost of RF/SiO2 aerogels. The hierarchical porous carbon monoliths are also converted from carbonized RF/SiO2 aerogels by an additional HF treatment. Hence, they could be further explored as multifunctional candidate materials for
thermal, mechanical, and electrochemical applications. 相似文献
19.
Hydroxyapatite (HAp) is a raw material used to fabricate scaffolds. Scaffolds are required to be porous to facilitate nutrient flow and vascularization. This study aims to produce porous HAp ceramics with macropores (>200 μm) and bioactivity and tune their macropore size. Polyethylene glycol (PEG) with molecular weights of 400, 3,400, and 8,300 was used to generate macropores. The macropore size increased as the molecular weight of PEG increased. In this method, emulsions were formed by hydrophobic PEG binding HAp nanoparticles during chemical syntheses. Water foams, as a core of the emulsion, were transformed into steam, and the steam expanded under heat treatment. Macropores were generated by the evaporation of the steam and consolidation of HAp nanoparticles. The difference in the molecular weight of PEG did not affect cell adhesion to the porous HAp ceramics. Cells adhered well to and spread widely on the HAp ceramics regardless of macropore size. 相似文献
20.
New method for obtaining highly dispersed manganese oxide under the action of a dc electric field was suggested. It was found that the electric field parameters affect the phase composition, shape, morphology and size of manganese oxide particles and the content of water. It is demonstrated that the manganese oxide synthesized can be used as a vulcanizing agent in manufacture of sealants based on thiocol and surpasses in application efficiency the analog produced by the conventional method. 相似文献