Zeolite nanoclusters coated onto the mesopore walls of SBA-15

Ultrahigh-field 27Al MAS and MQMAS NMR and 129Xe NMR were used to characterize the zeolite-coated SBA-15 materials. This study shows evidence that zeolite nanoclusters are coated on the mesopore surface of SBA-15. These techniques are useful for the detection of zeolite nanoclusters and different aluminum environments in zeolite/aluminosilicate composites, which are difficult or even impossible to detect by conventional techniques.     

Phenylboronic acid functionalized SBA-15 for sugar capture

The synthesis and characterization of organic-inorganic hybrid materials that selectively capture sugars from model biomass hydrolysis mixtures are reported. 3-Aminophenylboronic acid (PBA) groups that can reversibly form cyclic esters with 1,2-diols, and 1,3-diols including sugars are attached to mesoporous SBA-15 via different synthetic protocols. In the first route, a coupling agent is used to link PBA and SBA-15, while in the second route poly(acrylic acid) brushes are first grafted from the surface of SBA-15 by surface-initiated atom transfer radical polymerization and PBA is then immobilized. The changes in pore structure, porosity, and pore size due to the loading of organic content are measured by powder X-ray diffraction and nitrogen porosimetry. The increase in organic content after each synthesis step is monitored by thermal gravimetric analysis. Fourier transform infrared spectroscopy and elemental analysis are used to characterize the chemical compositions of the hybrid materials synthesized. D-(+)-Glucose and D-(+)-xylose, being the most commonly present sugars in biomass, are chosen to evaluate the sugar adsorption capacity of the hybrid materials. It is found that the sugar adsorption capacity is determined by the loading of boronic acid groups on the hybrid materials, and the hybrid material synthesized via route two is much better than that through route one for sugar adsorption. Mathematical modeling of the adsorption data indicates that the Langmuir model best describes the sugar adsorption behavior of the hybrid material synthesized through route one, while the Freundlich model fits the data most satisfactorily for the hybrid material prepared via route two. The adsorption kinetics, reusability, and selectivity toward some typical chemicals in cellulose acidic hydrolysis mixtures are also investigated.     

Sonosynthesis of spiroindolines using functionalized SBA-15

Functionalized SBA-15 (immobilization of Pd on the modified SBA-15) has been used as an efficient catalyst for the preparation of spiroindolines by multi-component reactions of isatins, cyclic-1,3-diketones, and 6-amino-1,3-dimethyluracil under ultrasonic irradiation in water. The catalyst has been characterized by X-ray diffraction spectroscopy (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FT-IR), N₂ adsorption analysis, temperature-programmed desorption (TPD), and thermogravimetric analysis (TGA). The advantages of this method include the reusability of the catalyst, low catalyst loading, excellent yields in short reaction times and easy separation of products, and use of ultrasonic irradiation as a valuable and powerful technology.

     

Bifunctionalized SBA-15 as a novel micropipette tip sorbent for selective removal and enrichment of biomolecules

Selective enrichment or removal of specific proteins prior to analysis can minimize nonspecific interferences as well as information loss, which has been an important issue in current proteomics fields. In this work, two kinds of mesoporous silica SBA-15 (mean pore diameter of 5 nm and 7 nm), bifunctionalized with quaternary ammonium and C18 groups via silylanization reaction, was used to investigate the adsorption behavior for different proteins (bovine serum albumin (BSA), ovalbumin (OVA), hemoglobin (Hb), lysozyme (Lys) and cytochrome c (cyt c)). As possessing anion exchange (quaternary ammonium) groups, the bifunctionalized SBA-15 showed selective adsorption of the negative charged proteins, BSA and OVA. Based on these properties, sequential fractionation based on different SBA-15 materials as micropipette tip sorbents was developed for sample preparation prior to protein analysis. As expected, after the sequential treatment of the sample, the detection signal of the high abundant BSA was significantly decreased and that of the low abundant cyt c was obviously enlarged, which solved the problem that low abundant protein was suppressed by adjacent high abundant protein. The sample preparation technique significantly improved protein identification and this sequential fractionation approach could be potentially applied to extend information on the protein identification for biological samples with a wide dynamic range.     

Mesoporous silica SBA-15 functionalized with phosphonate and amino groups for uranium uptake

Mesoporous silicas have a very attractive ability of sorption and enrichment of metal ions due to their huge surface area and facile functionalization by organic ligands.In this work,phosphonate-amino bifunctionalized mesoporous silica SBA-15(PA-SBA-15) as U(VI) sorbent was fabricated through post-grafting method.The obtained mesoporous silica was characterized by SEM,XRD,NMR and nitrogen sorption/desorption experiments,which revealed the existence of ordered mesoporous structure with uniform pore diameter and large surface area.The adsorptivity of PA-SBA-15 for U(VI) from aqueous solution was investigated using batch sorption technique under different experimental conditions.The preliminary results show that the U(VI) sorption by PA-SBA-15 is very quick with equilibrium time of less than 1 h,and the U(VI) uptake is as large as 373 mg/g at pH 5.5 under 95 ℃.The sorption isotherm has been successfully modeled by the Langmuir isotherm,suggesting a monolayer homogeneous sorption of U(VI) in PA-SBA-15.The sorption is pH-dependent due to the pH-dependent charge of sorbent in the aqueous solution.The thermodynamics research shows that the sorption is a feasible and endothermic process.Based on these results,PA-SBA-15 could be a promising solid phase sorbent for highly-efficient removal of U(VI) ions from waste water and enrichment of U(VI) from a solution at a very low level.     

A novel dichromate-sensitive fluorescent nano-chemosensor using new functionalized SBA-15

A novel fluorescence nano-chemosensor for Cr₂O₇²⁻ anion has been developed by assembly of fluorescent aluminum complex of 8-hydroxyquinoline (AlQ_x) within the channels of modified SBA-15. SBA-SPS-AlQ_x shows a fluorescence emission at 486 nm. The observed remarkable fluorescence of SBA-SPS-AlQ_x quenches in presence of Cr₂O₇²⁻ anion. The results showed that this fluorescent nano-material can be a useful chemo-sensor for determination of dichromate anions in aqueous solutions. The linear detecting range of fluorescent nano-chemosensor for Cr₂O₇²⁻ anion was 0.16–2.9 μmol L⁻¹. The lowest limit of detection (LDL) was also found to be 0.2 ng mL⁻¹ in aqueous solutions. SBA-SPS-AlQ_x showed selectively and sensitively fluorescent quenching response toward Cr₂O₇²⁻ ion in comparison with I₃⁻, NO₃⁻, CN⁻, CO₃²⁻, Br⁻, Cl⁻, F⁻, H₂PO₄⁻ and SO₄²⁻ ions, which was because of the higher stability of its inorganic complex with dichromate ion.     

Aqueous solubilities of praseodymium,europium, and lutetium sulfates

The aqueous solubilities of finely divided Pr₂(SO₄)₃·8H₂O(cr), Eu₂(SO₄)₃·8H₂O(cr), and Lu₂(SO₄)₃·8H₂O(cr) have been measured as a function of time at 25°C using isothermal saturation. Solubilities of the latter two salts showed a steady decrease with time, whereas Pr₂(SO₄)₃·8H₂O(cr) showed no such variation within the accuracy of the determinations. The turbidities of these filtered saturated solutions also decreased with time, and indicate that some colloidal rare earth sulfates were present. These colloidal particles (<0.2 m) have a large surface area, which contributes to the Gibbs energy of the solid phase, thus giving rise to enhanced solubilities. The micro-particles also grow with time, thereby reducing the surface area contribution to the Gibbs energy and also leaving fewer particles to pass through the filters. Extrapolation of solubilities to infinite time gives the solubilities of macrocurstalline Eu₂(SO₄)₃·8H₂O and Lu₂(SO₄)₃·8H₂O. Previous solubility data for Lu₂(SO₄)₃, at 20 and 40°C, yield an interpolated value at 25°C that is about 30% low. Densities were also measured at several concentrations of each salt.     

HPWA-SBA-15催化合成ETBE

TEM, FTIR and XRD techniques are used to investigate the structure of HPWA-SBA-15. The results show that pores of HPWA-SBA-15 have regular two-dimensional hexagonal structure, and HPWA disperses well in the pore or pore wall of HPWA-SBA-15. NH3-TPD shows the HPWA-SBA-15 catalyst has acidic properties. ETBE is synthesized by the etherification reaction of alcohol and tert-butyl alcohol over several catalysts. Solid acid catalyst HPWA-SBA-15 is the appropriate catalyst which has the highest yield of ETBE than PW12/C and cation resin. The influences of reaction temperature, ratio of alcohol to tert-butyl alcohol are studied. At optimal operation condition, 30% HPWA on HPWA-SBA-15, reaction temperature 100℃, alcohol/tert-butyl alcohol molar ratio 2, the quality catalyst 0.9 g and raw material 10 g, the yield of ETBE is 59.55% and the selectivity is 90.2%.     

一种新的高活性CO氧化催化剂Ag/SBA-1

 以SBA-15为载体,采用后修饰法制备了Ag/SBA-15催化剂. XRD和TEM结果表明,金属Ag粒子均匀分散于SBA-15的纳米孔道中,粒子平均大小为4～5 nm. 同时,负载金属Ag纳米粒子后,载体的介孔结构仍然能很好地保持. CO催化氧化测试结果表明,Ag/SBA-15具有很高的催化活性,120 ℃时就能使CO完全氧化. 而在富H2气氛下,80 ℃时CO的转化率达到最大值(48%),此时O2的选择性为28%. 高温H2还原是活化Ag/SBA-15的必要步骤.     

One pot synthesis of functionalized SBA-15 by using an 8-hydroxyquinoline-5-sulfonamide-modified organosilane as precursor

A novel functionalized SBA-15 mesoporous material was prepared through co-condensation of tetraethylorthosilicate with an 8-hydroxyquinoline-5-sulfonamide-modified organosilane precursor in the presence of P123 as structure-directing agent. After removal of template, the obtained material was characterized by powder X-ray diffraction (XRD), nitrogen adsorption-desorption, Fourier transform infrared (FT-IR), thermal analysis (TGA-DTA), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and elemental analysis. Then, aluminum quinolate complex was attached covalently to this functionalized SBA-15 by using coordinating ability of grafted 8-HQ and its emission spectra showed a slightly blue shift in comparison with AlQ(3) complex.     

Carbon dioxide adsorption over DIPA functionalized MCM-41 and SBA-15 molecular sieves

The capture of carbon dioxide was carried out using MCM-41 and SBA-15 as adsorbents. These mesoporous materials were synthesized by the hydrothermal method, and subsequently functionalized with the di-iso-propylamine (DIPA). Then, they were characterized by XRD, BET, and TG/DTG. The X-ray diffraction patterns of the synthesized samples showed the characteristic peaks of MCM-41 and SBA-15, indicating that the structures of these materials were obtained. The functionalized samples presented a decrease of the intensities of these peaks, suggesting a decreasing in the structural organization of the material; however, the mesoporous structure was preserved. For the adsorption capacity measurements, the materials were previously saturated with carbon dioxide at 75 °C, and then desorbed in a thermobalance in the temperature range of 25–900 °C, under helium atmosphere. Desorption tests showed that the functionalized MCM-41 presented a weight loss of 7.5 wt%, against 5.9 wt% for SBA-15. The obtained values indicate that these nanostructured materials can be used as adsorbent for carbon dioxide capture.     

Highly ordered acid functionalized SBA-15: a novel organocatalyst for the preparation of xanthenes

Post-synthesis modification of SBA-15 has been carried out to design highly ordered acid functionalized hybrid mesoporous organosilica, AFS-1. This material has been used as an efficient heterogeneous organocatalyst for the syntheses of xanthenes under mild conditions in the absence of any other metal co-catalyst.     

Synthesis, characterization and catalytic behavior of functionalized mesoporous SBA-15 with various organo-silanes

Mesoporous silica SBA-15 has been synthesized and functionalized by one-step synthesis method to widen their various application possibilities. In this study, phenyltrimethoxysilane (PTMS), 3-mercaptopropyltrimethoxysilane (MPTMS) and trimethoxypropylsilane (TMPS) were used as silane precursors for the functionalization, and after treated with HCl solution, their catalytic activities were evaluated in the lactic acid-methanol esterification. The presence of anchoring of functional groups on SBA-15 was proved by XRD, FT-IR, BET surface area and pore size distributions. Good catalytic activity was observed especially for SBA-15-SO(3)H-MPTMS, and the catalytic activity order was determined as follows: SBA-15-SO(3)H-MPTMS>SBA-15-TMPS>SBA-15-PTMS, which is directly associated with the surface area, pore size and pore volume. As compared with homogeneous catalyst, SBA-15-SO(3)H-MPTMS heterogeneous catalyst shows remarkable performance, such as separation, recovery and reusability.     

Preparation, characterization and catalytic activity towards green reactions of sulfonic functionalized SBA-15

Acidic heterogeneous catalysts based on the anchorage of sulfonic groups on SBA-15 mesoporous silica were synthesized. In a first synthesis step, samples containing mercapto groups were prepared by co-condensation of tetraethylorthosilicate with 3-mercaptopropyltrimethoxysilane, in presence of ethylene-propylene block copolymer as mesoporous silica structure director. In other samples, mercapto groups were introduced by post-functionalization of the traditional calcined SBA-15. In a second step, these mercapto groups were oxidized in order to get sulfonic acid groups on the surface. Characterization of the samples was carried out by N₂ adsorption-desorption, FTIR, XPS and acid-base titration. Spectroscopic techniques showed that the effective incorporation of sulfonic groups depends on the synthesis methodology used. In turn, the SBA-15 post-synthesis functionalization produces changes in structural characteristics like a decrease in BET surface and changes in the pore size distribution. The as-prepared materials were tested as acid catalysts in the alkylation of isobutane with 1-butene, and in the esterification of free fatty acids with methanol. The results obtained show a lack of activity in the alkylation reaction which can be associated with the formation and stabilization of the intermediate carbocation species.     

Influence of mesoporous structure type on the controlled delivery of drugs: release of ibuprofen from MCM-48, SBA-15 and functionalized SBA-15

Ordered mesoporous materials exhibit potential features to be used as controlled drug delivery systems, including their wide range of chemical compositions and their outstanding textural and structural properties. Therefore, it is possible to control the drug release kinetics by tailoring such parameters. In this paper, mesoporous materials such as MCM-48 and SBA-15, which present different pore sizes (3.7 and 8.8 nm) and structural characteristics (3D-bicontinuous cubic and 2D-hexagonal, respectively) have been synthesized to evaluate their application as drug delivery system and to determine their influence on release kinetic of ibuprofen. Moreover, a chemical modification of the SBA-15 mesoporous material with octadecyltrimethoxysilane has also been performed to study its influence on the release rate of ibuprofen. The structural characteristics (3D cubic and 2D hexagonal pore system) do not affect the release kinetic profiles of ibuprofen. On the contrary, the pore size affects highly to the release kinetic profiles from first-order kinetic to zero-order kinetic for MCM-48 and SBA-15, respectively. Moreover, the importance of surface functionalization was demonstrate through the very fast delivery of ibuprofen from SBA-15 mesoporous materials functionalized with octadecyl chains.     

Immobilization of acetylcholinesterase on functionalized SBA-15 mesoporous molecular sieve for detection of organophosphorus and carbamate pesticide

A novel method for the immobilization of acetylcholinesterase (AChE) on amino modified SBA-15 mesoporous molecular sieves was developed via electrostatic adsorption and glutaraldehyde crosslinking. The immobilized AChE could be exploited as a fast, sensitive and low-cost biocatalyst towards the detection of pesticides residues which could be stored at room temperature for a long time.     

Novel inorganic-organic hybrid fluorescence chemosensor derived from SBA-15 for copper cation

A novel mesoporous SBA-15 type of hybrid material (3-trimethoxysilylpropyl)[4-(2-hydroxyphenyl)methylene] benzenesulfonamide (Schiff-SBA-15) has been obtained by co-condensation of tetraethyl orthosilicate and the organosilane, and the result of XRD confirms the order hexagonal structure of the composite. This hybrid mesoporous material is fluorescent-active, exhibiting high selectivity for sensing Cu2+ in polar solution. The remarkable fluorescence quenching in emission spectrum upon the addition of Cu2+ is attributed to the intramolecular charge transfer after the formation of a coordinate complex of a large conjugate system and Cu2+ ions.