Hydrothermal Stability of Modified Silica Membranes for Gas Separation

A new class of hybrid molecular sieve silica (MSS) membranes is developed and tested against standard and organic templated membranes. The hybrid membrane is synthesized by the standard sol-gel process, integrating a template (methyltriethoxysilane - MTES) and a C6 surfactant (triethylhexylammonium bromide) into the silica film matrix. After hydro treatment under a relative humidity of 96% for 50h, the hybrid membrane shows no changes in its gas separation capabilities or energy of mobility. The structural characteristics and integrity of the hybrid membrane are retained due to a high concentration of organophilic functional groups and alkoxides observed using 29 Si NMR. In contrast, the structural integrity of the membranes prepared with non-templated films deteriorated during the hydro treatment due to a large percentage of silanol groups (Si-OH) which react with water. The hybrid membranes underwent a decrease in the H2/CO2 selectivity of only 1% whereas for the non-templated membrane a 21% decrease was observed. The transport mechanism of the hybrid membranes is activated as permeation increased with temperature. The activation energy for the permeation of H2 is positive while negative for CO2. The H2 permeation obtained was 3x 10 -8 mol.m -2 .s -1 .Pa -1 and permselectivities for H2/CO2 and H2/N2 varied between 1-7 and 31-34, respectively.

Role of the crystallite phase of TiO2 in heterogeneous photocatalysis for phenol oxidation in water

A series of TiO2 samples with different anatase-to-rutile ratios was prepared by calcination, and the roles of the two crystallite phases of titanium(IV) oxide (TiO2) on the photocatalytic activity in oxidation of phenol in aqueous solution were studied. High dispersion of nanometer-sized anatase in the silica matrix and the possible bonding of Si-O-Ti in SiO2/TiO2 interface were found to stabilize the crystallite transformation from anatase to rutile. The temperature for this transformation was 1200 degrees C for the silica-titania (ST) sample, much higher than 700 degrees C for Degussa P25, a benchmarking photocatalyst. It is shown that samples with higher anatase-to-rutile ratios have higher activities for phenol degradation. However, the activity did not totally disappear after a complete crystallite transformation for P25 samples, indicating some activity of the rutile phase. Furthermore, the activity for the ST samples after calcination decreased significantly, even though the amount of anatase did not change much. The activity of the same samples with different anatase-to-rutile ratios is more related to the amount of the surface-adsorbed water and hydroxyl groups and surface area. The formation of rutile by calcination would reduce the surface-adsorbed water and hydroxyl groups and surface area, leading to the decrease in activity.

A novel method for fast enrichment and monitoring of hexavalent and trivalent chromium at the ppt level with modified silica MCM-41 and its determination by inductively coupled plasma optical emission spectrometry

Chromium(III) at the ng L-1 level was extracted using partially silylated MCM-41 modified by a tetraazamacrocyclic compound (TAMC) and determined by inductively coupled plasma optical emision spectrometry (ICP OES). The extraction time and efficiency, pH and flow rate, type and minimum amount of stripping acid, and break- through volume were investigated. The method's enrichment factor and detection limit are 300 and 45.5 pg mL-1, respectively. The maximum capacity of the 10 mg of modified silylated MCM-41 was found to be 400.5±4.7 µg for Cr(III). The method was applied to the determination of Cr(III) and Cr(VI) in the wastewater of the chromium electroplating industry and in environmental and biological samples (black tea, hot and black pepper).

Stereoselective syntheses of (+)- isoretronecanol and (+)-5-epi-tashiromine via addition of chiral titanium (iv) enolates to cyclic n-acyliminium ions

The stereoselective addition of the titanium (IV) enolates derived from (S)-4-isopropyl-N-4-chlorobutyryl-1,3-thiazolidine-2-thione (8) and from (S)-4-isopropyl-N-4-chloropentanoyl-1,3-thiazolidine-2-thione (9) to N-Boc-2-methoxypyrrolidine (5b) afforded the addition products (+)-10 and (+)-11 in 84% yield in both cases, as 8.6:1 and 10:1 diastereoisomeric mixtures, respectively. A three-step sequence allowed to convert these adducts to (+)-isoretronecanol (1) and (+)-5-epi-tashiromine (2) in 43% and 49% overall yield, respectively.

Determination of Copper, Iron, Nickel and Zinc in fuel kerosene by FAAS after adsorption and pre-concentration on 2-aminothiazole-modified silica gel

Silica gel chemically modified with 2-Aminotiazole groups, abbreviated as SiAT, was used for preconcentration of copper, zinc, nickel and iron from kerosene, normally used as a engine fuel for airplanes. Surface characteristics and surface area of the silica gel were obtained before and after chemical modification using FT-IR, Kjeldhal and surface area analysis (B.E.T.). The retention and recovery of the analyte elements were studied by applying batch and column techniques. The experimental parameters, such as shaking time in batch technique, flow rate and concentration of the eluent (HCl- 0.25-2.00 mol L-1) and the amount of silica, on retention and elution, have been investigated. Detection limits of the method for copper, iron, nickel and zinc are 0.77, 2.92, 1.73 and 0.097 mg L-1, respectively. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in kerosene using flame AAS for their quantification.

Determination of Hg in water by CVAAS using 2-aminothiazole modified silica

This paper discusses a rapid and sensitive method developed to determine trace levels of mercury in natural water samples by cold vapor atomic absorption spectrometry using a preconcentration system composed by mini-column packed with 100 mg of 2-aminothiazol modified silica gel (SiAT) coupled on-line with the spectrometer's cold vapor generator system. The optimum preconcentration conditions are also described here. The preconcentrated Hg(II) ions were eluted directly from the column to the spectrometer's cold vapor generator system using 100 µL of 2 mol L-1 hydrochloric acid and the retention efficiency achieved exceeded 95%. The enrichment factors determined were 29, 38 and 46 using 3, 4 and 5 mL of preconcentrated aqueous solutions containing 400 ng L-1 of Hg. The detection limit calculated was 5 ng L-1. The preconcentration procedure was applied to determine trace level mercury in spiked river water samples.

Use of modified silica gel for concentrating Pb (II) and Cd (II) occurring in form of complex anions

The performance of silica gel, modified by the impregnation with a high molecular weight quaternary amine (triethyl octadecyl ammonium iodide), used for the concentration of heavy metals occurring in water is studied. The material under study captures Cd, Pb, which are capable of forming stable complexes with I- ions.The results obtained about the metal capture, under dynamic conditions, are described and metal ions are removed by desorption with EDTA and quantified by AAS.

Catalysis by sulphated tin oxide modified with some transition metal oxides

In the present work, we have tried to evaluate systematically the surface properties of sulphated tin oxide systems modified with three different transition metal oxides viz. iron oxide, tungsten oxide and molybdenum oxide. The catalytic activities of these systems are checked and compared by carrying out some industrially important reactions such as oxidative dehydrogenation of ethylbenzene and Friedel-Crafts reactions.

An electroanalytical application of 2-aminothiazole-modified silica gel after adsorption and separation of Hg(II) from heavy metals in aqueous solution

2-Aminothiazole covalently attached to a silica gel surface was prepared in order to obtain an adsorbent for Hg(II) ions having the following characteristics: good sorption capacity, chemical stability under conditions of use, and, especially, high selectivity. The accumulation voltammetry of mercury(II) was investigated at a carbon paste electrode chemically modified with silica gel functionalized with 2-aminothiazole (SIAMT-CPE). The repetitive cyclic voltammogram of mercury(II) solution in the potential range -0.2 to + 0.6 V versus Ag/AgCl (0.02 mol L-1 KNO3; V = 20 mV s(-1)) show two peaks one at about 0.1 V and other at 0.205 V. The anodic wave peak at 0.205 V is well defined and does not change during the cycles and it was therefore further investigated for analytical purposes using differential pulse anodic stripping voltammetry in differents supporting electrolytes. The mercury response was evaluated with respect to pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. The precision for six determinations (n = 6) of 0.02 and 0.20 mg L-1 Hg(II) was 4.1 and 3.5% (relative standard deviation), respectively. The detection limit was estimated as 0.10 mu g L-1 mercury(II) by means of 3:1 current-to-noise ratio in connection with the optimization of the various parameters involved and using the highest-possible analyser sensitivity. (c) 2006 Elsevier Ltd. All rights reserved.

4-amine-2-mercaptopyrimidine modified silica gel applied in Cd(II) and Pb(II) extraction from an aqueous medium

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Preconcentration and determination of Cu(II) in a fresh water sample using modified silica gel as a solid-phase extraction adsorbent

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Copper Hexacyanoferrate Formation on the Modified Silica Surface with DAB-Am-16 Dendrimer

The third generation (G-3) polypropylenimine hexadecaamine dendrimer (DAB-Am-16) was grafted onto the silica gel surface. The modified silica interacts easily with Cu(2+) and then with potassium ferrocyanide to form copper hexacyanoferrate. The modified silica was characterized by the following techniques: Nuclear Magnetic Resonance (NMR), FTIR spectroscopy, Energy Dispersive X-ray (EDX) and Cyclic Voltammetry. The modified silica containing copper hexacyanoferrate (CuHCFSD) was tested for a voltammetric determination of nitrite using a modified graphite paste electrode.

Synthesis, characterization, and application of modified silica in the removal and preconcentration of lead ions from natural river water

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Determination of metal ions in natural waters by flame-AAS after preconcentration on a 5-amino-1,3,4-thiadiazole-2-thiol modified silica gel.

5-amino-1,3,4-thiadiazole-2-thiol groups attached on a silica gel surface have been used for adsorption of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II) and Zn(II) from aqueous solutions. The adsorption capacities for each metal ion were (in mmol.g(-1)): Cd(II)= 0.35, Co(II)= 0.10, Cu(II)= 0.15, Fe(III)= 0.20, Hg(Il)= 0.46, Ni(II)= 0.16, Pb(II)= 0.13 and Zn(II)= 0.15. The modified silica gel was applied in the preconcentration and quantification of trace level metal ions present in water samples (river, and bog water).

Determination of Cu, Ni, and Zn in fuel ethanol by FAAS after enrichment in column packed with 2-aminothiazole-modified silica gel

This work describes the synthesis and characterization of 2-aminothiazole-modified silica gel (SiAT), as well as its application for preconcentration (in batch and column technique) of Cu(II), Ni(II) and Zn(II) in ethanol medium. The adsorption capacities of SiAT determined for each metal ion were (mmol g(-1)): Cu(II)=1.20, Ni(II)=1.10 and Zn(II)=0.90. In addition, results obtained in flow experiments, showed a recovery of ca. 100% of the metal ions adsorbed in a column packed with 500 mg of SiAT. The eluent was 2.0 mol L-1 HCl. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in fuel ethanol using flame AAS for their quantification.