Titanium species in titanium silicalite TS-1 prepared by hydrothermal method

The titanium species existing in titanium silicalite TS-1, which is prepared by hydrothermal method, were investigated using chemical analysis, XRD, FT-IR, Si-29 MAS NMR, UV-VIS, ESR. It has been observed that several kinds of titanium species may exist in titanium silicalite. The form that titanium atoms incorporate into the framework of titanium silicalite synthesized using tetrapropylammonium bromide (TPABr) as template differs from that using the classical method. But, the symmetry of titanium silicalite, changes from monoclinic to orthorhombic with the increase of titanium content in both methods. The Ti-O-2(-) originated from framework titanium and H2O2 has the moderate stability and may be active site in oxidation reaction. TS-1 synthesized using TPABr as template does not contain anatase, but contains a kind of partly condensed titanium species with six-fold coordination. The titanium species may correspond to 270-280 mn band in UV-VIS spectra and also can form Ti-O-2(-). But, this kind of Ti-O-2(-) is very stable and cannot be catalytic active site. So, the six-fold coordination titanium species may be inactive in both the oxidation reaction and the decomposition of H2O2. The hypothesis has been further proved by the phenomena that the titanium species is easily washed off using acid, and acid treating will not influence the catalytic performance of TS-1. (C) 2001 Elsevier Science B.V. All rights reserved.

Highly ordered periodic mesoporous ethanesilica synthesized under neutral conditions

Highly ordered mesoporous ethanesilica (MES) with 2D hexagonal structure was synthesized from 1,2-bis(trimethoxysilyl) ethane under neutral conditions for the first time. Divalent salts, such as NiCl2, MgCl2, ZnCl2, ZnSO4 and Zn(NO3)(2), were used to help the formation of the ordered mesostructure. The MES samples were characterized by powder X-ray diffraction, nitrogen sorption, transmission electron microscopy, FT-IR, C-13 and Si-29 solid-state NMR and thermal gravimetric analysis. A phase transition from a disordered wormhole-like structure to an ordered P6mm structure was observed upon the addition of inorganic salts. The pore size of the MES decreases from 4.7 to 3.9 nm with increasing content of the inorganic salts. Fluoride was also found to be important for the formation of ordered MES under neutral conditions.

Structural relation properties of hydrothermally stable functionalized mesoporous organosilicas and catalysis

The surfactant assistant syntheses of sulfonic acid functionalized periodic mesoporous organosilicas with large pores are reported. A one-step condensation of tetramethoxysilane (TMOS) with 1,2-bis(trimethoxysilyi)ethane (BTME) and 3-mercaptopropyltrimethoxysilane (MPTMS) in highly acidic medium was performed in the presence of triblock copolymer Pluronic P123 and inorganic salt as additive. During the condensation process, thiol (-SH) group was in situ oxidized to sulfonic acid (-SO3H) by hydrogen peroxide (30 wt % H2O2). X-ray diffraction studies along with nitrogen and water sorption analyses reveal the formation of stable, highly hydrophobic, and well-ordered hexagonal mesoscopic structures in a wide range of -CH2CH2-concentrations in the mesoporous framework. The resultant materials were also investigated by Si-29 MAS and C-13 CP MAS NMR, thermogravimetric analyses, UV-Raman spectroscopy, and FT-IR spectroscopy. The role of the bridged organic group on the hydrothermal stability of the mesoporous materials was established, which revealed an enhancement in hydrothermal stability of the materials with incorporation of the bridged organic groups in the network. The catalytic performance of -SO3H functionalized mesoporous materials was investigated in the esterification of ethanol with acetic acid, and the results demonstrate that the ethane groups incorporated in the mesoporous framework have a positive influence on the catalytic behavior of the materials.

Hydroisomerization of long-chain alkane over Pt/SAPO-11 catalysts synthesized from nonaqueous media

SAPO-11 molecular sieves were synthesized from nonaqueous media. The effects of Si and Al sources as well as solvents on the catalytic performance of SAPO-11 were investigated by the hydroisomerization reaction of n-dodecane. The samples were characterized by XRD, XRF, N-2-adsorption, SEM, NH3-TPD, IR-NH3 and Si-29 CP MAS NMR. The SAPO-11 samples synthesized with tetraethoxysilane as the Si source showed higher Si incorporation contents than the SAPO molecular sieves prepared with polymeric Si sources (fumed silica and Si colloidal gel). The reaction results showed that Pt/SAPO-11 catalysts synthesized from ethylene glycol and glycerol media with the monomeric Si and Al sources (tetraethoxysilane, aluminum isopropoxide) exhibited higher catalytic activities than those catalysts with the polymeric Si or Al (pseudo-boehmite) sources, due to the larger external surface area and higher acidity of the former ones. Especially, the catalyst synthesized in an ethylene glycol medium possessed the highest catalytic activity. Over this catalyst, 88% conversion of n-dodecane was achieved at a low temperature of 250 degrees C.

Immobilisation of heavy metal in cement-based solidification/stabilisation: a review

Heavy metal-bearing waste usually needs solidification/stabilization (s/s) prior to landfill to lower the leaching rate. Cement is the most adaptable binder currently available for the immobilisation of heavy metals. The selection of cements and operating parameters depends upon an understanding of chemistry of the system. This paper discusses interactions of heavy metals and cement phases in the solidification/stabilisation process. It provides a clarification of heavy metal effects on cement hydration. According to the decomposition rate of minerals, heavy metals accelerate the hydration of tricalcium silicate (C3S) and Portland cement, although they retard the precipitation of portlandite due to the reduction of pH resulted from hydrolyses of heavy metal ions. The chemical mechanism relevant to the accelerating effect of heavy metals is considered to be H+ attacks on cement phases and the precipitation of calcium heavy metal double hydroxides, which consumes calcium ions and then promotes the decomposition Of C3S. In this work, molecular models of calcium silicate hydrate gel are presented based on the examination of Si-29 solid-state magic angle spinning/nuclear magnetic resonance (MAS/NMR). This paper also reviews immobilisation mechanisms of heavy metals in hydrated cement matrices, focusing on the sorption, precipitation and chemical incorporation of cement hydration products. It is concluded that further research oil the phase development during cement hydration in the presence of heavy metals and thermodynamic modelling is needed to improve effectiveness of cement-based s/s and extend this waste management technique. (C) 2008 Elsevier Ltd. All rights reserved.

Textural and structural properties of bioactive glasses in the system CaO-SiO2

Gel-derived CaO-SiO2 binary glasses of CaO mole fractions 0. 2, 0.3 and 0. 4 have been prepared and characterised. Pore diameter specific pore volume, skeletal density and porosity were found to increase with increasing CaO-content, whereas a concomitant decrease in specific surface area was observed. Si-29 NMR indicated that the 0.2 CaO mole fraction glass consisted of higly polymerized Q(4) and Q(3) silicate species, with some Q(2) units. With increasing CaO mole fraction, these silicate species became progressively depolymerised such that isolated SiO4 tetrahedra were detected within the 0.4 CaO glass matrix. Unusually, the glasses retained a proportion of Q(4) and Q(3) species as the CaO mole fraction was increased. All glass formulations exhibited in vitro bioactivity. The rate of hydroxyapatite precipitation followed the order 0.2 CaO > 0.4 CaO > > 0.3 CaO, an effect that is attributed to differences in the rate of dissolution of calcium from these glasses. This, in turn, appears to be dependent upon the proportion of Ca 21 participating in the formation of the glassy network.

Selective oxidation of a pyrimidine thioether using supported tantalum catalysts

Ta2O5-SiO2 catalysts were prepared by a sol-gel method using tetraethyl orthosilicate (TEOS) and tantalum (V) ethoxide as the sources of silicon and tantalum, and two families of quaternary ammonium salts, [CnH(2n+1)(CH3)(3)N]Br (n = 14, 16, 18) and [(CnH(2n+1))(4)N]Br (n = 10, 12, 16, 18) as surfactants. The catalysts were compared for the selective suffoxidation of 4,6-dimethyl-2-thiomethylpyrimidine using peroxide as an oxidising agent in a range of ionic liquids and organic solvents. The sol-gel catalysts were also compared with tantalum on MCM-41 prepared by grafting. The catalysts were characterized from adsorption-desorption isotherms of N-2, XRD patterns, small-angle X-ray scattering, IR spectra from adsorbed pyridine and CDCl3, XPS spectra, and Si-29 magic angle spinning (MAS) NNIR experiments. The effect of recycling on the catalyst leaching and selectivity/activity was also studied. High activities and selectivities were found in [NTf2](-) based ionic liquids and organic solvents with good recyclability of the catalyst. Tantalum was found in the solution after reaction; however, this was determined to be due to entrapment of catalyst particulates, as opposed to leaching of the active metal. (c) 2005 Elsevier Inc. All rights reserved.

Synthesis and NMR Characterization of Titanium and Zirconium Oxides Incorporated in SBA-15

Single oxides of Ti and Zr incorporated SBA-15 were prepared and characterized by N-2 adsorption, NMR, and XPS techniques. Si-29 MAS NMR results suggest the formation of Si-O-X linkages (X: Ti or Zr) by an increase in the ratio of Q(3)/Q(4) in the presence of Ti or Zr. XPS analysis of Ti-SBA-15 catalysts indicate the presence of Ti-O-Si bonds in addition to Ti-O-Ti and Si-O-Si bonds, supporting the NMR evidence.

Immobilisation of eta(3)-allyidicarbonyl complexes of Mo-II with bidentate nitrogen ligands within aluminium-pillared clays

Molybdenum(II) complexes [MOX(CO)(2)(eta(3)-allyl)(CH3CN)(2)] (X = Cl or Br) were encapsulated in an aluminium-pillared natural clay or a porous clay heterostructure and allowed to react with bidentate diimine ligands. All the materials obtained were characterised by several solid-state techniques. Powder XRD, and Al-27 and Si-29 MAS NMR were used to investigate the integrity of the pillared clay during the modification treatments. C-13 CP MAS NMR, FTIR, elemental analyses and low-temperature nitrogen adsorption showed that the immobilisation of the precursor complexes was successful as well as the in situ ligand-substitution reaction. The new complex [MoBr(CO)(2)(eta(3)-allyl)(2-aminodipyridyl)] was characterised by single-crystal X-ray diffraction and spectroscopic techniques, and NMR studies were used to investigate its fluxional behaviour in solution. The prepared materials are active for the oxidation of cis-cyclooctene using tert-butyl hydroperoxide as oxidant, though the activity of the isolated complexes is higher. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

Effect of Lithium Nitrate on the Alkali-Silica Reaction Gel

Lithium nitrate has been used to prevent and to mediate the expansion caused by alkali-silica reaction (ASR). However, there is limited information on how it affects the existing reaction products caused by ASR. The aim of the present work is to determine the modifications caused by the LiNO3 treatment on the structure of the gel produced by ASR. ASR gel samples obtained from a concrete dam were exposed to an aqueous solution of lithium nitrate and sodium hydroxide with molar LiNO3/NaOH = 0.74, and the resulting products were analyzed by X-ray diffraction, infrared spectroscopy, and solid-state nuclear magnetic resonance of Si-29, Na-23, and Li-7. The treatment of the gel samples produces significant structural modifications in ASR products. A new amorphous silicate compound incorporating Li+ ions is formed, with an average silicate network that can be described as linear in contrast with the layered structure of the original gel. This elimination of the layered structure after the Li-based treatments may be related to the reduction of the tendency of the gel to expand. Also, several crystalline compounds containing potassium indicate the release of this species from the original ASR gel.

Hexagonal mesoporous silica modified with 2-mercaptothiazoline for removing mercury from water solution

A method for the attachment of 2-mercaptothiazoline (MTZ) to modified silica gel has been developed. In the first step, a new silylant agent was synthesized, named SiMTZ, by the reaction between MTZ molecule and chloropropyltrimethoxysilane (SiCl). SiMTZ and tetraethylortosilicate were co-condensed in the presence of n-dodecylamine, a neutral surfactant template, to produce a modified ordered hexagonal mesoporous silica named HMTZ. The modified material contained 0.89 +/- 0.03 mmol of 2-mercaptothiazoline per gram of silica. FT-IR, FT-Raman, Si-29- and C-13-NMR spectra were in agreement with the proposed structure of the modified mesoporous silica in the solid state. HMTZ material has been used for divalent mercury adsorption from aqueous solution at 298 I K. The series of adsorption isotherms were adjusted to a modified Langmuir equation. The maximum number of moles of mercury adsorbed gave 2.34 +/- 0.09 mmol/g of material. The same interaction was followed by calorimetric titration on an isoperibol calorimeter. The HMTZ presented a high capacity for the removal of the contaminant mercury from water. The Delta H and Delta G values for the interaction were determined to be -56.34 +/- 1.07 and -2.14 +/- 0.11 kJ mol(-1). This interaction process was accompanied by a decrease of entropy value (- 182 J mol(-1) K-1). Thus, the interaction between mercury and HMTZ resulted in a spontaneous thermodynamic system with a high favorable exothermic enthalpic effect. (c) 2007 Elsevier B.V. All rights reserved.

Preparation, characterization and application of a nanostructured composite: Octakis(cyanopropyldimethylsiloxy)octasilsesquioxane

Octakis(cyanopropyldimethylsiloxy)octasilsesquioxane was prepared and characterized by C-13, Si-29 NMR (MAS), SEM, FF-IR, XRD and thermogravimetric techniques. The four groups alpha, beta, gamma, kappa (to the terminal silicon atom), associated with an acrylonitrile, were clearly seen in the C-13 NMR (alpha-CH2 at 17.9; P-CH2 at 31.3; gamma-CH, at 50.4; K-C N at 59.0 ppm). The Si-29 NMR spectrum of the final product, exhibits only Q type silicon signal, ascribed to Q(4) (-118.0 ppm). The presence of acrylonittile substituted for octameric cube confers a relative change phase and thermal stability to the material. With regard to the applications for this new material, it was intended, in this case, to react with Na-2[Fe(CN)(5)NH3] by chemical substitution. This composite was incorporated into a carbon paste electrode and the electrochemical studies were performed by cyclic voltammetry. The cyclic voltammogram of the modified graphite paste electrode, showed one redox couples with formal potential (E-1/2(ox)) = 0.24 V versus SCE. (c) 2006 Elsevier B.V. All rights reserved.

Adsorption and electropolymerization of toluidine blue on the nano structured octakis(hydridodimethylsiloxy)-octasilsesquioxane surface

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

Study on soluble heavy metals with preconcentration by using a new modified oligosilsesquioxane sorbent

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

An Oligosilsesquioxane Cage Functionalized with Molybdenum(II) Organometallic Fragments

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