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PubMed1998

Silicon-29 NMR Studies of Tetraalkylammonium Silicate Solutions. 2. Polymerization Kinetics.

The kinetics of formation of the silicate cubic octamer, Q(3)(8), in aqueous tetramethylammonium (TMA) silicate solutions was investigated by (29)Si NMR. The rate equation for solutions at pH 13.2-13.6 is d[Q(3)(8)]/dt = k(f) [H(+)](1.6)(+/-)(0.1)[TMA(+)](0.36)(+/-)(0.08)[Si](0.8)(+/-)(0.3) where k(f) = (2.2 +/- 0.8) x 10(16) mol(-)(1.8) kg(1.8) s(-)(1) at 296 K. The findings prove unequivocally that alkylammonium cations participate directly in the formation and subsequent stabilization of cagelike polysilicate anions. This implies a radically different mechanistic role than "templating" for alkylammonium cations in the synthesis of molecular sieves.

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PubMed2001

Novel microporous europium and terbium silicates.

The synthesis and structural characterization of the first examples of microporous europium(III) and terbium(III) silicates (Na(4)K(2)X(2)Si(16)O(38) x 10H(2)O, X = Eu, Tb) are reported. The structure of these solids was solved by powder X-ray diffraction ab initio (direct) methods and further characterized by chemical analysis (EDS), thermogravimetric analysis (TGA), scanning electron microscopy (SEM), (23)Na and (29)Si magic-angle spinning (MAS) NMR, and luminescence spectroscopy. Both materials display interesting photoluminescence properties and present potential for applications in optoelectronics. This work illustrates the possibility of combining in a given silicate microporosity and optical activity.

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PubMed2002

Open-framework and microporous vanadium silicates.

A series of novel vanadium silicates with open-framework and microporous structures has been synthesized under mild hydrothermal conditions. Ten distinct framework types have been identified that all have structures based on cross-linking single silicate sheets with square pyramidal V(IV)O(5) units to give compounds with the general formula A(r)[(VO)(s)(Si(2)O(5))(p)(SiO(2))(q)].tH(2)O, where A is Na, K, Rb, Cs, or a combination. The vanadosilicate (VSH-n) structures have free channel diameters up to 6.5 A and show good thermal stability, absorption, and ion-exchange properties, suggesting their potential for technological applications as molecular sieves or in catalysis.

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PubMed2003

Novel microporous lanthanide silicates with tobermorite-like structure.

The synthesis and structural characterization of microporous lanthanide silicates (Na(1.08)K(0.5)Ln(1.14)Si(3)O(8.5).1.78H(2)O, Ln = Eu, Tb, Sm, Ce) are reported. The structure of these solids is closely related with the structure of hydrated calcium silicate minerals known as tobermorites and was solved by powder X-ray diffraction ab initio (direct) methods and further characterized by chemical analysis, thermogravimetry, scanning electron microscopy, (23)Na and (29)Si MAS NMR and luminescence spectroscopy. These materials combine microporosity with interesting photoluminescence properties, and their structural flexibility allows fine-tuning of luminescence properties, by introducing a second type of lanthanide ion in the framework. Thus, they may find applications in new types of sensors.

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PubMed2003

Structure of the first silicate molecular sieve with 18-ring pore openings, ECR-34.

The three-dimensional microporosity of zeolite frameworks have allowed their widespread use in industry as heterogeneous catalysts, absorbents, and ion-exchangers. While the phosphate analogues of zeolites having up to 24 tetrahedral atoms in the pore openings are known, silicate-based zeolites have, until now, been limited to 14-membered ring pore openings. We now disclose the structure and characterization of the synthetic zeolite ECR-34, which can be prepared from a mixed alkali metal reaction gel containing tetraethylammonium (TEA) cations. Its structure has been determined from powder diffraction data and shows ECR-34 to be hexagonal with the dimensions a, b = 21.030(1) A, c = 8.530(1) A, containing one-dimensional, 18-ring pores with 10 A diameter free openings. ECR-34 is stable to 800 degrees C and is able to absorb and ion-exchange large organic molecules. The existence of ECR-34 suggests the potential of preparing other thermally stable silicate molecular sieves with extra-large pores.

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PubMed2003

Stereochemically controlled PMMA-exfoliated silicate nanocomposites using intergallery-anchored metallocenium cations.

Representative C2v-, C2-, and Cs-symmetric metallocene complexes were effectively anchored inside the silicate galleries via a non-cation-exchange approach involving protonolysis. These intergallery-anchored metallocenium cations allow for the first synthesis of in situ polymerized nanocomposites comprising exfoliated silicate nanoplatelets homogeneously dispersed in the atactic, isotactic, or syndiotactic PMMA matrixes.

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PubMed2004

Structure of a surfactant-templated silicate framework in the absence of 3d crystallinity.

The structure of a novel molecularly ordered two-dimensional (2D) silicate framework in a surfactant-templated mesophase has been established by using a combination of solid-state nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction, and quantum chemical and empirical force-field modeling. These materials are unusual in their combination of headgroup-directed 2D crystalline framework ordering, zeolite-like ring structures within the layers, and long-range mesoscopic organization without three-dimensional (3D) atomic periodicity. The absence of registry between the silicate sheets, resulting from the liquidlike disorder of the alkyl surfactant chains, has presented significant challenges to the determination of framework structures in these and similar materials lacking 3D crystalline order. Double-quantum (29)Si NMR correlation experiments establish the interactions and connectivities between distinct intra-sheet silicon sites from which the structure of the molecularly ordered inorganic framework is determined.

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PubMed2006

Silicate glass and mineral dissolution: calculated reaction paths and activation energies for hydrolysis of a q3 si by H3O+ using ab initio methods.

Molecular orbital energy minimizations were performed with the B3LYP/6-31G(d) method on a [((OH)3SiO)3SiOH-(H3O+).4(H2O)] cluster to follow the reaction path for hydrolysis of an Si-O-Si linkage via proton catalysis in a partially solvated system. The Q3 molecule was chosen (rather than Q2 or Q1) to estimate the maximum activation energy for a fully relaxed cluster representing the surface of an Al-depleted acid-etched alkali feldspar. Water molecules were included in the cluster to investigate the influence of explicit solvation on proton-transfer reactions and on the energy associated with hydroxylating the bridging oxygen atom (Obr). Single-point energy calculations were performed with the B3LYP/6-311+G(d,p) method. Proton transfer from the hydronium cation to an Obr requires sufficient energy to suggest that the Si-(OH)-Si species will occur only in trace quantities on a silica surface. Protonation of the Obr lengthens the Si-Obr bond and allows for the formation of a pentacoordinate Si intermediate ([5]Si). The energy required to form this species is the dominant component of the activation energy barrier to hydrolysis. After formation of the pentacoordinate intermediate, hydrolysis occurs via breaking the [5]Si-(OH)-Si linkage with a minimal activation energy barrier. A concerted mechanism involving stretching of the [5]Si-(OH) bond, proton transfer from the Si-(OH2)+ back to form H3O+, and a reversion of [5]Si to tetrahedral coordination was predicted. The activation energy for Q3Si hydrolysis calculated here was found to be less than that reported for Q3Si using a constrained cluster in the literature but significantly greater than the measured activation energies for the hydrolysis of Si-Obr bonds in silicate minerals. These results suggest that the rate-limiting step in silicate dissolution is not the hydrolysis of Q3Si-Obr bonds but rather the breakage of Q2 or Q1Si-Obr bonds.

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PubMed2005

Three-dimensional morphological chirality induction using high magnetic fields in membrane tubes prepared by a silicate garden reaction.

Using a vertical superconducting magnet (max. 15 T), we studied magnetic field effects on membrane tube morphology prepared by a silicate garden reaction. At zero field, semipermeable membrane tubes grew upward when metal salts were added to a sodium silicate aqueous solution. In the presence of a magnetic field (15 T, downward) right-handed helical membrane tubes grew along a glass vessel's inner surface when magnesium chloride and copper sulfate were added. Referring to membrane tubes by the names of metal cations used in their preparation, in the case of Mg(II) and Zn(II) membrane tubes, the left-handed helical tubes grew when the field direction was reversed upward. The left-handed helical Mg(II) membrane tubes grew in the magnetic field when a glass rod was placed in a vessel. Mg(II) and Zn(II) tubes, separate from a vessel wall, grew in a twisted shape in the magnetic field. In situ observation of the solution's motion during the reaction revealed that the Lorentz force on the outflow from the opened top of the hollow membrane tube induced convection of the solution near the tube exit, engendering chiral growth of the membrane tubes. Relative orientation of the outflow and a boundary (a vessel wall or glass rod surface) helped to determine the convection's direction.

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PubMed2005

Adsorption and structural properties of ordered mesoporous carbons synthesized by using various carbon precursors and ordered siliceous P6mm and Ia3d mesostructures as templates.

Adsorption and structural properties of inverse carbon replicas of two ordered siliceous P6mm and Ia3d mesostructures have been studied by nitrogen adsorption, powder X-ray diffraction, and transmission electron microscopy. These carbon replicas were prepared by filling the pores of SBA-15 and KIT-6 siliceous templates with various carbon precursors followed by carbonization and silica dissolution. Sucrose, furfuryl alcohol, acenaphthene, mesophase pitch, and petroleum pitch were used to obtain inverse carbon replicas of SBA-15 and KIT-6. While structural properties of the resulting ordered mesoporous carbons are mainly determined by the hard template used, their adsorption properties depend on the type of the carbon precursor.

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PubMed2006

Formation of the C-S-H Layer during early hydration of tricalcium silicate grains with different sizes.

Portland cement is a mixture of solid phases which all react with water. Tricalcium silicate (Ca3SiO5) is its main component and is often used in model systems to study cement hydration. It is generally recognized that setting and hardening of cement are due to the formation, by a dissolution-precipitation process, of a calcium silicate hydrate (C-S-H) on anhydrous grains during Ca3SiO5 hydration. The purpose of this paper is to study the effect of Ca3SiO5 particle size on the nucleation-growth process of C-S-H. An experimental study of the rate of hydration by using different grain sizes under controlled conditions has been performed. The experimental data have been compared with results obtained by numerical simulation based on a particles-aggregation model. The thickness of the C-S-H layer when the reaction becomes limited by diffusion has been then estimated.

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PubMed2006

Functionalized mesoporous silicates for the removal of ruthenium from reaction mixtures.

[reaction: see text] The removal of residual ruthenium after olefin metathesis reactions and asymmetric hydrogenations has been described using amine-functionalized mesoporous silicates. Aminopropyltriethoxy silane-derivatized silicates were found to be the most effective. More than 99.99% of RuCl(3) could be removed in a single treatment. Scavenging of Ru after metathesis reactions using a Grubbs generation 1 catalyst gave a product with concentrations of less than 10 microg/5 mg after two treatments with amine-modified silica. Most importantly, no chromatography was required.

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PubMed2006

A new family of oxide ion conductors based on tricalcium oxy-silicate.

Tricalcium oxy-silicates, Ca3(SiO4)O and Ca2.93Mg0.07(Si0.98Al0.02O4)O0.99 [square]0.01, have been prepared as crystalline single phases. Ca3(SiO4)O and Ca2.93Mg0.07(Si0.98Al0.02O4)O0.99 [square]0.01 have triclinic and monoclinic structures, respectively. The samples show oxide anion conductivity with a small p-type electronic contribution under oxidizing conditions. At 1023 K, the oxide transport numbers range between 0.97 and 0.85 from reducing (dry 5%-H2-Ar/air gradient) to oxidizing (O2/air gradient) conditions in the 1023-1173 K interval. The thermal analyses showed a large weight loss on heating due to the presence of water in the materials. The monoclinic compound has ionic conductivities higher than those of the triclinic stoichiometric oxy-silicate, as expected due to the introduction of oxide vacancies. Typical total conductivities for these un-optimised solids are 10(-5)-10(-4) S cm(-1) at 1100 K. These compounds may contain a small amount of water, approximately 0.05 H2O moles per chemical formula, and they display an important proton contribution under a humidified atmosphere.

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PubMed2000

Silicate pneumoconiosis in hens.

Thirteen cases of silicate pneumoconiosis in 3- to 4-year-old hens are described. Ten of the birds were raised in the suburbs of a city near several chalk quarries and two cement-works; the remaining three hens (aged 3 years) had lived in an environment with high particulate pollution from a nearby brick-works in which large amounts of clay were used daily. Silicotic granulomas composed of dust-laden macrophages were scattered over the lungs. They were located mainly in the infundibula and atria of tertiary bronchi and around vessels; more rarely they occurred in the lamina propria mucosae of primary and secondary bronchi. Energy dispersive x-ray microanalysis coupled with both transmission and scanning electron microscopy revealed that the dust was composed mainly of silicon, aluminium, calcium, iron and potassium. Titanium, sulphur, magnesium, zinc, copper and chlorine were also found. It is concluded that animals raised in polluted environmental conditions may serve as an important indicator of risks to human health and pathogenetic mechanisms. Thirteen cases of silicate pneumoconiosis in 3- to 4-year-old hens are described. Ten of the birds were raised in the suburbs of a city near several chalk quarries and two cement-works; the remaining three hens (aged 3 years) had lived in an environment with high particulate pollution from a nearby brick-works in which large amounts of clay were used daily. Silicotic granulomas composed of dust-laden macrophages were scattered over the lungs. They were located mainly in the infundibula and atria of tertiary bronchi and around vessels; more rarely they occurred in the lamina propria mucosae of primary and secondary bronchi. Energy dispersive x-ray microanalysis coupled with both transmission and scanning electron microscopy revealed that the dust was composed mainly of silicon, aluminium, calcium, iron and potassium. Titanium, sulphur, magnesium, zinc, copper and chlorine were also found. It is concluded that animals raised in polluted environmental conditions may serve as an important indicator of risks to human health and pathogenetic mechanisms.

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PubMed2005

Determining the geometry of strongly hydrogen-bonded silanols in a layered hydrous silicate by solid-state nuclear magnetic resonance.

High-resolution solid-state NMR spectroscopy is exploited to obtain structural constraints involving strongly hydrogen-bonded silanols in octosilicate, a prominent member of the layered hydrous sodium silicates. Proton-silicon cross-polarization dynamics reveals that octosilicate contains two types of Q(3) silicons present in hydrogen-bonded -Si-O-Hcdots, three dots, centeredO-Si- and -Si-O(-)-type sites which can only be distinguished by their different abilities to cross polarize and the different mobilities of neighboring hydrous species. The theoretical analysis of the oscillating components of the polarization transfer buildup curves suggests that the model of heteronuclear pairs is an adequate description of the quantum spin system within hydrogen-bonded -Si-O-Hcdots, three dots, centeredO-Si- fragments. We also show that dipolar modulated, slow speed magic-angle (29)Si NMR spectrum provides unique geometric information on strongly hydrogen-bonded silanols. The dipolar modulated spinning sidebands contain all the information necessary to determine the internuclear Sicdots, three dots, centeredH distances as well as the magnitude and orientation of the principal elements of the (29)Si chemical shielding tensor in the molecular frame. The data provide definite proof of the intralayer character of strongly hydrogen-bonded silanol groups in a bridging, albeit not symmetric, position between neighboring tetrahedra. The approach developed in this work may be useful to obtain structural information on related layered alkali metal silicates, silica gels as well as on other classes of microporous materials.

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PubMed2001

Constraints on nebular dynamics and chemistry based on observations of annealed magnesium silicate grains in comets and in disks surrounding Herbig Ae/Be stars.

Understanding dynamic conditions in the Solar Nebula is the key to prediction of the material to be found in comets. We suggest that a dynamic, large-scale circulation pattern brings processed dust and gas from the inner nebula back out into the region of cometesimal formation-extending possibly hundreds of astronomical units (AU) from the sun-and that the composition of comets is determined by a chemical reaction network closely coupled to the dynamic transport of dust and gas in the system. This scenario is supported by laboratory studies of Mg silicates and the astronomical data for comets and for protoplanetary disks associated with young stars, which demonstrate that annealing of nebular silicates must occur in conjunction with a large-scale circulation. Mass recycling of dust should have a significant effect on the chemical kinetics of the outer nebula by introducing reduced, gas-phase species produced in the higher temperature and pressure environment of the inner nebula, along with freshly processed grains with "clean" catalytic surfaces to the region of cometesimal formation. Because comets probably form throughout the lifetime of the Solar Nebula and processed (crystalline) grains are not immediately available for incorporation into the first generation of comets, an increasing fraction of dust incorporated into a growing comet should be crystalline olivine and this fraction can serve as a crude chronometer of the relative ages of comets. The formation and evolution of key organic and biogenic molecules in comets are potentially of great consequence to astrobiology.

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PubMed2001

Ultralow compressibility silicate without highly coordinated silicon.

The bulk modulus of scheelite-structured ZrSiO(4) is 301.4+/-12.5 GPa, as derived from static compression experiments to 52.5 GPa. It is as stiff as the most incompressible known silicate, SiO(2) stishovite. This high incompressibility indicates that octahedrally coordinated silicon is not required to generate ultrastiff silicates: ZrSiO(4) scheelite is the most incompressible material containing SiO(4) tetrahedra. Its incompressibility is in accord with a semitheoretical relation we derive for the bulk modulus of scheelite-structured materials. Based upon correlations between incompressibility and hardness, scheelite-structured oxides may thus represent a new family of ultrahard materials.

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