Templated assembly of mu(5)-CO32- decanuclear praseodymium and neodymium clusters through spontaneous fixation of atmospheric carbon dioxide

Reactions of Ln(III) acetate (Ln = Pr and Nd) and a polydentate Schiff-base in a mixture of methanol and acetonitrile resulted in the unprecedented assembly of novel Ln(10) aggregates containing two Ln(5) pentagons templated by mu(5)-CO32-, introduced via spontaneous fixation of atmospheric carbon dioxide. Magnetic analysis using an expression including the ligand field effects and molecular field approximation indicates weak antiferromagnetic coupling between the metal ions. This synthetic approach may represent a promising new route toward the design of new lanthanide clusters and novel multifunctional materials.

Synthesis and photoluminescence of Y2O3 : RE3+ (RE = Eu, Tb, Dy) porous nanotubes templated by carbon nanotubes

Y2O3:RE3+ (RE = Eu, Tb, Dy) porous nanotubes were first synthesized using carbon nanotubes as template. The morphology of the coated precursors and porous Y2O3:Eu3+ nanotubes was determined by scanning electron Microscopy (SEM) and transmission electron microscopy (TEM). It was found that the coating of precursors on carbon nanotubes (CNTs) is continuous and the thickness is about 15 nm, after calcinated, the Y2O3:Eu3+ nanotubes are porous with the diameter size in the range of 50-80 nm and the length in micrometer scale. X-ray diffraction (XRD) patterns confirmed that the samples are cubic phase Y2O3 and the photoluminescence studies showed that the porous rare earth ions doped nanotubes possess characteristic emission of Eu3+, Tb3+, and Dy3+. This method may also provide a novel approach to produce other inorganic porous nanotubes used in catalyst and sensors.

Oxygen and carbon isotope data from late calcite and zeolite pore-fill cements at DSDP Site 445

Oxygen isotopic composition of zeolite pore-fill cements in andesitic volcaniclastic sandstones recovered from DSDP Site 445 ranges from +30.1 to +17.8? (SMOW) downhole. This change is controlled by large heat flow from the basement which caused early diagenetic emplacement of zeolites during early basin rifting. d18O-values of late calcite cements range from +25.1 to +27.4? (SMOW); their petrographic relation and inferred temperature of formation suggest that calcite cements were formed during late stages of diagenesis. Isotopic composition in these sandstones is in agreement with mineral paragenesis determined microscopically.

Reaction of glucose catalyzed by framework and extraframework tin sites in zeolite beta

The isomerization of glucose into fructose is a large-scale reaction for the production of high-fructose corn syrup, and is now being considered as an intermediate step in the possible route of biomass conversion into fuels and chemicals. Recently, it has been shown that a hydrophobic, large pore, silica molecular sieve having the zeolite beta structure and containing framework Sn⁴⁺ (Sn-Beta) is able to isomerize glucose into fructose in aqueous media. Here, I have investigated how this catalyst converts glucose to fructose and show that it is analogous to that achieved with metalloenzymes. Specifically, glucose partitions into the molecular sieve in the pyranose form, ring opens to the acyclic form in the presence of the Lewis acid center (framework Sn⁴⁺), isomerizes into the acyclic form of fructose and finally ring closes to yield the furanose product. Akin to the metalloenzyme, the isomerization step proceeds by intramolecular hydride transfer from C2 to C1. Extraframework tin oxides located within hydrophobic channels of the molecular sieve that exclude liquid water can also isomerize glucose to fructose in aqueous media, but do so through a base-catalyzed proton abstraction mechanism. Extraframework tin oxide particles located at the external surface of the molecular sieve crystals or on amorphous silica supports are not active in aqueous media but are able to perform the isomerization in methanol by a base-catalyzed proton abstraction mechanism. Post-synthetic exchange of Na⁺ with Sn-Beta alters the glucose reaction pathway from the 1,2 intramolecular hydrogen shift (isomerization) to produce fructose towards the 1,2 intramolecular carbon shift (epimerization) that forms mannose. Na⁺ remains exchanged onto silanol groups during reaction in methanol solvent, leading to a near complete shift in selectivity towards glucose epimerization to mannose. In contrast, decationation occurs during reaction in aqueous solutions and gradually increases the reaction selectivity to isomerization at the expense of epimerization. Decationation and concomitant changes in selectivity can be eliminated by addition of NaCl to the aqueous reaction solution. Thus, framework tin sites with a proximal silanol group are the active sites for the 1, 2 intramolecular hydride shift in the isomerization of glucose to fructose, while these sites with Na-exchanged silanol group are the active sites for the 1, 2 intramolecular carbon shift in epimerization of glucose to mannose.

Skeletal isomerization of 1-hexene to isohexenes over zeolite catalysts

Several zeolite catalysts such as SAPO-11, ZSM-11, ZSM-12, etc. were selected to convert I-hexene to branched hexenes in this work. Pore size of the zeolite catalyst plays an important role on the yield and the distribution of branched isohexenes. And the zeolite catalysts with the pore size of 0.6nm are optimum to produce dimethylbutenes (DMB). SAPO-11 zeolite is a suitable skeletal isomerization catalyst, especially in the production of methyl pentenes. Under the following reaction conditions: WHSV=1.0 h(-1), H-2/hexene=8, T=250 degreesC, P=0.2 MPa, the yield of skeletal isohexenes remains above 80% at the prolonged time-on stream of 80 h, accompanying low C5-, C7+ products and low carbon deposition on the catalyst.

Electrospun palladium nanoparticle-loaded carbon nanofibers and their electrocatalytic activities towards hydrogen peroxide and NADH

Palladium nanoparticle-loaded carbon nanofibers (Pd/CNFs) were synthesized by the combination of electrospinning and thermal treatment processes. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images show that spherical Pd nanoparticles (NPs) are well-dispersed on the surfaces of CNFs or embedded in CNFs. X-ray diffraction (XRD) pattern indicates that cubic phase of Pd was formed during the reduction and carbonization processes, and the presence of Pd NPs promoted the graphitization of CNFs. This nanocomposite material exhibited high electric conductivity and accelerated the electron transfer, as verified by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV).

Carbon dioxide/propylene oxide coupling reaction catalyzed by chromium salen complexes

A series of chromium/Schiff base complexes N,N'-bis(salicylidene)-1,2-phenylenediamino chromium(III) X were prepared and employed for the alternating copolymerization of carbon dioxide with racemic propylene oxide in the presence of (4-dimethylamino)pyridine. The effect of the complex structure and reaction conditions on the catalytic activity, the poly(propylene carbonate)/cyclic carbonate (PPC/PC) selectivity, and the polymer head-to-tail linkages was examined. The experiments indicated that N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-phenylenediamino chromium(III) (NO3) exhibited the highest PPC/PC selectivity as well as polymer head-to-tail linkages and N,N'-bis(3,5-dichlorosalicylidene)-1,2-phenylenediimino chromiu(III) (NO3) possessed the highest catalytic activity among these chromium/Schiff base complexes. The structure of the produced copolymer was characterized by the IR, H-1 NMR, and C-13 NMR measurements.

CNT Templated Regioselective Enzymatic Polymerization of Phenol in Water and Modification of Surface of MWNT Thereby

Carbon nanotubes (CNTs) are used as templates to synthesize regioselective polymers from enzymatic polymerization of phenol in water. About 90% of total polymeric units in the obtained polymers are the highly thermally stable oxyphenylene units. The polymer-yields are dependent on the quantities of CNTs used. On the basis of MWNT-templated enzymatic polymerization of phenol, covalent attachment of polyphenol chains to the surface of MWNT by way of a linking molecule, hydroquinone, is achieved. This approach supplies a novel way for producing high-performance polymers and for functionalization of the surface of CNT.

Templated assembly of gold nanoparticles into microscale tubules and their application in surface-enhanced Raman scattering

We report a simple procedure to assemble gold nanoparticles into hollow tubular morphology with micrometer scale, wherein the citrate molecule is used not only as a reducing and capping agent, but also as an assembling template. The nanostructure and growth mechanism of microtubes are explored via SEM, TEM, FTIR spectra, and UV-vis spectra studies. The incorporation of larger gold nanoparticles by electroless plating results in an increase in the diameter of microtubes from 900 nm to about 1.2 mu m. The application of the microtubes before and after electroless plating in surface-enhanced Raman scattering (SERS) is investigated by using 4-aminothiophenol (4-ATP) as probe molecules. The results indicate that the microtubes both before and after electroless plating can be used as SERS substrates. The microtubes after electroless plating exhibit excellent enhancement ability.

Method for the in situ preparation of a single layer of zeolite Beta crystals on a molybdenum substrate for microreactor applications

A method for the hydrothermal synthesis of a single layer of zeolite Beta crystals on a molybdenum substrate for microreactor applications has been developed. Before the hydrothermal synthesis, the surface of the substrate was modified by an etching procedure that increases the roughness at the nanoscale level without completely eliminating the surface lay structure. Then, thin films of Al2O3 (170 nm) and TiO2 (50 nm) were successively deposited by atomic layer deposition (ALD) on the substrate. The internal Al2O3 film protects the Mo substrate from oxidation up to 550 degrees C in an oxidative environment. The high wettability of the external TiO2 film after UV irradiation increases zeolite nucleation on its surface. The role of the metal precursor (TiCl4 vs TiI4), deposition temperature (300 vs 500 degrees C), and film thickness (50 vs 100 nm) was investigated to obtain titania films with the slowest decay in the superhydrophilic behavior after UV irradiation. Zeolite Beta coatings with a Si/Al ratio of 23 were grown at 140 degrees C for 48 It. After ion exchange with a 10(-4) M cobalt acetate solution, the activity of the coatings was determined in the ammoxidation of ethylene to acetonitrile in a microstructured reactor. A maximum reaction rate of 220 mu mol C2H3N g(-1) s(-1) was obtained at 500 degrees C, with 42% carbon selectivity to acetonitrile. (C) 2007 Elsevier Inc. All rights reserved.

Dry gel conversion of organosilane templated mesoporous silica: from amorphous to crystalline catalysts for benzene oxidation

Mesoporous silica grown using [3-(trimethoxysilyl)propyl]octadecyldimethylammonium chloride as the mesoporogen in the presence of Fe and Al is X-ray amorphous, but contains very small domains with features of MFI zeolite as evidenced by IR and Raman spectroscopy. When applied as a catalyst, this amorphous sample shows good performance in the selective oxidation of benzene using nitrous oxide. Addition of tetrapropylammonium as structure directing agent to the as-synthesized mesoporous silica and subsequent dry gel conversion results in the formation of hierarchical Fe/ZSM-5 zeolite. During dry gel conversion the wormhole mesostructure of the initial material is completely lost. A dominant feature of the texture after crystallization is the high interconnectivity of micropores and mesopores. Substantial redistribution of low-dispersed Fe takes place during dry gel conversion towards highly dispersed isolated Fe species outside the zeolite framework. The catalytic performance in the oxidation of benzene to phenol of these highly mesoporous zeolites is appreciably higher than that of the parent material.

Monte Carlo studies of phase transitions and adsorption : application to n-6 Lennard-Jones, C60 and zeolite systems

The solid-fluid transition properties of the n - 6 Lennard-Jones system are studied by means of extensive free energy calculations. Different values of the parameter n which regulates the steepness of the short-range repulsive interaction are investigated. Furthermore, the free energies of the n < 12 systems are calculated using the n = 12 system as a reference. The method relies on a generalization of the multiple histogram method that combines independent canonical ensemble simulations performed with different Hamiltonians and computes the free energy difference between them. The phase behavior of the fullerene C60 solid is studied by performing NPT simulations using atomistic models which treat each carbon in the molecule as a separate interaction site with additional bond charges. In particular, the transition from an orientationally frozen phase at low temperatures to one where the molecules are freely rotating at higher temperatures is studied as a function of applied pressure. The adsorption of molecular hydrogen in the zeolite NaA is investigated by means of grand-canonical Monte Carlo, in a wide range of temperatures and imposed gas pressures, and results are compared with available experimental data. A potential model is used that comprises three main interactions: van der Waals, Coulomb and induced polarization by the permanent electric field in the zeolite.