Effect of acidity in TS-1 zeolites on product distribution of the styrene oxidation reaction

The role of Bronsted acidity of titanium silicalite zeolite (with different ratios of Si/Ti) in oxidation reactions of styrene has been investigated and discussed. For zeolites with Si/Ti > 42, most of the titanium is in the zeolite framework. These framework titanium species, which act both as the isolated titanium centers and as Bronsted acidity centers (together with the Bronsted acidity produced by the tetrahedral aluminum impurity introduced during synthesis), can catalyze both the epoxidation and the succeeding rearrangement reactions, thus promoting the formation of phenylacetaldehyde. With an increase in the titanium content of the zeolite, titanium will tend to stay outside the zeolite lattice, except for the TiOx nanophases which can be occluded in the zeolite channels or on the external surface. These non-framework titanium species are favorable for the carbon-carbon bond scission, leading to the production of additional benzaldehyde. The catalytic performances of these zeolites with different Si/Ti ratios are correlated here with their structural information by using solid-state NMR and UV-Vis methods. (C) 2003 Elsevier B.V. All rights reserved.

On the surface sites Of MOP/SiO2 catalyst under sulfiding conditions: IR spectroscopy and catalytic reactivity studies

The surface sites of MoP/SiO2 catalysts and their evolution under sulfiding conditions were characterized by IR spectroscopy using CO as the probe molecule. The HDS activities of thiophene were measured on the MoP/SiO2 catalyst that was subjected to different sulfidation and reactivation pretreatments. Cus Modelta+ (0 < delta less than or equal to 2) sites are probed on the surface of fresh MoP/SiO2 by molecularly adsorbed CO, exhibiting a characteristic IR band at 2045 cm(-1). The surface of MoP/SiO2 is gradually sulfided in HDS reactions, as revealed by the shift of the IR band at 2045 to ca. 2100 cm(-1). Although the surface of a MoP/SiO2 catalyst becomes partially sulfided, the HDS activity tests show that MoP/SiO2 is fairly stable in the initial stage of the HDS reaction, providing further evidence that molybdenum phosphide is a promising catalytic material for industrial HDS reactions. Two kinds of surface sulfur species are formed on the sulfided catalyst: reversibly and irreversibly bonded sulfur species. The MoP/SiO2 catalyst remains stable in the HDS of thiophene because most sulfur species formed under HDS conditions are reversibly bonded on the catalyst surface. A detrimental effect of presulfidation on the HDS activity is observed for the MoP/SiO2 catalyst treated by H2S/H-2 at temperatures higher than 623 K, which is ascribed to the formation of a large amount of the irreversibly bonded sulfur species. The irreversibly sulfided catalyst can be completely regenerated by an oxidation and a subsequent reduction under mild conditions. (C) 2003 Elsevier Inc. All rights reserved.

The Effect of MMT/Modified MMT on the Structure and Performance of the Superabsorbent Composite

A series of superabsorbent composites containing Montmorillonite (MMT), modified- Montmorillonite (OMMT) and sodium acrylate were synthesized by free-radical polymerization in aqueous solution. The structure of composites was characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray diffraction (XRD), and the results showed that the polymer chains were grafted onto the edge and the surface of MMT or OMMT. At the same time, the equilibrium swelling ratio of the composites was investigated as a function of the clay content and the results showed that the equilibrium swelling ratio of composites was improved by the introduction of clay.

Facile fabrication of large area of aggregated gold nanorods film for efficient surface-enhanced Raman scattering

An effective and facile method for fabrication of large area of aggregated gold nanorods (AuNRs) film was proposed by self-assembly of AuNRs at a toluene/water interface for the first time. It was found that large area of aggregated AuNRs film could be formed at the interface of toluene and water due to the interfacial tension between the two phases. The obtained large area of aggregated AuNRs film exhibits strong surface-enhanced Raman scattering (SERS) activity with 4-aminothiophenol (4-ATP) and 2-aminothiophenol (2-ATP) as the probe molecules based on the strong electromagnetic coupling effect between the very adjacent AuNRs.

Effect of interfacial roughness on dewetting behavior of polystyrene/poly(methyl methacrylate) bilayer film

The dewetting behavior of polystyrene (PS) film on poly(methyl methacrylate) (PMMA) sublayer was investigated by changing the short-range roughness of the PMMA sublayer systemically. When the bilayer film was heated to the temperature above both Tgs, the protuberances formed in both layers to reduce the system energy. By tracing the dewetting process of the PS up-layer, the dewetting velocity was found to increase with the roughness of the sublayer.

Effect of annealing on the deformation mechanism of a styrene/n-butyl acrylate copolymer latex film investigated by synchrotron small-angle X-ray scattering

The deformation mechanism of a styrene/n-butyl acrylate copolymer latex film subjected to uniaxial tensile stress was studied by small-angle X-ray scattering. The influence of annealing at 23, 60, 80, and 100 degrees C for 4 h on microscopic deformation processes was elucidated. It was demonstrated that the microscopic deformation mechanism of the latex films transformed gradually from nonaffine deformation behavior to affine deformation behavior with increasing annealing temperature.

Surface potential images of polycrystalline organic semiconductors obtained by Kelvin probe force microscopy

P-type copper phthalocyanine (CuPc) and n-type hexadecafluorophthalocyanina-tocopper (F16CuPc) polycrystalline films were investigated by Kelvin probe force microscopy (KPFM). Topographic and corresponding surface potential images are obtained simultaneously. Surface potential images are related with the local work function of crystalline facets and potential barriers at the grain boundaries (GBs) in organic semiconductors. Based on the spatial distribution of surface potential at GBs, donor- and acceptor-like trapping states in the grain boundaries (GBs) of p-CuPc and n-F16CuPc films are confirmed respectively.

Mechanism on flame retardancy of polystyrene/clay composites-The effect of surfactants and aggregate state of organoclay

Effects of organically modified montmorillonites (OMMTs) with different type and amount of modifiers on flame retardancy of polystyrene (PS) have been studied. The results from morphology analysis, gas chromatography-mass spectrometry and cone calorimeter have showed different mechanisms for the flame retardancy of PS/OMMTs composites, depending on surface property of OMNTrs. One is the catalysis of acid sites formed on the surface of octadecylammonium modified MMT (c-MMT) via Hoffman decomposition on the carbonization of degradation products, which promotes the formation of clay-enriched char barrier.

Composition effect on dewetting of ultrathin films of miscible polymer blend

Two kinds of dewetting and their transition induced by composition fluctuation due to different composition in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on SiOx substrate at 145 degrees C have been studied by in-situ atomic force microscopy (AFM). The results showed that morphology and pathway of dewetting depended crucially on the composition. Possible reason is the variation in intensity of composition fluctuation resulted from the change of components in polymer blend. Based on the discussion of this fluctuation due to the composition gradient, parameter of U-q0/E, which describes the initial amplitude of the surface undulation and original thickness of film respectively, has been employed to distinguish the morphologies of spontaneous dewetting including bicontinuous structures and holes.

Facile synthesis of PtRu/C electrocatalyst with high activity and high loading for passive direct methanol fuel cell by synergetic effect of ultrasonic radiation and mechanical stirring

The PtRu/C electrocatalyst with high loading (PtRu of 60 wt%) was prepared by synergetic effect of ultrasonic radiation and mechanical stirring. Physicochemical characterizations show that the size of PtRu particles of as-prepared PtRu/C catalyst is only several nanometers (2-4 nm), and the PtRu nanoparticles were homogeneously dispersed on carbon surface. Electrochemistry and single passive direct methanol fuel cell (DMFC) tests indicate that the as-prepared PtRu/C electrocatalyst possessed larger electrochemical active surface (EAS) area and enhanced electrocatalytic activity for methanol oxidation reaction (MOR). The enhancement could be attributed to the synergetic effect of ultrasound radiation and mechanical stirring, which can avoid excess concentration of partial solution and provide a uniform environment for the nucleation and growth of metal particles simultaneously hindering the agglomeration of PtRu particles on carbon surface.

Design of Fluorescent Assays for Cyanide and Hydrogen Peroxide Based on the Inner Filter Effect of Metal Nanoparticles

We have demonstrated the design of a new type fluorescent assay based on the inner filter effect (IFE) of metal nanoparticles (NPs), which is conceptually different from the previously reported metal NPs-based fluorescent assays. With a high extinction coefficient and tunable plasmon absorption feature, metal NPs are expected to be capable of functioning as a powerful absorber to tune the emission of the fluorophore in the IFE-based fluorescent assays. In this work, we presented two proof-of-concept examples based on the IFE of Au NPs by choosing MDMO-PPV as a model fluorophore, whose fluorescence could be tuned by the absorbance of Au NPs with a much higher sensitivity than the corresponding absorbance approach.

Turn-on fluorescent detection of cyanide based on the inner filter effect of silver nanoparticles

A simple, sensitive fluorescent method for detecting cyanide has been developed based on the inner filter effect (IFE) of silver nanoparticles (Ag NPs). With a high extinction coefficient and tunable plasmon absorption feature, Ag NPs are expected to be a powerful absorber to tune the emission of the fluorophore in the IFE-based fluorescent assays. In the present work, we developed a turn-on fluorescent assay for cyanide based on the strong absorption of Ag NPs to both excitation and emission light of an isolated fluorescence indicator. In the presence of cyanide, the absorber Ag NPs will dissolve gradually, which then leads to recovery of the IFE-decreased emission of the fluorophore. The concentration of Ag NPs in the detection system was found to affect the fluorescence response toward cyanide greatly. Under the optimum conditions, the present IFE-based approach can detect cyanide ranging from 5.0 x 10 (7) to 6.0 x 10 (4) M with a detection limit of 2.5 x 10 (7) M, which is much lower than the corresponding absorbance-based approach and compares favorably with other reported fluorescent methods.

Effect of buffer capacity on electrochemical behavior of dopamine and ascorbic acid

It is well known that the electrochemical oxidation of dopamine and ascorbic acid includes the proton and electron transfers at a glassy carbon electrode and their redox potentials are dependent on the pH of solution. When the concentration of the buffer is not enough to neutralize the protons produced by electrochemical oxidation of dopamine and ascorbic acid, two peaks of them can be observed in cyclic voltammograms. The height of the new peak is in proportion to the concentration of proton acceptor including HPO42-, 2,4,6-trimethylpyridine, tris (hydroxymethyl) aminomethane. Moreover, the potential of it is dependent on the type and the concentration of buffer at the same pH of bulk solution. However, this phenomenon cannot be attributed to the interaction between proton acceptor and dopamine or ascorbic acid. So, we think the phenomenon is caused by the acute change of pH at the surface of working electrode. Similar results were also observed in the rotating disk voltammograms. It can be concluded that the electrochemical behavior of some compounds is dependent on the concentration of buffer when this concentration is not enough to neutralize the protons produced in electrochemical oxidation.

Wet-chemical approach to three-dimensional gold nanocorallines: Synthesis and application in surface-enhanced Raman spectroscopy

The shape-con trolled synthesis of micrometer- sized gold nanocoralline was simply realized via a wet-chemical approach. The as-prepared hierarchical gold nanocorallines (HGNs) on the solid substrate were initially applied in SERS analysis with 4-aminothiophenol (4-ATP) as the probe molecule. The HGN-modified glass substrate exhibits a higher SERS effect (one order of magnitude higher) than the aggregated gold nanoparticle (similar to 25 nm)-modified glass substrate.