Simple preparation method of Pd nanoparticles on an Au electrode and its catalysis for dioxygen reduction

A simple method for the fabrication of Pd nanoparticles is described. The three-dimensional Pd nanoparticle films are directly formed on a gold electrode surface by simple electrodeposition at -200 mV from a solution of 1 M H2SO4+0.01 mM K2PdCl4. X-Ray photoelectron spectroscopy verifies the constant composition of the Pd nanoparticle films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 45-60 nm. It is confirmed that the morphology of the Pd nanoparticle films are correlated with the electrodeposition time and the state of the Au substrate. The resulting Pd-nanoparticle-film-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen in 0.1 M KCl solution. Freshly prepared Pd nanoparticles can catalyze the reduction of O-2 by a 4-electron process at -200 mV in 0.1 M KCl, but this system is not very stable. The cathodic peaks corresponding to the reduction of O-2 gradually decrease with potential cycling and at last reach a steady state. Then two well-defined reduction peaks are observed at -390 and -600 mV vs. Ag/AgCl/KCl (sat.). Those two peaks correspond to a 2-step process for the 4-electron reduction pathway of O-2 in this neutral medium.

Surface morphology control of immiscible polymer-blend thin films

The effects of the molecular weights (molecular weight of polystyrene, M-w,M-PS, varying from 2.9 to 129 k) on the surface morphologies of spin-coated and annealed polystyrene/poly (methyl methacrylate) (PS/PMMA = 50/50, w/w) blend films were investigated by atomic force microscopy and X-ray photoelectron spectroscopy. For the spin-coated films, when the M-w,M-PS varied from 2.9 to 129 k, three different kinds of surface morphologies (a nanophase-separated morphology, a PMMA cellular or network-like morphology whose meshes filled with PS, a sea-island like morphology) were observed and their formation mechanisms are discussed, respectively. Upon annealing, two different morphology-evolution processes were observed. It is found that a upper PS-rich phase layer is formed when M-w,M-PS < 4 k, and this behavior is mainly attributed to the low interfacial tension between PS and PMMA component. When M-w,M-PS > 4 k, the PS-rich phase forms droplets on top of the PMMA-rich phase layer which wets the SiOx substrate. These results indicate that the surface morphology of the polymer blend films can be controlled by the polymer molecular weight and annealing conditions.

Surface phase separations of PMMA/SAN blends investigated by atomic force microscopy

The thin films of poly(methyl methacrylate) (PMMA), poly(styrene-co-acrylonitrile) (SAN) and their blends were prepared by means of spin-coating their corresponding solutions onto silicon wafers, followed by being annealed at different temperatures. The surface phase separations of PMMA/SAN blends were characterized by virtue of atomic force microscopy (AFM). By comparing the tapping mode AFM (TM-AFM) phase images of the pure components and their blends, surface phase separation mechanisms of the blends could be identified as the nucleation and growth mechanism or the spinodal decomposition mechanism. Therefore, the phase diagram of the PMMA/SAN system could be obtained by means of TM-AFM. Contact mode AFM was also used to study the surface morphologies of all the samples and the phase separations of the blends occurred by the spinodal decomposition mechanism could be ascertained. Moreover, X-ray photoelectron spectroscopy was used to characterize the chemical compositions on the surfaces of the samples and the miscibility principle of the PMMA/SAN system was discussed.

Preparation of poly(thionine) modified screen-printed carbon electrode and its application to determine NADH in flow injection analysis system

A poly(thionine) modified screen-printed carbon electrode has been prepared by an electrooxidative polymerization of thionine in neutral phosphate buffer. The modified electrodes are found to give stable and reproducible electrocatlytic responses to NADH and exhibit good stability. Several techniques, including cyclic voltammetry, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), have been employed to characterize the poly(thionine) film. Further, the modified screen-printed carbon electrode was found to be promising as an amperometric detector for the flow injection analysis (FIA) of NADH, typically with a dynamic range of 5-100 muM.

Synthesis, characterization and electrical properties of the new solid electrolyte materials Ce6-xErxMoO15-delta (0.0 < x < 1.5)

A new series of oxides, Ce6-xErxMoO15-delta (0.0 less than or equal to x less than or equal to 1.5), was synthesized using wet-chemistry techniques. The precursors and resultant oxide powders were characterized by differential thermal analysis/thermogravimetry, x-ray diffraction, and IR, Raman and x-ray photoelectron spectroscopy. The formation temperature of the powders was found to be as low as 350degreesC. Ce6-xErxMoO15-delta crystallized to a fluorite-related cubic structure. The electrical conductivity of the samples was investigated by using ac impedance spectroscopy. This showed that the presence of Er was related to the oxygen-ion conductivity, and that the highest oxygen-ion conductivity was found in Ce6-xErxMoO15-delta (x = 0.4), ranging from 5.9 x 10(-5) S cm(-1) at 300degreesC to 1.26 x 10(-2) S cm(-1) at 700degreesC, respectively. This kind of material shows a potential application in intermediate-temperature solid oxide fuel cells.

Miscibility and hydrogen-bonding interactions in blends of carbon dioxide/epoxy propane copolymer with poly (p-vinylphenol)

The miscibility and hydrogen-bonding interactions of carbon dioxide and epoxy propane copolymer to poly(propylene carbonate) (PPC)/poly(p-vinylphenol) (PVPh) blends were investigated with differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The single glass-transition temperature for each composition showed miscibility over the entire composition range. FTIR indicates the presence of strong hydrogen-bonding interassociation between the hydroxyl groups of PVPh and the oxygen functional groups of PPC as a function of composition and temperature. XPS results testify to intermolecular hydrogen-bonding interactions between the oxygen atoms of carbon-oxygen single bonds and carbon-oxygen double bonds in carbonate groups of PPC and the hydroxyl groups of PVPh by the shift of C-1s peaks and the evolution of three novel O-1s peaks in the blends, which supports the suggestion from FTIR analyses.

Preparation and characterization of a novel beta-cyclodextrin modified poly(N-acetylaniline) film

Hydroquinone was chosen as an electroactive probe to study the beta-cyclodextrin (beta-CD) modified poly(N-acetylaniline) (PNAANI) electrode. The beta-CD modified PNAANI electrode was prepared by electrooxidation of the PNAANI electrode in a beta-CD/DMSO solution. The electrochemical properties of the beta-CD inclusion complex of hydroquinone on the PNAANI electrode and hydroquinone on the beta-CD modified PNAANI electrode were studied. In the cyclic voltammogram of hydroquinone at the beta-CD/PNAANI electrode, DeltaE(p) of the peaks is sharpening and the area of the peaks is increasing, which can be due to the inclusion of hydroquinone into the cavity of beta-CD immobilized at the electrode surface. The beta-CD/PNAANI film was characterized by X-ray photoelectron spectroscopy and H-1 NMR. The mechanism for beta-CD incorporation into the polymer film was also proposed.

Incorporation of surface-derivatized gold nanoparticles into electrochemically generated polymer films

Stable colloidal solutions of gold nanoparticles surface-derivatized with a thiol monolayer have been prepared using two-phase (water-nitrobenzene) reduction of AuCl4- by sodium borohydride in the presence of 2-mercapto-3-n-octylthiophene (MOT). This kind of surface-functionalized gold nanoparticles can be easily incorporated into the poly(3-octylthiophene) (POT) films on electrode in the process of electrochemical polymerization leading to POT-gold nanoparticle (POT-Au) composite films. Scanning probe microscopy (SPM) and X-ray photoelectric spectroscopy (XPS) have been employed to characterize the surface-derivatized particles and the resulting films. The method of incorporation of nanoparticles into polymer by surface-derivatization and in situ polymerization can also be employed to prepare many other polymer-nanoparticle compostie materials.

Annealing of nylon-1010 under high pressure

Full Paper: A study has been made on the annealing of nylon-1010 under high pressures. Heat treatment of melt-crystallized nylon-1010 was performed at 250degreesC for 30 min in the pressure range 0.7 similar to 2.5 GPa. It was found that the triclinic crystals of virgin nylon-1010 were retained at pressures less than 1.0 GPa or larger than 1.2 GPa. The X-ray diffraction intensity of (100) planes decreased with increasing pressure. The diffraction peaks shifted slightly to higher angles (2theta) relative to the virgin nylon-1010, indicating dense packing of polymer chains at high pressures. The highest melting temperature was 208degreesC for the sample annealed at 1.5 GPa. No extended-chain crystals were formed under the experimental conditions. Crosslinking occurred in the pressure range 1.0 similar to 1.2 GPa. The structure of the crosslinked samples was characterized by means of infrared spectroscopy and X-ray photoelectron spectroscopy. It is concluded that a mechanism of crosslinking via carbodiimide can explain the nature of crosslinking of nylon-1010 annealed at high pressures. The remarkable changes of the structure of annealed nylon-1010 are also discussed in this article.

Fabrication and characterization of ordered oligoaniline film

highly organized phenyl-capped teraniline (PC-teraniline) film at the molecular level was fabricated on carbon surfaces by electrochemical reduction of diazonium salts. Cyclic voltammetry (CV). scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) were employed for the characterization of the film.

Synthesis of tetra-iron substituted sandwich-type pentadecatungstodiarsenate and its multilayers on glassy carbon electrode by self-assembly with electrocatalytic properties

A novel sandwich-type compound, Na-12 [Fe-4 (H2O)(2) (As2W15O56)(2)] . 38H(2)O (denoted as Fe(4)AS(4)W(30)) was synthesized. The compound was well characterized by means of IR, UV-Vis, W-138 NMR and elemental analyses. Redox electrochemistry of the compound has been studied in acid buffer solutions using cyclic voltammetry(CV). The compound containing multilayer films has been fabricated on the 4-aminobenzoic acid(4-ABA) modified glassy carbon electrode(GCE) surface by alternate deposition with a quaternized poly (4-vinylpyridine) partially completed with [Os(bpy)(2)Cl](2+/-) (denoted as QPVP-Os). CV, X-ray photoelectron spectroscopy (XPS) and UV-Vis spectroscopy were used to characterize the asprepared multilayer films. It is proved that the multilayer films are uniform and stable. The electrocatalytic activities of the multilayer films were investigated on the reduction of two substrates of important analytical interest, NO2- and H2O2.

An organic-inorganic hybrid ultrathin film: preparation and characterization of copper phthalocyanine derivative-ferric oxide nanoparticles

A nanoparticulate ferric oxide-copper tris(2,4-di-tert-amylphenoxy)-8-quinolinolylphthalocyanine hybrid ultrathin film was constructed from alternate layers by the Langmuir-Blodgett technique. The composition, morphology and structure of the film were studied by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy, atomic force microscopy, small-angle X-ray diffraction, visible spectroscopy and polarized UV-Vis spectroscopy. All the above analyses suggest that the thin film is a kind of one-dimensional superlattice, composed of organic and inorganic components. The XPS data reveal that the nanoparticulate ferric oxide exists as an alpha-Fe2O3 phase in the films. Gas-sensing measurements show that the hybrid LB film has very fast response-recovery characteristics towards 2 ppm C2H5OH vapor.

Gas sensitivity of composite Langmuir-Blodgett films of Fe2O3 nanoparticle-copper phthalocyanine

The Langmuir-Blodgett (LB) composite films, ferric oxide nanoparticle composite with tris-(2,3-di-t-amylphenoxy)-(8-quinolinolinolyl) copper phthalocyanine (CuPcA(2)), were obtained by capped type and alternated type and characterized by X-ray photoelectron spectroscopy (XPS) and visible spectra. The gas sensitivity of the composite films and the pure ferric oxide and pure CuPcA(2) LB films to ammonia and ethanol were measured at room temperature. The composite films could be used as the C2H5OH sensors in the range of 2-8 or 100-200 ppm. The XPS data suggested that the adduct complex NH3-CuPcA(2) was formed after the capped film was exposed to the detected gas of ammonia. (C) 2000 Elsevier Science B.V. All rights reserved.

Grafting of diaminoalkane on glassy carbon surface and its functionalization

Diaminoalkanes (NH2(CH2)(n)NH2, n = 7,10,12) were grafted onto a glassy carbon electrode (GCE) surface by amino cation radical formed during electrooxidation of amino group. The presence of diamine grafted layer at the GCE is demonstrated by X-ray photoelectron spectroscopy. The effect of the grafted layer at the GCE surface on the redox responses of Ru(NH3)(6)(3+) and Fe(CN)(6)(3-) redox probes has been investigated. Electrochemical impedance experiments indicate that the kinetics of electron transfer are slowed down when the scan rate taken to modify the GCE is low, and that diaminoalkane with longer alkyl-chain used has higher blocking characteristics. The amine-functionalized GCE is versatile not only to further covalently immobilize ferrocene acetic acid via carbodiimide coupling, but also as a charge-rich substrate to successfully adsorb heteropolyanion P2W18 in acidic solution by electrostatic interaction. (C) 2000 Elsevier Science S.A. All rights reserved.

Effect of LB monolayers on the mixed crystals of Lead and barium sulfate

The effect of LB monolayers on the mixed crystal was investigated by using X-ray photoelectron spectroscopy (XPS), Transmission electron microscopy (TEM), and Inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The results show that LB monolayer has selectivity for the different nucleation ions with equal charge numbers and about the same ion radius. The selectivity is dependent on the head groups of monolayer. The monolayer and the doped ions have also an effect on the crystal morphology. (C) 2000 Published by Elsevier Science B.V. All rights reserved.