Kinetics of atomic force microscope-based scanned probe oxidation on an octadecylated silicon(111) surface

Atomic force microscope (AFM)-based scanned probe oxidation (SPO) nanolithography has been carried out on an octadecyl-terminated Si(111) surface to create dot-array patterns under ambient conditions in contact mode. The kinetics investigations indicate that this SPO process involves three stages. Within the steadily growing stage, the height of oxide dots increases logarithmically with pulse duration and linearly with pulse voltage. The lateral size of oxide dots tends to vary in a similar way. Our experiments show that a direct-log kinetic model is more applicable than a power-of-time law model for the SPO process on an alkylated silicon in demonstrating the dependence of oxide thickness on voltage exposure time within a relatively wide range. In contrast with the SPO on the octodecysilated SiO2/silicon surface, this process can be realized by a lower voltage with a shorter exposure time, which will be of great benefit to the fabrication of integrated nanometer-sized electronic devices on silicon-based substrates. This study demonstrates that the alkylated silicon is a new promising substrate material for silicon-based nanolithography.

Electrooxidation of COad intermediated from methanol oxidation on polycrystalline Pt electrode

The poisonous intermediate of methanol oxidation on a Pt electrode was validated to be COad by electrochemical method. An approximate treatment to bimolecular elementary reactions on an electrode was advanced and then was applied to the stripping normal pulse voltammetry (NPV) for complex multistep multielectron transfer processes on plane electrodes to study the kinetics of completely irreversible process Of COad oxidation to CO2. The kinetic parameters for this process, such as standard rate constant (0) and anodic transfer coefficient (alpha) for this irreversible heterogeneous electron-transfer process at electrode/solution interface and apparent diffusion coefficient (D-app) for charge-transfer process within the monolayer of COad on electrode surface, were obtained with stripping NPV method. The effect of the approximate treatment on the kinetic parameters was also analyzed.

Modification of electrode surface through electrospinning followed by self-assembly multilayer film of polyoxometalate and its photochromic

Electrospun poly (vinyl alcohol) (PVA) nanofibers mat was collected on indium tin oxide (ITO) substrate. Heat crosslinked nanofibers mat became water-insoluble and firmly fixed on ITO substrate even in water. Oppositely charged poly (allylamine hydrochloride) (PAH) and Dawson-type polyoxometalate (POM), Na6P2Mo18O62 (P2Mo18), were alternately assembled on PVA nanofibers-coated ITO substrate to construct multilayer film through an electrostatic layer-by-layer (LBL) technique. The scanning electron microscope (SEM) images showed that P2Mo18 multilayer film was selectively deposited on PVA nanofibers while the unoccupied space by nanofibers on bare ITO was acted as substrate at the same time because the electrospun nanofibers have larger surface area and surface energy than the flat substrate. The cyclic voltammograms current responses of the P2Mo18 multilayer film on PVA/ITO electrode showed three well-defined redox couples of P2Mo18, but very small because P2Mo18 multilayer film was selectively deposited on PVA nanofibers with poor conductivity. In addition, the photochromic behavior of P2Mo18 multilayer film on PVA/ITO was investigated through UV-vis spectra and electron spin resonance (ESR). Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) proved that the charge-transfer complex was formed between PAH and P2Mo18 after UV irradiation.

Novel chemical synthesis of Pt-Ru-P electrocatalysts by hypophosphite deposition for enhanced methanol oxidation and CO tolerance in direct methanol fuel cell

A novel method was developed to prepare the highly active Pt-Ru-P/C catalyst. The deposition of phosphorus significantly increased electrochemical active surface (EAS) area of catalyst by reduces Pt-Ru particle size. TEM images show that Pt-Ru-P nanoparticles have an uniform size distribution with an average diameter of 2 nm. Cyclic voltammetry (CV), Chronoamperometry (CA), and CO stripping indicate that the presence of non-metal phosphorus as an interstitial species Pt-Ru-P/C catalyst shows high activity for the electro-oxidation of methanol, and exhibit enhanced performance in the oxidation of carbon monoxide compared with Pt-Ru/C catalyst. At 30 degrees C and pure oxygen was fed to the cathode, the maximum power density of direct methanol fuel cell (DMFC) with Pt-Ru-P/C and Pt-Ru/C catalysts as anode catalysts was 61.5 mW cm(-2) and 36.6 mW cm(-2), respectively. All experimental results indicate that Pt-Ru-P/C catalyst was the optimum anode catalyst for direct methanol fuel cell.

Scanned probe oxidation on an octadecyl-terminated silicon (111) surface with an atomic force microscope: kinetic investigations in line patterning

Scanned probe oxidation (SPO) nanolithography has been performed with an atomic force microscope (AFM) on an octadecyl-terminated silicon (111) surface to create protuberant oxide line patterns under ambient conditions in contact mode. The kinetic investigations of this SPO process indicate that the oxide line height increases linearly with applied voltage and decreases logarithmically with writing, speed. The oxide line width also tends to vary with the same law. The ambient humidity and the AFM tip state can remarkably influence this process, too. As compared with traditional octadecylsilated SiO2/Si substrate, such a substrate can guarantee the SPO with an obviously lowered voltage and a greatly increased writing speed. This study demonstrates that such alkylated silicon is a promising silicon-based substrate material for SPO nanolithography.

Preparation of a carbon supported Pt catalyst using an improved organic sol method and its electrocatalytic activity for methanol oxidation

The organic sol method for preparing ultrafine transition metal colloid particles reported for the first time by Bonnemann et al. [H. Bonnemann, W Brijoux, R. Brinkmann, E. Dinjus, T. Jou beta en, B. Korall, Angew. Chem. Int. Ed. Engl., 30 (1991) 1312] has been improved in this paper. The improved organic sol method uses SnCl2 as the reductant and methanol as the organic solvent. Thus, this method is very simple and inexpensive. It was found that the average size of the Pt particles in the Pt/C catalysts can be controlled by adjusting the evaporating temperature of the solvent. Therefore, the Pt/C catalysts prepared by the same method are suitable for evaluating the size effect of the Pt particles on electrocatalytic performance for methanol oxidation. The results of the X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed that when the evaporating temperatures of the solvent are 65, 60, 50, 40, and 30 degrees C, the average sizes of the Pt particles in the Pt/C catalysts prepared are: 2.2, 3.2, 3.8, 4.3, and 4.8 nm, respectively. The X-ray photoelectron spectroscopic (XPS) results demonstrated that the small Pt particles are easily oxidized and the decomposition/adsorption of methanol cannot proceed on the surfaces of Pt oxides.

Synthesis using electrospinning and stabilization of single layer macroporous films and fibrous networks of poly(vinyl alcohol)

We demonstrated in this paper an electrospinning technique could be employed to prepare the single layer macroporous films and fibrous networks of poly(vinyl alcohol) (PVA). A crucial element using electrospinning on the development of these electrospun structures was to shorten the distance of from the needle tip to the collector (L), which resulted in the bond of the wet fibers deposited on the collector at the junctions. The morphologies and average pore size of electrospun structures of PVA were mainly predominated by L and the time of collecting wet fibers on the collector. In addition, experimental results showed that an increase of the PVA concentration or a decrease of the applied voltage could also diminish slightly the average pore size of electrospun productions. Furthermore, a 60 degrees C absolute ethanol soak to PVA electrospun production led them to be able to stabilize in water for 1 month against disintegration. Differential scanning calorimetry (DSC) demonstrated that the 60 degrees C ethanol soak enhanced the degree of crystallinity of PVA production. The structural characteristic of macroporous films and networks in combination with their easy processability suggests potential utility in issue engineering applications.

Effect of cations in solution on the oxidation of methanol on the surface of platinum electrode

The effect of metal cations in solution on the oxidation of methanol on the electrode surface of platinum is a neglected aspect to direct methanol fuel cell (DMFC). In this paper, a smooth platinum electrode absorbing metal cations as the working electrode was applied to investigate the methanol oxidation with the cyclic voltammetry (CV) in 1.0 mol L-1 H2SO4. From the analysis of experiment, it is found that the cations, Li+, Ce4+, Mn2+, Ni2+, Cu2+, have some negative effect on the catalytic oxidation of methanol on the surface of platinum. The degree of the effect from different cations was analyzed.

Physical and electrochemical characterizations of PtRu/C catalysts by spray pyrolysis for electrocatalytic oxidation of methanol

In this paper, it was reported that the carbon-supported Pt-Ru(Pt-Ru/C) catalyst used as the anodic catalyst in the direct methanol fuel cell (DMFC) was synthesized with a two-step spray pyrolysis (SP) method using the Pt and Ru metal salt as the precursors and polyethylene glycol (PEG) with the different molecular weights (Mw= 200,600,and 1000 analytical reagent) as cosolvent. PEG as a cosolvent plays a crucial role in producing PtRu/C catalysts. It was found that the Mw of PEG could affect the electrocatalytic activity of Pt-Ru and the morphology of the Pt-Ru particles in the Pt-Ru/C catalysts prepared with this method. When the Mw of PEG is 600, the Pt-Ru particles in the Pt-Ru/C catalyst prepared with this method possess the small average size, narrow size distribution, uniform dispersion, and high electrochemically active specific surface area. The electrocatalytic activity of the Pt-Ru/C catalyst prepared with this method using the cosolvent PEG with Mw = 600 for the methanol oxidation is much higher than that of the commercial E-TEK Pt-Ru/C catalyst. Therefore, the two-step SP method is an excellent method for the preparation of the Pt-Ru/C catalyst used in DMFCs.

Crystal structure and morphology of phenyl-capped tetraaniline in the leucoemeraldine oxidation state

A series of crystals of phenyl-capped tetraaniline in the leucoemeraldine oxidation state were obtained at different isothermal temperatures and were observed directly under transmission electron microscope. The crystals obtained at higher temperatures exhibit more perfect structures than those obtained at lower temperatures. Both the lamella thickness and the crystal size increase with crystallization temperature. The tetraaniline is apt to form larger scale crystals under lower degree of supercooling. However, their crystal structures keep steady with the crystallization temperature. The tetramer was found to adopt a monoclinic lattice with unit cell parameter of a = 13.93 angstrom, b = 8.82 angstrom, c = 23.20 angstrom, and beta = 95.03 degrees, as determined using electron diffraction tilting method combined with wide-angle X-ray diffraction experiment.

Direct oxidation of benzene to phenol on manganese pyrophosphate with hydrogen peroxide

A solid catalyst manganese pyrophosphate based on non-sieves to oxidize benzene to phenol with oxidant hydrogen peroxide has shown good conversion with good selectivity in CH3CN at 65 degrees C investigating water contact angle data of three manganese salts, it is found manganese pyrophosphate has certain repulsive water character. It is further to be confirmed by benzene and phenol adsorption experiments onto catalyst surface by GC. With benzene/H2O2 ratio of 1, the benzene conversion of 13.8% with phenol selectivity of 85.0% was achieved. It is noteworthy that no any products are obtained using manganese pyrophosphate as catalyst in the oxidation of phenol in CH3CN solvent.

Medicated wound dressings based on poly(vinyl alcohol)/poly(N-vinyl pyrrolidone)/chitosan hydrogels

Poly(vinyl alcohol) /poly(N-vinyl pyrrolidone) (PVP)/chitosan hydrogels were prepared by a low-temperature treatment and subsequent Co-60 -gamma-ray irradiation and then were medicated with ciprofloxacin lactate (an antibiotic) and chitosan oligomer (molecular weight = 3000 g/mol). The gel content, swelling ratio, tensile strength, and crystallinity of the hydrogels were determined. The effects of the chitosan molecular weight, the low-temperature treatment procedure, and the radiation dosage on the hydrogel properties were examined. The molecular weight of chitosan was lowered by the irradiation, but its basic polysaccharide structure was not destroyed. Repeating the low-temperature treatment and gamma-ray irradiation caused effective physical crosslinking and chemical crosslinking, respectively, and contributed to the mechanical strength of the final hydrogels. The incorporation of PVP and chitosan resulted in a significant improvement in the equilibrium swelling ratio. and elongation ratio of the prepared hydrogels. The ciprofloxacin lactate and chitosan oligomer were soaked into the hydrogels. Their in vitro release behaviors were examined, and they were found to follow diffusion-controlled kinetics.

Study of CH4 and CO oxidation from electrochemical method

CH4 and CO oxidation reaction on perovskite-like oxides La2-xSrxMO4 (0.01 <= x <= 1.0; M = Cu, Ni) was investigated from cyclic voltammetry method, finding that for suprafacial CO oxidation reaction, the catalyst activity has a close correlation to the area of redox peaks measured in the cyclic voltammetry, the larger the peak area is, the higher the activity will be, while for interfacial CH4 oxidation reaction, the activity depends mainly on the difference in redox potentials (Delta E), and the smaller the difference in redox potentials is, the higher the activity will be.

Cyclic voltammetry for predicting oxidation process in heterogeneous catalysis

Catalytic reactions with different oxidation process were investigated and correlated to the electrochemical properties of the catalysts. The activity of suprafacial reaction is closely related to the area of redox peak, while that of the intrafacial one is to the match of redox potentials. Accordingly, it is supposed that cyclic voltammetry (CV) measurement could be a means for predicting the oxidation process in heterogeneous catalysis.