Catalytic Mo2C coatings for the water gas shift reaction: Electrosynthesis in molten salts

Electrosynthesis methods using molten salts are suggested for obtaining a new catalytic system based on the Mo2C/Mo composition for the water gas shift reaction. The coatings obtained by the discharge of the carbonate ion on a molybdenum substrate and by the simultaneous reduction of the electroactive species MoO42 and CO32- are catalytically more active than bulk Mo2C or the commercial catalyst Cu-ZnO-Al2O3 by one and three orders of magnitude, respectively.

Electrochemical synthesis of Mo2C catalytical coatings for the water-gas shift reaction

The electroreduction of CO32- ions on a molybdenum cathode in a NaCl-KCl-Li2CO3 melt was studied by cyclic voltarnmetry. The electrochemical synthesis of Mo2C on molybdenum substrates has been performed at It 23 K for 7 h with a cathodic current density of 5 mA cm(-2). If molybdenum carbide is present as a thin (ca. 500 nm) film on a molybdenum substrate (Mo2C/Mo), its catalytic activity in the water gas-shift reaction is enhanced by at least an order of magnitude compared to that of the bulk Mo2C phase.

Investigation of the effect of the preparation method on the activity and stability of Au/CeZrO4 catalysts for the low temperature water gas shift reaction

The impact of the preparation method on the activity and stability of gold supported on ceria-zirconia low temperature water-gas shift (WGS) catalysts have been investigated. The influence of the gold deposition method, nature of the gold precursor, nature of the washing solution, drying method, Ce: Zr ratio of the support and sulfation of the support have been evaluated. The highest activity catalysts were obtained using a support with a Ce: Zr mole ratio 1: 1, HAuCl4 as the gold precursor deposited via deposition precipitation using sodium carbonate as the precipitation agent and the catalyst washed with water or 0.1 M NH4OH solution. In addition, the drying used was found to be critical with drying under vacuum at room temperature found to be most effective.

A test for psychometric function shift

A nonparametric, small-sample-size test for the homogeneity of two psychometric functions against the left- and right-shift alternatives has been developed. The test is designed to determine whether it is safe to amalgamate psychometric functions obtained in different experimental sessions. The sum of the lower and upper p-values of the exact (conditional) Fisher test for several 2 × 2 contingency tables (one for each point of the psychometric function) is employed as the test statistic. The probability distribution of the statistic under the null (homogeneity) hypothesis is evaluated to obtain corresponding p-values. Power functions of the test have been computed by randomly generating samples from Weibull psychometric functions. The test is free of any assumptions about the shape of the psychometric function; it requires only that all observations are statistically independent. © 2011 Psychonomic Society, Inc.

Immunophenotypic shift in a case of mycosis fungoides with vitreous invasion

The case of an 82-year-old man who developed intraocular extension from mycosis fungoides, a cutaneous T-cell lymphoma, is presented. The patient died soon after intra-ocular involvement occurred. Immunohistochemistry of a skin biopsy, taken early in the course of the disease, disclosed a predominance of T cells with a helper/inducer phenotype (CD4). However, an intraocular infiltrate obtained 7 years later contained mostly T cells with a suppressor/cytotoxic phenotype (CD8). The occurrence of ocular invasion, the change in immunophenotype, and the predominant proliferation of CD8 lymphocytes may have been related to the poor outcome in this patient.

Deactivation mechanism of a Au/CeZrO4 catalyst during a low-temperature water gas shift reaction

On-stream deactivation during a water gas shift (WGS) reaction over gold supported on a ceria-zirconia catalyst was examined. Although the fresh catalyst has very high low temperature (<200 degrees C) for WGS activity, a significant loss of CO conversion is found under steady-state operations over hours. This has been shown to be directly related to the concentration of water in the gas phase. The same catalyst also undergoes thermal deactivation above 250 degrees C, and using a combined experimental and theoretical approach, a common deactivation mechanism is proposed. In both cases, the gold nanoparticles, which are found under reaction conditions, are thought to detach from the oxide support either through hydrolysis, <200 degrees C, or thermally, > 200 degrees C. This process reduces the metal-support interaction, which is considered to be critical in determining the high activity of the catalyst.

Pulse-response TAP studies of the reverse water-gas shift reaction over a Pt/CeO2 catalyst

The temporal analysis of products (TAP) technique was successfully applied for the first time to investigate the reverse water-gas shift (RWGS) reaction over a 2% Pt/CeO2 catalyst. The adsorption/desorption rate constants for CO2 and H-2 were determined in separate TAP pulse-response experiments, and the number of H-containing exchangeable species was determined using D-2 multipulse TAP experiments. This number is similar to the amount of active sites observed in previous SSITKA experiments. The CO production in the RWGS reaction was studied in a TAP experiment using separate (sequential) and simultaneous pulsing Of CO2 and H-2. A small yield of CO was observed when CO2 was pulsed alone over the reduced catalyst, whereas a much higher CO yield was observed when CO2 and H-2 were pulsed consecutively. The maximum CO yield was observed when the CO2 pulse was followed by a H-2 pulse with only a short (1 s) delay. Based on these findings, we conclude that an associative reaction mechanism dominates the RWGS reaction under these experimental conditions. The rate constants for several elementary steps can be determined from the TAP data. In addition, using a difference in the time scale of the separate reaction steps identified in the TAP experiments, it is possible to distinguish a number of possible reaction pathways. (c) 2005 Elsevier Inc. All rights reserved.

A dramatic shift from multiple to simple exchange in the cyclopentane/D-2 probe reaction on palladium catalysts

Electron deficient active sites in Pd catalysts, either as films or on supports, are deliberately generated by calcining in O-2 at high temperature followed by the mildest possible reduction (with the reaction mixture itself), and are manifested by a marked shift from multiple to simple exchange in the cyclopentane/D-2 probe reaction.

The water-gas shift reaction over CeO/CuO:Operando SSITKA-DRIFTS-mass spectrometry study of low temperature mechanism

An inverse CeO2/CuO catalyst has been investigated by operando steady-state isotopic transient kinetic analysis (SSITKA) in combination with diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under 3% CO +3% H2O reactant mixture at 473 K with the aim of determining intermediates involved in the water gas shift reaction at relatively low temperatures. Among the various species detected in the infrared spectra which may be involved in the reaction, i.e. formates, copper carbonyls and carbonates, a particular type of carbonate species is identified as a reaction intermediate on the basis of detailed analysis of the spectra during isotopic exchange in comparison with the change in the corresponding isotopically labelled CO2 product. 

Mean shift based gradient vector flow for image segmentation

In recent years, gradient vector flow (GVF) based algorithms have been successfully used to segment a variety of 2-D and 3-D imagery. However, due to the compromise of internal and external energy forces within the resulting partial differential equations, these methods may lead to biased segmentation results. In this paper, we propose MSGVF, a mean shift based GVF segmentation algorithm that can successfully locate the correct borders. MSGVF is developed so that when the contour reaches equilibrium, the various forces resulting from the different energy terms are balanced. In addition, the smoothness constraint of image pixels is kept so that over- or under-segmentation can be reduced. Experimental results on publicly accessible datasets of dermoscopic and optic disc images demonstrate that the proposed method effectively detects the borders of the objects of interest.