Understanding silica-supported metal catalysts: Pd/silica as a case study

Supported metal catalysts, particularly noble metals supported on SiO₂, have attracted considerable attention due to the importance of the silica–metal interface in heterogeneous catalysis and in electronic device fabrication. Several important issues, e.g., the stability of the metal–oxide interface at working temperatures and pressures, are not well-understood. In this review, the present status of our understanding of the metal–silica interface is reviewed. Recent results of model studies in our laboratories on Pd/SiO₂/Mo(1 1 2) using LEED, AES and STM are reported. In this work, epitaxial, ultrathin, well-ordered SiO₂ films were grown on a Mo(1 1 2) substrate to circumvent complications that frequently arise from the silica–silicon interface present in silica thin films grown on silicon.     

Nitric oxide reduction and carbon monoxide oxidation over carbon-supported copper-chromium catalysts

Carbon supported copper-chromium catalysts are shown to be very active for both the reduction of nitric oxide with carbon monoxide and the oxidation of carbon monoxide with oxygen. Mixed copper-chromium oxide active phases have good activity in the simultaneous removal of nitric oxide and carbon monoxide from exhaust gases. The influence of several catalyst variables has been investigated. The activity per volume of catalyst increases with increasing loading, while the intrinsic activity shows a maximum around C/M=100−50. An optimum catalyst for nitric oxide reduction and carbon monoxide oxidation has a copper/chromium ratio of 2/1. The apparent activation energy for the carbon monoxide oxidation over carbon supported copper-chromium catalysts is 77 kJ/mol, suggesting that the Cu---O bond rupture is the rate-limiting process. The reduction of nitric oxide takes place at higher temperatures. Since all catalysts have a low selectivity for molecular nitrogen formation at lower temperatures, the dissociation of nitric oxide is probably rate determining, resulting in a slightly reduced catalyst system. In an excess of carbon monoxide the reaction is first-order in nitric oxide and zero-order in carbon monoxide. Moisture inhibits the reaction by reversible competitive adsorption, whereas carbon dioxide does not. Oxygen completely inhibits the reduction of nitric oxide due to the more rapid reoxidation of the catalytic sites compared to nitric oxide. Therefore, the reduction of nitric oxide takes place only when all oxygen has been converted and, hence, is shifted to higher temperatures. As a possible consequence, the production of nitrous oxide is reduced. Nitric oxide and molecular oxygen react preferentially with carbon monoxide, so, in an excess of oxidizing component, gasification of the carbon support occurs at higher temperatures after carbon monoxide has been completely consumed.     

Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

Bootstrapping the Local Periodogram of Locally Stationary Processes

Abstract. Locally stationary processes are non‐stationary stochastic processes the second‐order structure of which varies smoothly over time. In this paper, we develop a method to bootstrap the local periodogram of a locally stationary process. Our method generates pseudo local periodogram ordinates by combining a parametric time and non‐parametric frequency domain bootstrap approach. We first fit locally a time varying autoregressive model so as to capture the essential characteristics of the underlying process. A locally calculated non‐parametric correction in the frequency domain is then used so as to improve upon the locally parametric autoregressive fit. As an application, we investigate theoretically the asymptotic properties of the bootstrap method proposed applied to the class of local spectral means, local ratio statistics and local spectral density estimators. Some simulations demonstrate the ability of our method to give accurate estimates of the quantities of interest in finite sample situations and an application to a real‐life data‐set is presented.     

3D velocity from 3D Doppler radial velocity

We present local least squares and regularization frameworks for computing 3D velocity (3D optical flow) from 3D radial velocity measured by a Doppler radar. We demonstrate the performance of our algorithms quantitatively on synthetic radial velocity data and qualitatively on real radial velocity data, obtained from the Doppler radar at Kurnell Radar station, Botany Bay, New South Wales, Australia. Radial velocity can be used to predict the future positions of storms in sequences of Doppler radar datasets.© 2005 Wiley Periodicals, Inc. Int J Imaging Syst Technol, 15, 189–198, 2005     

DSS research and practice in perspective

The aim of this paper is to assess the state-of-the-art in the Decision Support Systems (DSS) field from both a research and a practice perspective. Three main dimensions of DSS research and practice are addressed: 1) supporting human decision-making processes, 2) integrating DSS into the organizational context, and 3) identifying new application domains. The related analysis and discussion provides a better understanding of past developments in the DSS field and insights into future evolution patterns.     

Practical method for generation expansion planning based on dynamic programming

This paper presents an efficient method which provides the optimal generation mix and the optimal generation construction process. The approximation method in which the dynamic programming technique and gradient method are combined is applied to determine the optimal generation mix with hydropower generation technologies. The successive approximations dynamic programming (SADP) technique, which is very suitable for high-dimensional multistage decision process problems, is used for obtaining the optimal generation construction process. The effectiveness and feasibility of the developed technique are demonstrated on a practical power system model which has five types of generation technologies including a hydropower generation technology.     

Computing distance transformations in convex and non-convex domains

It is shown that the well known two-pass sequential local transformation algorithm for computing a distance transformation in rectangular domains may fail in some convex integer domains, but that a four-pass algorithm is sufficient in all two-dimensional convex domains. For non-convex domains the number of passes necessary is shown to be generally greater. Two propagation algorithms for computing the distance transformation are described and shown theoretically and experimentally to be computationally more efficient than the sequential local transformation algorithm in non-convex domains of complex shape. The relationship of the distance transformation in non-convex domains to some more general transformations is explored.     

A new family of sugar-inducible expression vectors for Escherichia coli

A set of 11 expression vectors was constructed, each of themharbouring a cloning cassette under the control of the promoter.Some of these vectors enable expression of foreign proteinsin the cytoplasm, while others include a synthetic sequencecoding for a very efficient secretion signal sequence. Otherfeatures are an fl origin of replication (in plus or minus orientation)and a promoter^up mutation that enhances the already very highlevel of expression from these vectors. With such a versatilevector family, cloning, sequencing and sitedirected mutagenesiscan be performed on the same vector, and the level of expressioncan be defined according to the specific constraints of a givenprotein.