Preparation of colloidal solutions of noble metals stabilized by polyoxometalates and supported catalysts based on these solutions

Conditions for the preparation of stable aqueous monometallic and bimetallic colloidal solutions (sols) of noble metals (Ru, Rh, Pd, Pt, Ir, Ag, and Au) in the presence of polyoxometalates containing W, Mo, V, and Nb were found. The stability of sols against coagulation at room temperature was studied. The metal/C samples prepared by metal adsorption from sols were studied by powder X-ray diffraction analysis and transmission electron microscopy. The following factors of importance for the preparation of a stable sol are discussed: (1) the formation of a sol of a metal polyhydroxo complex stabilized by a polyoxometalate (preliminary stage) and (2) the formation of polyoxometalate-metal clusters in the course of reduction of polyhydroxo complexes.Translated from Kinetika i Kataliz, Vol. 45, No. 6, 2004, pp. 921–929.Original Russian Text Copyright © 2004 by Maksimova, Chuvilin, Moroz, Likholobov, Matveev.     

Scaling laws for the spatial distributions of the plasma parameters in the positive column of a dc oxygen discharge

Comprehensive self-consistent simulations of the positive column plasma of a dc oxygen discharge are performed with the help of commercial CFDRC software (), which enables one to carry out computations in an arbitrary 3D geometry using fluid equations for heavy components and a kinetic equation for electrons. The main scaling laws for the spatial distributions of charged particles are determined. These scaling laws are found to be quite different in the parameter ranges that are dominated by different physical processes. At low pressures, both the electrons and negative ions in the inner discharge region obey a Boltzmann distribution; as a result, a flat profile of the electron density and a parabolic profile of the ion density are established there. In the ion balance, transport processes prevail, so that ion heating in an electric field dramatically affects the spatial distribution of the charged particles. At elevated pressures, the volume processes prevail in the balance of negative ions and the profiles of the charged particle densities in the inner region turn out to be similar to each other.     

Near-Optimal Controls of Discrete-Time Dynamic Systems Driven by Singularly-Perturbed Markov Chains

This work is devoted to near-optimal controls of large-scale discrete-time nonlinear dynamic systems driven by Markov chains; the underlying problem is to minimize an expected cost function. Our main goal is to reduce the complexity of the underlying systems. To achieve this goal, discrete-time control models under singularly-perturbed Markov chains are introduced. Using a relaxed control representation, our effort is devoted to finding near-optimal controls. Lumping the states in each irreducible class into a single state gives rise to a limit system. Applying near-optimal controls of the limit system to the original system, near-optimal controls of the original system are derived.     

Two scenarios for phase-transformation in disordered media

The reasons for the existence of various scenarios for structural transformations in disordered condensed media, such as liquids and amorphous substances, where both smeared transformations and sharp first-order transitions may occur, were analyzed. The ratio between the spatial scale of structural correlations and the size of the smallest possible region occupied by a new phase in the matrix of initial modification is the key parameter determining the scenario for equilibrium phase transformations in liquids. In amorphous substances, the experimentally observed transformations occur far from equilibrium, and the possible size of the region occupied by the new phase corresponds to the minimal nucleus size. For some amorphous solids, quantitative analysis of the transformation width was carried out and the main classes of covalent substances, in which the smeared or sharp transitions occur, were revealed. Specific features of the interparticle interactions determining various transformation scenarios are discussed.     

Potent New Heterogeneous Asymmetric Catalysts

A set of new, air‐stable, Rh^I‐based heterogeneous asymmetric hydrogenation catalysts have been synthesised, characterised, and tested. Individual members of this new family all exhibit good enantioselectivity.     

High-resolution infrared spectra of NCCN and NCCN

High-resolution spectra of ¹⁵N¹²C¹²C¹⁵N and ¹⁴N¹³C¹³C¹⁴N have been measured and analyzed from 200 to 3600 cm⁻¹. All the vibrational levels below 900 cm⁻¹ have been observed and characterized. The Fermi resonance between ν₂ and 2ν₄ has been studied and the resonance constant has been determined for several cases. Several Σ⁻ states have been directly observed for the first time for each isotopomer, the (0001111)0f, (0011111)0f, and (0002222)0f states. The pattern of the energy levels for clusters of l-type resonance coupled levels, such as 0001131,3, has been determined for cyanogen for the first time. Among other things this involved the determination of the vibrational l-type resonance constant, r₄₅. Many of the power series constants, α_i and x_ij, and higher order constants have been determined.