Conversion of Methane into Methanol and Ethanol over Nickel Oxide on Ceria–Zirconia Catalysts in a Single Reactor

The conversion of methane into alcohols under moderate reaction conditions is a promising technology for converting stranded methane reserves into liquids that can be transported in pipelines and upgraded to value‐added chemicals. We demonstrate that a catalyst consisting of small nickel oxide clusters supported on ceria–zirconia (NiO/CZ) can convert methane to methanol and ethanol in a single, steady‐state process at 723 K using O₂ as an abundantly available oxidant. The presence of steam is required to obtain alcohols rather than CO₂ as the product of catalytic combustion. The unusual activity of this catalyst is attributed to the synergy between the small Lewis acidic NiO clusters and the redox‐active CZ support, which also stabilizes the small NiO clusters.     

Hydrogen bonding in polymer mixtures

The enthalpy–infrared frequency shift correlation for simple acids and bases is extended to study hydrogen bonding in polymer systems. The acidity of a polymer is calibrated by comparing the shifts in hydroxyl absorption frequency of the acidic polymer when mixed with a series of bases with the corresponding spectral shifts of known acids with the same bases. The basicity of a polymer is calibrated by measuring the hydroxyl frequency shifts of known acids when mixed with the basic polymer. For polymers containing carbonyl groups, the shift in carbonyl absorption is also a measure of basicity. The acidity and basicity constants obtained for polymers are in good agreement with the values for small-molecule analogs. The enthalpies of hydrogen bond formation in polymer mixtures are calculated from the acidity or basicity constants.     

Electronic quasiparticles and evolution of Fermi level spin states in thin magnetic layers

Here we report on high-resolution photoemission of iron layers grown on a W(1 1 0) substrate. The evolution of the substrate states upon sub-monolayer adsorption of Fe atoms leads to a shift in surface state binding energy. For thicker (1 1 0) films, sharp metallic surface states are obtained. Their dispersion displays the signature of quasiparticle renormalization due to dressing with excitations. The energy scale is characteristic for the spin wave spectrum in iron, thereby giving evidence of electron-magnon coupling. Furthermore, it is found that quantum well states occur as a function of layer thickness. These modify the spin density of states at the Fermi level in the ferromagnetic film.     

Asynchronous and corrected-asynchronous finite difference solutions of PDEs on MIMD multiprocessors

A major problem in achieving significant speed-up on parallel machines is the overhead involved with synchronizing the concurrent processes. Removing the synchronization constraint has the potential of speeding up the computation, while maintaining greater computation flexibility (e.g. differences in processors speed; differences in the data input to processors). We construct asynchronous (AS) finite difference schemes for the solution of PDEs by removing the synchronization constraint. We analyze the numerical properties of these schemes. Based on the analysis, we develop corrected-asynchronous (CA) finite difference schemes which are specifically constructed for an asynchronous processing. We present asynchronous (AS) and corrected-asynchronous (CA) finite difference schemes for the multi-dimensional heat equation. Although our discussion concentrates on the Euler scheme it should serve only as a sample, as it can be extended to other schemes and other PDEs.These schemes are implemented on the shared-memory multi-userSequent Balance machine. Numerical results for one and two dimensional problems are presented. It is shown experimentally that synchronization penalty can be about 50% of run time: in most cases, the asynchronous scheme runs twice as fast as the parallel synchronous scheme. In general, the efficiency of the parallel schemes increases with processor load, with the time-level, and with the problem dimension. The efficiency of the AS may reach 90% and over, but it provides accurate results only for steady-state values. The CA, on the other hand, is less efficient but provides more accurate results for intermediate (non steady-state) values. The results show the potential of developing asynchronous finite deference schemes for steady-state as well as non steadystate problems.This research was partially supported by a grant from The Basic Research Foundation administrated by The Israel Academy of Sciences and Humanities.A reduced version of the paper was presented at the 4th SIAM Conference on Parallel Processing for Scientific Computing, Dec. 11–13, 1989, Chicago, USA.The work by this author was supported by research grant 337 of the Israeli National Council for Research and Development in the years 1990–1991.This research was supported by the National Aeronautics and Space Administration under NASA Contract No. NASI-18107 while the author was in residence at the Institute for Computer Applications in Sciences and Engineering (ICASE), NASA Langley Research Center, Hampton, VA 23665, USA.     

Orthogonal polynomials for exponential weights on

Let I=[0,d), where d is finite or infinite. Let , where and Q is continuous and increasing on I, with limit ∞ at d. We study the orthonormal polynomials associated with the weight , obtaining bounds on the orthonormal polynomials, zeros, and Christoffel functions. In addition, we obtain restricted range inequalities.     

Influence of Solution Volume on the Dissolution Rate of Silicon Dioxide in Hydrofluoric Acid

Experimental data and modeling of the dissolution of various Si/SiO₂ thermal coatings in different volumes of hydrofluoric acid (HF) are reported. The rates of SiO₂‐film dissolution, measured by means of various electrochemical techniques, and alteration in HF activity depend on the thickness of the film coating. Despite the small volumes (0.6–1.2 mL) of the HF solution, an effect of SiO₂‐coating thickness on the dissolution rate was detected. To explain alterations detected in HF activity after SiO₂ dissolution, spectroscopic analyses (NMR and FTIR) of the chemical composition of the solutions were conducted. This is associated with a modification in the chemical composition of the HF solution, which results in either the formation of an oxidized species in solution or the precipitation of dissolution products. HF₂^? accumulation in the HF solution, owing to SiO₂ dissolution was identified as the source of the chemical alteration.