Time‐Resolved,In Situ DRIFTS/EDE/MS Studies on Alumina‐Supported Rhodium Catalysts: Effects of Ceriation and Zirconiation on Rhodium–CO Interactions

The effects of ceria and zirconia on the structure–function properties of supported rhodium catalysts (1.6 and 4 wt % Rh/γ‐Al₂O₃) during CO exposure are described. Ceria and zirconia are introduced through two preparation methods: 1) ceria is deposited on γ‐Al₂O₃ from [Ce(acac)₃] and rhodium metal is subsequently added, and 2) through the controlled surface modification (CSM) technique, which involves the decomposition of [M(acac)_x] (M=Ce, x=3; M=Zr, x=4) on Rh/γ‐Al₂O₃. The structure–function correlations of ceria and/or zirconia‐doped rhodium catalysts are investigated by diffuse reflectance infrared Fourier‐transform spectroscopy/energy‐dispersive extended X‐ray absorption spectroscopy/mass spectrometry (DRIFTS/EDE/MS) under time‐resolved, in situ conditions. CeO_x and ZrO₂ facilitate the protection of Rh particles against extensive oxidation in air and CO. Larger Rh core particles of ceriated and zirconiated Rh catalysts prepared by CSM are observed and compared with Rh/γ‐Al₂O₃ samples, whereas supported Rh particles are easily disrupted by CO forming mononuclear Rh geminal dicarbonyl species. DRIFTS results indicate that, through the interaction of CO with ceriated Rh particles, a significantly larger amount of linear CO species form; this suggests the predominance of a metallic Rh phase.     

Direct On‐Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature

We report herein an efficient, fast, and simple synthesis of an imine‐based covalent organic framework (COF) at room temperature (hereafter, RT‐COF‐1 ). RT‐COF‐1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N₂ and CO₂. The room‐temperature synthesis has enabled us to fabricate and position low‐cost micro‐ and submicropatterns of RT‐COF‐1 on several surfaces, including solid SiO₂ substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink‐jet printing.     

Free convection effects and radiative heat transfer in MHD Stokes problem for the flow of dusty conducting fluid through porous medium

The present note deals with the effects of radiative heat transfer and free convection in MHD for a flow of an electrically conducting, incompressible, dusty viscous fluid past an impulsively started vertical non-conducting plate, under the influence of transversely applied magnetic field. The heat due to viscous dissipation and induced magnetic field is assumed to be negligible. The governing linear partial differential equations are solved by finite difference technique. The effects of various parameters (like radiation parameter N, Prandtl number Pr, porosity parameter K) entering into the MHD Stokes problem for flow of dusty conducting fluid have been examined on the temperature field and velocity profile for both the dusty fluid and dust particles.     

A RECONSIDERATION OF THE PROPERTIES OF A PULSED RUBY LASER IN RELATION TO MICROSURGERY

Abstract— The properties of a pulsed ruby laser beam focused through a triocular microscope were studied in relation to microsurgery. Quantitative studies on 'model tissues' with different absorbencies at 6943 Å revealed that the spot diameter of the focused microbeam was dependent upon several factors. It decreased with (1) a decrease in the absorption by the object at 6943 Å; (2) a decrease in the energy of the microbeam; and (3) an increase in the magnification of the microscope. The existence of the 'tube of effect' in the optical path of the focused micro-beam was realized by irradiating the object at different planes. The depth of the tube of effect increased with (1) increase in laser energy or (2) decrease in magnification. By employing certain plant species ( Spirogyra praetensis Transeau, Ulva lactuca Linnaeus, Porphyra miniata (Lyngbye) C. Agardh and Elodea sp.) the reaction of the protoplasm to the laser microbeam in terms of 'primary damage' and 'secondary damage' was defined. Based on these experimental data the concept of minimal visible spot size in laser microsurgery and its limitations are discussed.     

X-ray absorption spectroscopy of hemes and hemeproteins in solution: multiple scattering analysis

A full quantitative analysis of Fe K-edge X-ray absorption spectra has been performed for hemes in two porphynato complexes, that is, iron(III) tetraphenylporphyrin chloride (Fe(III)TPPCl) and iron(III) tetraphenylporphyrin bis(imidazole) (Fe(III)TPP(Imid)2), in two protein complexes whose X-ray structure is known at atomic resolution (1.0 A), that is, ferrous deoxy-myoglobin (Fe(II)Mb) and ferric aquo-myoglobin (Fe(III)MbH2O), and in ferric cyano-myoglobin (Fe(III)MbCN), whose X-ray structure is known at lower resolution (1.4 A). The analysis has been performed via the multiple scattering approach, starting from a muffin tin approximation of the molecular potential. The Fe-heme structure has been obtained by analyzing independently the Extended X-ray Absorption Fine Structure (EXAFS) region and the X-ray Absorption Near Edge Structure (XANES) region. The EXAFS structural results are in full agreement with the crystallographic values of the models, with an accuracy of +/- 0.02 A for Fe-ligand distances, and +/-6 degrees for angular parameters. All the XANES features above the theoretical zero energy (in the lower rising edge) are well accounted for by single-channel calculations, for both Fe(II) and Fe(III) hemes, and the Fe-N p distance is determined with the same accuracy as EXAFS. XANES evaluations of Fe-5th and Fe-6th ligand distances are determined with 0.04-0.07 A accuracy; a small discrepancy with EXAFS (0.01 to 0.05 A beyond the statistical error), is found for protein compounds. Concerns from statistical correlation among parameters and multiple minima in the parameter space are discussed. As expected, the XANES accuracy is slightly lower than what was found for polarized XANES on Fe(III)MbCN single crystal (0.03-0.04 A), and states the actual state-of-the-art of XANES analysis when used to extract heme-normal parameters in a solution spectrum dominated by heme-plane scattering.     

Development and testing of a compact basis set for use in effective core potential calculations on rhodium complexes

We present a set of effective core potential (ECP) basis sets for rhodium atoms which are of reasonable size for use in electronic structure calculations. In these ECP basis sets, the Los Alamos ECP is used to simulate the effect of the core electrons while an optimized set of Gaussian functions, which includes polarization and diffuse functions, is used to describe the valence electrons. These basis sets were optimized to reproduce the ionization energy and electron affinity of atomic rhodium. They were also tested by computing the electronic ground state geometry and harmonic frequencies of [Rh(CO)₂μ‐Cl]₂, Rh(CO)₂ClPy, and RhCO (neutral and its positive, and negative ions) as well as the enthalpy of the reaction of [Rh(CO)₂μ‐Cl]₂ with pyridine (Py) to give Rh(CO)₂ClPy, at different levels of theory. Good agreement with experimental values was obtained. Although the number of basis functions used in our ECP basis sets is smaller than those of other ECP basis sets of comparable quality, we show that the newly developed ECP basis sets provide the flexibility and precision required to reproduce a wide range of chemical and physical properties of rhodium compounds. Therefore, we recommend the use of these compact yet accurate ECP basis sets for electronic structure calculations on molecules involving rhodium atoms. © 2012 Wiley Periodicals, Inc.     

Heat transfer in MHD flow of dusty viscoelastic (Walters’ liquid model-B) stratified fluid in porous medium under variable viscosity

The paper investigates the effects of heat transfer in MHD flow of viscoelastic stratified fluid in porous medium on a parallel plate channel inclined at an angle θ. A laminar convection flow for incompressible conducting fluid is considered. It is assumed that the plates are kept at different temperatures which decay with time. The partial differential equations governing the flow are solved by perturbation technique. Expressions for the velocity of fluid and particle phases, temperature field, Nusselt number, skin friction and flow flux are obtained within the channel. The effects of various parameters like stratification factor, magnetic field parameter, Prandtl number on temperature field, heat transfer, skin friction, flow flux, velocity for both the fluid and particle phases are displayed through graphs and discussed numerically.     

Effect of Zr,Ti substitutions onT c in superconducting YBa2Cu3O7−δ system

Zr and Ti have been substituted in the system Y_1−x M _x Ba₂Cu₃O_7−δ(M=Zr, Ti,x=0.05,0.1). We find that theT _c value is unchanged, ∼90K for Zr substitutions up to 10% and in the case of Ti substitutions theT _c drops significantly. These changes may arise from their site preference.     

钙钛矿结构荧光材料MZrO3:Eu3+,A (M=Ca2+, Ba2+; A=Li+, Na+, K+)的制备及其发光性质

Calcium and barium zirconate powders based upon CaZrO₃:Eu³⁺,A and BaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) were prepared by combustion synthesis method and heating to ~1000℃ to improve crystallinity.The structure and morphology of materials were examined by X-ray diffraction (XRD) and scanningelectron microscopy (SEM). XRD results showed that CaZrO₃:Eu³⁺,A and BaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) perovskites possessed orthorhombic and cubic structures, respectively. The morphologies of all powderswere very similar consisting of small, coagulated, cubical particles with narrow size distributions andsmooth and regular surfaces. The characteristic luminescences of Eu³⁺ ions in CaZrO₃:Eu³⁺,A (A=Li⁺, Na⁺, K⁺) lattices were present with strong emissions at 614 and 625 nm for ⁵D₀→⁷F₂ transitions with other weakeremissions observed at 575, 592, 655, and 701 nm corresponding to ⁵D₀→⁷F_n transitions (where n=0, 1, 3, 4 respectively). In BaZrO₃:Eu³⁺ both the ⁵D₀→⁷F₁ and ⁵D₀→⁷F₂ transitions at 595 and 613 nm were strong.Photoluminescence intensities of CaZrO₃:Eu³⁺ samples were higher than those of BaZrO₃:Eu³⁺ lattices. Thisremarkable increase of photoluminescence intensity (corresponding to ⁵D₀→⁷F_n transitions) was observedin CaZrO₃:Eu³⁺ and BaZrO₃:Eu³⁺ if co-doped with Li⁺ ions. An additional broad band composed of manypeaks between 440 to 575 nm was observed in BaZrO₃:Eu³⁺,,A samples. The intensity of this band wasgreatest in Li⁺ co-doped samples and lowest for K⁺ doped samples.