溶胶-凝胶制备技术与新型催化材料Ⅲ.溶胶粒子表面修饰方法制备催化膜

提出用溶胶粒子表面修饰方法，结合溶胶凝胶技术制备无机催化膜．该方法的基本原理是利用合适的金属配合物在胶粒表面的吸附作用，经溶胶凝胶过程，将活性组分结合到无机膜中．实验测定结果表明：（ＮｉＥＤＴＡ）２－，ＶＯ－３，ＭｏＯ２－４，（Ｐｄ（ＮＨ３）４）２＋，ＰｄＣｌ２－４，ＰｔＣｌ２－６和ＲｈＣｌ３－６可用来修饰ＡｌＯＯＨ溶胶．以Ｐｄ／γＡｌ２Ｏ３催化膜的制备为例，经三次溶胶凝胶过程，可制得无裂缺的厚度为９μｍ的Ｐｄ／γＡｌ２Ｏ３催化膜，膜材料的平均孔直径为６ｎｍ，Ｐｄ被均匀地分布在膜的顶层，其平均粒径为２３ｎｍ．     

Microwave-assisted, efficient and regioselective Pd-catalyzed C-phenylation of halopyrimidines

We herein report that flash heating microwave irradiation is a helpful tool in the formation of arylpyrimidines from the corresponding halopyrimidines. The palladium-catalyzed cross-coupling reactions of 2,4-di- and 2,4,5-trihalopyrimidines with phenylboronic acid under the above conditions are described. By use of the appropriate catalyst and the adequate halopyrimidine, good regioselectivity can be achieved in the 2-, 4-, or 5-positions of the heterocycle. In addition, we show that this methodology is ameneable for the stepwise preparation of mono-, di-, and triphenylpyrimidines.     

Al-pillared clays supported rare earths and palladium catalysts for deep oxidation of low concentration of benzene

Al-pillared clays supported rare earths (RE/Al-PILC) are prepared and used as supports of palladium catalysts for deep oxidation of low concentrations of benzene (130-160 ppm). The supports and catalysts are characterized by X-ray powder diffraction (XRD), FT-IR, BET, transmission electron microscopy (TEM) and temperature-programmed reduction (H₂-TPR). The results show that Al-pillaring results in a strong increase in the basal spacing (d_0 0 1) from about 1.2 to 1.8 nm, and an increase in the BET surface area from 63.6 (±3.2) to 238.8 (±11.9) m²/g. Activity tests of deep oxidation of low concentration benzene show catalysts supported on Al-PILC and RE/Al-PILC are obviously more active than that on raw clay. Pd/6% Ce/Al-PILC, in particular, can catalyze the complete oxidation of low concentration benzene at a temperature as low as about 290 °C.     

Surface structures formed by individual adsorption and coadsorption of Mn and Bi on Cu(0 0 1), studied by LEED

We have studied the individual adsorption of Mn and Bi, and their coadsorption on Cu(0 0 1) by low-energy electron diffraction (LEED). For Mn, we have determined the c(2 × 2) structure formed at 300 K, whose structure had been determined by several methods. We reconfirmed by a tensor LEED analysis that it is a substitutional structure and that a previously reported large corrugation (0.30 Å) between substitutional Mn and remaining surface Cu atoms coincides perfectly with the present value. In the individual adsorption of Bi, we have found a c(4 × 2) structure, which is formed by cooling below ∼250 K a surface prepared by Bi deposition of ∼0.25 ML coverage at 300 K where streaky half-order LEED spots appear. The c(4 × 2) structure has been determined by the tensor LEED analysis at 130 K and it is a substitutional structure. In the coadsorption, we found a c(6 × 4) structure, which has been determined by the tensor LEED analysis. It is very similar to the previously determined structure of the c(6 × 4) formed by coadsorption of Mg and Bi, and embedded MnBi₄ clusters are arranged in the top Cu layer instead of MgBi₄. Large lateral displacements of Bi atoms in the c(6 × 4)-(Mn + Bi) suggest that the Mn atoms undergo the size-enhancement caused by their large magnetic moment.     

Investigations of Solid State Dynamics at the NRSSR Beamline at PETRA II. An Overview

The present status of the new nuclear resonance beamline PETRA 1 at HASYLAB, DESY, Hamburg is described. Besides an overview of the experimental setup some examples of recent experiments are given. Those cover the main applications, i.e., inelastic scattering from iron alloys and quasielastic scattering from glass-forming liquids. This revised version was published online in August 2006 with corrections to the Cover Date.     

Co-Segregation Effects on Boundary Migration

We analyze the effect of co-segregation on the mobility of grain boundaries within the framework of the impurity drag theory originally proposed by Cahn and Lücke and Stüwe for an ideal solution. The new derivation extends this model to the case where there are two types of impurities (or three components in the alloy). Since the resultant expression for the boundary mobility is complicated, numerical solutions were obtained for several cases to show how co-segregation affects the boundary mobility. Depending on the relative diffusivities of the two impurities which are both attracted to the boundary, the mobility may either increase or decrease with increasing concentration of one of the impurities. When one of the impurities is attracted to the boundary and the other repelled from the boundary, increasing the concentration of the attractive impurity can lead to a sharp decrease in the boundary mobility.     

Experimental observation of quantum corrections to electrical resistivity in nanocrystalline soft magnetic alloys

X-ray diffraction patterns of nanocrystalline Fe-Cu-Nb-Si-B (FINEMET) alloys reveal that bcc α-Fe/α-FeSi crystallites with the average grain size of 20(5) nm are dispersed in amorphous matrix. Enhanced electron—electron interaction (EEI) and quantum interference (QI) effects as well as electron-magnon (and/or electron-spin fluctuation) scattering turn out to be the main mechanisms that govern the temperature dependence of resistivity. Of all the inelastic scattering processes, inelastic electron-phonon scattering is the most effective mechanism to destroy phase coherence of electron wave functions. The diffusion constant, density of states at the Fermi level and the inelastic scattering time have been estimated, for the first time, for the alloys in question Article presented at the International Symposium on Advances in Superconductivity and Magnetism: Materials, Mechanisms and Devices, ASMM2D-2001, 25–28 September 2001, Mangalore, India.     

Palladium-catalysed three component synthesis of α,β-unsaturated amidines and imidates

Palladium-catalysed three component coupling of an alkenylbromide, isonitrile and an amine or alkoxide/phenoxide affords α,β-unsaturated-amidines and -imidates.     

Preparation and properties of the biodegradable graded blend of poly(L‐lactic acid) and poly(ethylene oxide)

We prepared biodegradable poly(ethylene oxide) (PEO)/poly(L ‐lactic acid) (PLLA) graded blends by the dissolution–diffusion process, and discussed the biodegradability and tensile strength of the graded blends by comparing isotropic blend and PLLA only. All the graded blends were degraded more largely than the PLLA only and isotropic blend (PEO: 37.5 wt %), which had the same content as the total content of those graded blends. The graded blend having most excellent wide compositional gradient was degraded most largely with the enzyme. Thus, graded structure of the blends promoted their biodegradabilities large. It was considered that the dissolution of PEO with water increased the surface area attacked by the enzyme, while PEO caught PLLA oligomers to promote the biodegradation of PLLA. Then, the biodegradabilities of the graded blends were suppressed by the increasing crystallinity of PLLA. Furthermore, the strengths of all the graded blends were larger than those of the isotropic blend. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2972–2981, 2007     

Palladium-catalyzed pseudo-domino cyclizations: An easy entry toward polycondensed pyrrolidone derivatives

A new type I palladium-catalyzed pseudo-domino process is developed, in which a single Pd-based catalytic system promotes two mechanistically unrelated, sequential catalytic cycles in chronologically distinct order. Suitable precursors undergo an allylic alkylation and a Heck coupling in sequence, affording polycondensed pyrrolidone derivatives. Depending on the starting precursors, intra/inter or doubly intramolecular processes can be obtained. The allylic alkylation process takes place always very smoothly. On the other hand, the Heck coupling turns out to be rather difficult either when the process is intermolecular, or when an intramolecular process generates polycondensed structures featuring three fused bonds connected to a common carbon atom. In such difficult cases, use of the Herrmann-Beller phosphapalladacycle allowed to catalyze the coupling. This study demonstrates also that allylic alkylations can be catalyzed by the Herrmann-Beller phosphapalladacycle.