SURFACE METALLIZATION OF CENOSPHERES AND PRECIPITATORS BY ELECTROLESS PLATING

This paper reports the use of a colloidal Pd^0 catalysis system to metallize the surface of precipitators separated from coal fly-ash, and metals such as Cu, Ni etc. are deposited on the precipitators surface. Alternatively, according to the characteristic surface of cenospheres, an Ag coating catalysis system is adopted to first deposit Ag on the cenospheres surface, followed, if necessary, by the deposition of other metals such as Cu, Ni, etc. on the Ag coating to produce monolayer and multilayer metal-coated cenospheres. The surface characteristics and the morphologies of the metal coatings are examined in detail with scanning electron microscopy (SEM), energy dispersive spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) techniques. It can be shown that the quality of metal coatings derived from the Aa coatina catalysis system, is better than that of the colloidal Pd^0 catalysis system.     

Tetradecanol dehydrogenation over CuO catalyst supported on BaO, CaO and MgO

Bimetallic Cu/Mg, Ca, Ba mixed oxide compounds acted as catalyst in the dehydrogenation of tetradecanol into tetradecanal, and were characterized by thermal gravimetric analysis, surface area, X-ray diffraction, temperature-programmed reduction and desorption of CO₂. Alkaline earth oxides increased the total basic site concentration in the order of Mg>Ca>Ba. A correlation was found between the total basic site concentration and initial dehydrogenation rate. This revised version was published online in June 2006 with corrections to the Cover Date.     

注入控制铜蒸气激光方向性时间过程测量

实验研究了注入控制对铜蒸气激光非稳腔输出光束质量的影响，从输出光发散角时间分辨过程的测量结果说明注入加速被注入腔内激光发散角的减小过程。由于被注入腔内放大自发辐射的存在，为得到较好的注入控制效果，注入光的脉宽和进入被注入腔的延时必须恰当。     

Novel platinum-containing initiators for ring-opening polymerizations

A novel class of platinum-based initiating systems for the ring-opening polymerization of a wide variety of heterocyclic compounds including epoxides, oxetanes, and 1,3,5-trioxane have been discovered. In addition to a platinum complex as a catalyst, a cocatalyst, consisting of a compound or polymer containing silicon-hydrogen bonds must also be present. This article reports on a preliminary survey of the scope and limitations of these new initiator systems. Particular emphasis in this article has been placed on the ring-opening polymerization of epoxides which have been studied in some detail and which proceed rapidly and exothermically at room temperature. A number of mechanistic studies have been conducted and the best current evidence suggests that polymerization proceeds by a cationic mechanism. Evidence is also presented which suggests that platinum metal colloids may function as the active initiating species.     

Metal complexation of crosslinked polyacrylamide-supported dithiocarbamates: Effect of the molecular character and extent of crosslinking on complexation

Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali. The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions. The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)> Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions.     

A density functional theory computational study of the role of ligand on the stability of CuI and CuII species associated with ATRP and SET‐LRP

Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with Cu^I and trigonal bipyramidal with axial halide complexes with [Cu^IIX]⁺ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [Cu^IIX]⁺ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [Cu^IIX]⁺ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007     

二氯和邻菲罗啉二酮的镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)配合物的合成与表征

以ＭＣｌ２和配体Ｌ（Ｌ＝１，１０－菲罗啉－５，６－二酮）为原料，合成了标题配合物ＭＬＣｌ２，Ｍ＝ＮｉⅡ，ＣｕⅡ，ＺｎⅡ，并经元素分析、热谱、ＩＲ和摩尔电导表征．三者均为四配位的电中性配合物，热稳定性高于５００Ｋ，易溶于ＤＭＦ、ＤＭＳＯ和吡啶，可溶于乙腈和水．它们在ＤＭＦ中于３５０ｎｍ和３１５ｎｍ附近显示出强的Ｍ－Ｌ荷移跃迁