Simple preparation method of multilayer polymer films containing Pd nanoparticles

A simple route to the fabrication of multilayer films containing Pd nanoparticles is described. Following layer-by-layer assembly of PdCl42- and polycation, QPVP-Os (a quaternized poly(4-vinylpyridine) complexed with [Os(bpy)(2)Cl](2+/+)), on 4-aminobenzoic acid-modified glassy carbon electrodes, the three-dimensional Pd nanoparticle multilayer films are directly formed on electrode surfaces via electrochemical reduction of PdCl42- sandwiched between polymers. The growth of PdCl42- is easy on electrode surfaces by electrostatic interaction, and the assembly processes are monitored by cyclic voltammetry and UV-vis spectroscopy. The depth profile analyses by X-ray photoelectron spectroscopy verify the constant composition of the Pd nanoparticle multilayer films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 3-7 mn. The resulting Pd nanoparticle multilayer-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen and oxidation of hydrazine compounds in aqueous solution.

Effect of FePc structure on the activity in the oxidation of cyclohexene catalyzed by pd (OAc)(2)/HQ/FePc

In an acidic aqueous solution of acetonitrile, the catalytic activity of the catalysts consisted of Pd(OAc)(2)/hydroquinone(HQ) with iron phthalocyanine (FePc) from various sources was obviously different in the oxidation of cyclohexene to cyclohexanone, The analysis of the FePc using IR spectroscopy, Mossbauer spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), scanning electron microscopy(SEM) and BET surface area measurement indicated that the catalytic activity of the multicomponent catalytic system composed of iron phthalocyanines depends on the amount of mu -oxo FePc, the crystallinity and the surface structure of iron phthalocyanine.

FePc结构对Pd(OAc)_2/HQ/FePc催化环己烯氧化活性的影响

在乙腈酸性水溶液中 ,不同来源酞菁铁 (FePc)和 Pd(OAc)2/HQ（氢醌）组成的催化体系在环己烯氧化反应中有明显不同的催化活性 .通过 IR、 M ssbauer、 XPS、 XRD、 SEM、 BET等技术对酞菁铁的分析表明 ,由酞菁铁组成的多组份催化体系的催化活性与酞菁铁中的μ-氧酞菁铁含量、酞菁铁结晶度和表面形态有关.

Spectroscopic study of the photophysical properties of rare earth ions encapsulated: Water soluble functional calixresorcin[4]arene

A novel macrocyclic compound-water soluble functional calixresorcin[4]arenes-tetra para sulfo-phenylmethyl-calixresorcin[4]are was synthesized for the first time. The photophysical properties of terbium and europium ions encapsulated in the macrocyclic ligand were studied in detail. The triplet state energy of the calixresorcin[4]arene was determined to be 24400 cm(-1) by the low temperature phosphorescence spectrum and it was found that it can sensitize both terbium ion and europium ion. The possible energy transfer process between the functional calixresorcin[4]arene and the encapsulated Tb3+ and Eu3+ was discussed. The luminescence quantum efficiency of Tb3+- calixresorcin[4]arene was calculated.

Pd/C催化剂在处理NO反应中的催化行为

研究了不同活性炭负载的Pd催化剂在NO＋CO反应中和单独处理NO时的催化行为．结果表明，Pd的引入可大大提高催化活性，且活性与Pd含量呈顺变关系．不同的载体对催化剂活性有很大影响．在NO＋CO反应中，由煤质炭为载体制得的催化剂活性很高，在低于550K时NO即可达到100%转化，而在单独NO时，由山桃核炭制得的催化剂有较高的活性，在低于650K时NO可达到100%转化．催化剂活性的差异与活性炭表面性质有关．当反应体系中有还原物质CO存在时，活性炭作为载体，Pd在其上的分散对活性有重要影响；当体系中没有还原物质时，活性炭作为还原剂参与反应，这时活性炭本身的性质变得十分重要.

Pd(OAc)_2/HQ/FePc、Pd(OAc)_2/FePc 催化烯烃氧化合成酮的研究

考察了在乙腈酸性水溶液中Ｐｄ（ＯＡｃ）２／氢醌（ＨＱ）／酞青铁（ＦｅＰｃ）和Ｐｄ（ＯＡｃ）２／ＦｅＰｃ对环己烯、环戊烯、苯乙烯、正癸烯氧化合成相应酮的催化活性．实验结果表明，两类催化体系对环戊烯的酮基化均呈现出较高的催化活性，环戊酮收率可达９８％．在其它烯烃的氧化反应中，三元催化体系Ｐｄ（ＯＡｃ）２／ＨＱ／ＦｅＰｃ的催化活性高于二元的Ｐｄ（ＯＡｃ）２／ＦｅＰｃ．这表明，在Ｗａｃｋｅｒ类催化体系中，电子传递体的作用是很重要的．对催化体系中各组分的作用进行了讨论，并给出了可能的催化作用机理.

Pd(OAc)_2/FePc催化环己烯氧化合成环己酮的研究

考察了几种Ｆｅ大环配合物与Ｐｄ（ＯＡｃ）２组成的双组分催化体系，在乙腈酸性水溶液中环己烯氧化合成环己酮的催化活性．实验结果表明，其中以酞菁铁（ＦｅＰｃ）与Ｐｄ（ＯＡｃ）２组成的催化体系活性最高，而ＦｅＴＰＰＣｌ与Ｐｄ（ＯＡｃ）２催化体系，虽然催化活性较高，但催化剂的稳定性较低．各种因素对Ｐｄ（ＯＡｃ）２／ＦｅＰｃ催化活性影响的研究结果指出，在无水和酸存在的非水溶液中，Ｐｄ（ＯＡｃ）２／ＦｅＰｃ对环己烯氧化未显现出任何催化活性．认为在乙腈酸性水溶液中，Ｐｄ（ＯＡｃ）２／ＦｅＰｃ催化环己烯氧化合成环己酮的作用机理与Ｗａｃｋｅｒ催化剂的作用机理相似，ＦｅＰｃ是起再生作用的催化剂.

Pd(Ⅱ)/BQ催化环己烯氧化合成环己酮的反应机理

在乙腈的酸性水溶液中，考察了Pd（OAc）2、Pd（NO3）2、PdCl2和苯醌（BQ）组成的催化体系在环己烯氧化合成环己酮反应中的催化活性，探索了酸度对Pd（OAC）2／BQ催化活性的影响．结果表明，Pd（OAc）2／BQ和Pd（NO3）2／BQ对环乙烯氧化合成环己酮显示了较高的催化活性，而PdCl2／BQ的活性则较低，无水和无酸存在的溶液中，Pd（OAc）2／BQ对环己烯氧化未显现任何催化活性．并用紫外可见光谱（UV－Vis）、循环伏安法考察了该催化体系的作用机理

Pd（OAc）_2／HQ／FePc催化环己烯氧化合成环己酮反应机理

在醋酸钯［Ｐｄ（ＯＡｃ）_２］／氢醌（ＨＱ）／酞菁铁（ＦｅＰｃ）催化环己烯氧化合成环己酮反应中，应用ＸＰＳ、ＵＶ－Ｖｉｓ、ＩＲ和循环伏安法考察了催化剂各组分在反应前后存在状态，以及Ｐｄ（ＯＡｃ）２、Ｐｄ（ＯＡｃ）２／ＢＱ（苯醌）对环己烯的作用，ＦｅＰｃ对ＨＱ的催化氧化。讨论了Ｐｄ（ＯＡｃ）２／ＨＱ／ＦｅＰｃ催化环己烯氧化合成环己酮的作用机理。