基于吲哚类半花菁染料的钯比率荧光探针

利用6-羟基萘-2-醛和碘化N-乙基-2,3,3-三甲基-3H-吲哚啉季铵盐的缩合反应生成的羟基半花菁染料2与氯甲酸烯丙酯的反应合成了荧光比率型钯探针1.研究表明:在含水介质中,探针1对钯(Pd0和Pd2+)显示出很高的敏感性、选择性和抗干扰性,其荧光比率增强大约72倍,对Pd2+的最低检测极限为0.23μmol/L.探针1对钯的作用机理是钯催化碳酸烯丙酯断裂导致比率荧光变化.     

负载型钯催化剂完全氧化性能的研究

研究了以含有稀土的Ｆｅ－Ｃｒ－Ａｌ合金为载体的铂催化剂的制备及其催化燃烧性能。实验表明：在苯蒸汽浓度为３２４０ｍｇ／ｍ３，空速为３００００／ｈ的催化燃烧实验条件下，经特殊工艺制得的最优催化剂，在９００℃高温下于空气中的烧后，完全燃烧温度为２４０℃，取得了令人满意的结果，同时，提出了催化剂制备的最优方案，并对其催化活性机理进行了初步探讨。     

Preparation of a tubular palladium membrane by photocatalytic deposition

A novel photocatalytic deposition method for the preparation of a thin tubular palladium membrane is presented in this paper. The membrane is prepared on a porous asymmetric TiO₂ support by photocatalytic reaction of palladium ion, followed by electroless plating. Gas permeation results show that the membrane exhibits increased hydrogen permeance with the increase of temperature. The hydrogen permeance and selectivity to nitrogen at 773 K are about 1.43×l0⁻⁶ mol m⁻² s⁻¹ Pa⁻¹ and 17, respectively, when the pressure in the feed side is 0.1 MPa. The activation energy of hydrogen permeation is 11.06 kJ/mol at the temperature range of 573–773 K.     

Oscillatory behaviour during the oxidation of methane over palladium metal catalysts

Oscillatory reactions over palladium foil and wire catalysts during the oxidation of methane have been investigated over a wide range of reaction temperatures and argon/methane/oxygen feed gas compositions. Characterisation of the catalyst has also been carried out using scanning electron microscopy (SEM) techniques, which revealed the presence of a porous surface. This suggested that the metal surface has undergone a change since the reaction commenced, and using X-ray powder diffraction (XRD) techniques the palladium phase was shown to be the dominant phase present. Hysteresis phenomena were observed in the activity of the reaction as the temperature was cycled up and down, showing that the metal surface was continually changing throughout the reaction. The activation energies of the reaction during the high reactivity mode, PdO, and low reactivity mode, Pd, were also calculated. Oscillation rates were observed to depend on the dominant surface. Oscillations were frequent when the high reactivity mode was dominant while the activation energy of this mode was found to be low. When the low reactivity mode was dominant, the oscillations were slower and the activation energy was three times larger. The results obtained imply that the behaviour of the palladium surface, switching back and forth from the reduced state to the oxidised state, is responsible for the oscillatory behaviour seen in this system.     

Hydrogen diffusivity enhancement in alumina pellets due to impregnated palladium

Single-pellet moment technique was used for the evaluation of effective diffusivities and adsorption equilibrium constants of hydrogen, carbon dioxide, and helium in pure alumina and palladium-impregnated alumina pellets. It was found that hydrogen was strongly adsorbed on palladium of Pd-alumina pellets, and significant enhancement of hydrogen diffusivity was observed due to impregnated palladium at 40°C. On the other hand, for carbon dioxide and helium, effective diffusivities obtained in Pd-alumina pellets were smaller than the corresponding values in pure alumina due to higher tortuosity factor values of Pd-alumina pellets.     

Direct Transesterification/Isomerization/Methoxycarbonylation of Various Plant Oils

A selection of plant oils was catalytically transferred into 1,19-nonadecanedioate by a direct transesterification, isomerization and methoxycarbonylation under mild conditions using Pd/o-C₆H₄(CH₂P ^t Bu₂)₂. Additionally, sulfuric acid was demonstrated as being able to substitute methane sulfonic acid as co-catalyst without any significant loss of activity and selectivity.     

Selective Hydrogenation of Ethyne in Ethene‐Rich Streams on Palladium Catalysts,Part 2: Steady‐State Kinetics and Effects of Palladium Particle Size,Carbon Monoxide,and Promoters

Developments in the last three decades of kinetics of selective hydrogenation of ethyne in ethene‐rich streams on palladium catalysts are reviewed. Most of the studies can be described comprehensively by a model that assumes carbonaceous deposits (i) create irreversibly on the palladium surface small A types of active site (selective to ethene) and large E types of active site (selective to ethane), and (ii) are involved in hydrogenation of ethene on E _s sites on the support. The relative importance of these sites, with varying (i) reaction conditions, (ii) palladium dispersion, (iii) process modifiers, and (iv) promoters, is discussed.     

First-principles investigation on the segregation of Pd at LaFe1-xPdxO3-y surfaces

First-principles calculations were performed to investigate the effect of Pd concentration and oxygen vacancies on the stability of Pd at LaFeO₃ surfaces. We found a much stronger tendency of Pd to segregate by taking the aggregation of Pd at LaFe_1-xPd_xO_3-y surfaces into consideration, resulting in a pair of Pd-Pd around a vacancy. Moreover, we predicted that one oxygen-vacancy-containing FeO₂-terminated surfaces would be stable at high temperatures by comparing the stability of LaFe_1-xPd_xO_3-y surfaces, which further supports our previous conclusion that a Pd-containing perovskite catalyst should be calcined at 1,073 K or higher temperatures in air to enhance the segregation of Pd in the vicinity of surfaces to rapidly transform the Pd catalyst from oxidized to reduced states on the perovskite support.     

Knowledge and Know‐How in Emission Control for Mobile Applications

Abstract

Concerns about emissions of carbon dioxide have created a need to develop more fuel‐efficient vehicles. Diesel engines are generally more efficient than gasoline engines but improvements in the latter can be achieved by operating under lean‐burn conditions. With both diesel and lean‐burn gasoline engines, the nitrogen oxides are emissted under oxidising conditions. It is scientifically very challenging to reduce nitrogen oxides under oxidising conditions. After a short survey of conventional three‐way catalysts, and the associated fundamental aspects of NO_x reduction under stoichoimetric conditions, this review focuses on the knowledge and know‐how that has been developed for lean engine emission control. Early research on hydrocarbon selective catalytic reduction on zeolite, oxide, and metal‐based systems is examined, and some of the key mechanistic models are described. Since none of these systems are of sufficient activity and stability to satisfy current legislation attention has turned to NO_x storage and reduction systems. The basic principles of these are described, and the present state of knowledge regarding the mechanisms of storage and regeneration are discussed. The many apparent discrepancies are highlighted and an attempt is made to rationalise the current state of knowledge by taking into account the varying experimental conditions reported nit he literature. For diesel engines, NO_x storage and reduction is not an ideal solution and so the final section of this review is concerned with silver‐based catalysts and especially with the dramatic effect of small amounts of hydrogen on the efficiency of these catalysts for hydrocarbons selective catalytic reduction.     

Pd-catalyzed hydrosilylation polymerization of a dihydrosilane with diyne/triyne mixed systems affording crosslinked silylene-divinylene polymers and their properties

Treatment of a dihydrosilane (methylphenylsilane, 1) with mixtures of a diyne (p- or m-diethynylbenzene, 2a or 2b) and a triyne (1,3,5-triethynylbenzene, 3a or B,B′,B″-triethynyl-N,N′,N″-trimethylborazine, 3b; 1:2:3=100:95:5, 100:90:10, 100:80:20) in the presence of Pd-PCy₃ (Cy=cyclohexyl) catalyst gave new crosslinked silylenedivinylene polycarbosilanes. In TGA the resulting crosslinked polymers tended to show higher Td₅ values and higher char yields than the corresponding linear polymers. On the other hand, UV/vis absorption spectra of the crosslinked polymers obtained in the reactions of 2a or 2b with 3a exhibited increased broad peaks around 390 nm for 2a or 360 nm for 2b. Coincidently, their fluorescence spectra showed significant increase of the emission peaks in 400-550 nm. The crosslinked polymer derived from 2a and 3b, however, showed decrease of the absorption peak around 390 nm and profound depression of fluorescence peaks in 400-550 nm.