Surface-appropriate lipophobicity - Application in isobutene oligomerization over Teflon-modified silica-supported 12-silicotungstic acid

A series of silica-supported 12-silicotungstic acid catalysts (H4SiW12O40, abbreviated as HSiW), modified with various loadings of Teflon (HSiW/SiO2-Teflon), were prepared by an impregnation method. The surface properties of the catalysts were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), BET, infrared (IR) spectroscopy, NH3-TPD and the Drop Shape Analysis (DSA). SEM results combined with energy-dispersive X-ray (EDX) measurements of HSiW/SiO2-Teflon revealed that F-compound (Teflon) is effectively coated on the catalyst surface. The contact angles for water and oil of 50 wt% HSiW/SiO2 and HSiW/SiO2-Teflon indicate that HSiW/SiO2-Teflon catalyst enhances not only the surface hydrophobicity but also the surface lipophobicity by means of the addition of Teflon. Silica-supported 12-silicotungstic acid modified with Teflon exhibits higher C-8(=) selectivity and longer lifetime than that of silica-supported 12-silicotungstic acid in isobutene oligomerization. Thus, surface-appropriate lipophobicity of catalysts may be effective for decreasing the interaction between coke precursors and the catalyst surface and for removing deposited coke more easily.

Concentration and time dependant behavior of chlorpromazine interaction with supported bilayer lipid membrane

The interaction of chlorpromazine (CPZ) with supported bilaver lipid (dipalmitoyphosphatidylcholine) membrane (s-BLM) on the glassy carbon electrode (GCE) was investigated using cyclic voltammetry and ac impedance spectroscopy. The experimental data, based on the voltammetric response of Ru(NH3)(6)(3+) associated with the oxidation of CPZ on the electrode, indicated that the interaction of CPZ with s-BLM was concentration and time dependant. The interaction between them could be divided into three stages by the concentration of CPZ: low, middle and high concentration. At the first stage, s-BLM was not affected by CPZ and the interaction was only a penetration of a small quantity of CPZ molecule into s-BLM. At the second stage, the defects formed in s-BLM due to the penetration of more CPZ molecule into s-BLM. At the last stage, a high CPZ:lipid ratio reached in s-BLM, resulting in the solubilization of s-BLM. The interaction time had different effect at three stages.

Study on charge transfer reactions at multilayers of polyoxometalates clusters and poly(allylamine hydrochloride) (Grotthuss-018)

Multilayers of anionic phosphotungstic acid (PTA) clusters and positively charged protonated poly(allylamine hydrochloride) (PAH) were assembled by layer-by-layer self-assembled method on Au electrode modified by 3-mercaptopropionic acid (3-MPA). The effect of the charge of the surface of the multilayer assembly on the kinetics of the charge transfer reaction was studied by using the redox probes [Fe(CN)(6)](3-)/(4-) [Ru(NH3)(6)](2+/3+). The cyclic voltammetry experiments showed that the peak currents and peak-to-peak potential differences changed after assembling different layers on the electrode surface indicating that the charge of the surface has a significant effect on the kinetics of the studied charge transfer reactions. These reactions were studied in more detail by electrochemical impedance spectroscopy. When [Fe(CN)(6)](3-/-) was used as the redox label, multilayers that terminated with negatively charged PTA showed a high charge transfer resistance but multilayers that terminated with positively charged PAH showed lower charge transfer resistance. With [Ru(NH3)(6)](2+/3+) as the redox label, the charge transfer resistance at multilayers that terminated with positively charged PAH was much higher than at the multilayer terminated by the negatively charged PTA.

Interaction of K7Fe3+P2W17O62H2 with supported bilayer lipid membranes on platinum electrode

The influence of K7Fe3+P2W17O62H2 on l-alpha-phosphatidylcholine/cholesterol bilayer lipid membrane on Pt electrode was studied by voltammetry and AC impedance spectroscopy. The interaction of the polyoxometalates with the BLM can promote the access of Ru(NH3)(6)(3+) and [Fe(CN)(6)](3-/4-) to the electrode surface. It was found that some kind of pores had been formed on the BLM by AFM. The phenomenon is attributed to the interaction of K7Fe3+P2W17O62H2 with phosphatidylcholine phosphate groups located in its outer leaflet. Experimental results are helpful to understand the biological activity of the polyoxometalates in vivo.

Ring-opening polymerization of epsilon-caprolactone and L-lactide using organic amino calcium catalyst

Poly (6-caprolactone) (PCL) and poly (L-lactide) (PLA) were prepared by ring-opening Polymerization catalyzed by organic amino calcium catalysts (Ca/PO and Ca/EO) which were prepared by reacting calcium ammoniate Ca(NH3)(6) with propylene oxide and ethylene oxide, respectively. The catalysts exhibited high activity and the ring-opening polymerization behaved a quasi-living characteristic. Based on the Fr-IR spectra and the calcium contents of the catalysts, and based on the H-1 NMR end-group analysis of the low molecular weight PCL prepared using catalysts Ca/PO and Ca/EO, it was proposed that the catalysts have the structure of NH2-Ca-O-CH(CH3)(2) and NH2-CaO-CH2CH3 for Ca/PO and Ca/EO, respectively. The ring-opening polymerization of CL and LA follows a coordination-insertion mechanism and the active site is the Ca-O bond.

低甲醇透过直接甲醇燃料电池

直接甲醇燃料电池(DMFC)是一种清洁能源,具有高效、安全、无污染等优点[1～3],因此受到广泛关注。目前,在DMFC中广泛使用Nafion膜作为电解质膜,但甲醇透过Nafion膜后,不但氧阴极处产生混合电位,引起阴极催化剂中毒,导致阴极极化增加,电池性能降低,而且透过的甲醇未经反应从电池中排出,既浪费燃料又污染环境。甲醇透过Nafion膜是阻碍Nafion膜型直接甲醇燃料电池应用的主要技术问题之一[4,5]。为解决Nafion膜的甲醇透过问题,Pu等[6] 将一层致密的不透甲醇的质子导体夹在 2层Nafion膜之间形成复合电解质膜来消除甲醇透过。但是由于不同层之间的结合和膜厚度的增加,会使电解质膜的导质子性能降低。Won等[7] 和Yoon等[8] 采用刻蚀溅射法在Nafion膜表面修饰一层金属钯来降低甲醇透过,但该方法存在钯和Nafion膜表面结合不牢固和钯的用量相对较大等缺点。本文首次报道采用化学镀钯修饰Nafion膜的方法来降低甲醇透过率。Pd(NH3 )4 Cl2 和NaBH4均为上海试剂一厂产品 ,其它试剂均为分析纯。所有的溶液均用三次蒸馏水配制。

Alternating LB film of ferric oxide nanoparticles-copper phthalocyanine derivative and its gas sensitivity

Nanoparticulate ferric oxide - tris - (2,4-di-t-amylphenoxy) - (8-quinolinolyl) copper phthalocyanine Langmuir-Blodgett Z-type multilayers were obtained by using monodisperse nanoparticle ferric oxide hydrosol as the subphase. XPS data reveal that the nanoparticle ferric oxide exist as alpha -Fe2O3 phase in the films. Transition electron microscopic (TEM) image of the alternating monolayer shows that the film was highly covered by the copper phthalocyanine derivative and the nanoparticles were arranged rather closely. IR and visible spectra all give the results that the nanoparticles were deposited onto the substrate with the copper phthalocyanine derivative. The gas-sensing measurements show that the alternating LB film had very fast response-recovery characteristic to 2 ppm C2H5OH gas, and also sensitive to larger than 200 ppm NH3.

Gas sensitivity of composite Langmuir-Blodgett films of Fe2O3 nanoparticle-copper phthalocyanine

The Langmuir-Blodgett (LB) composite films, ferric oxide nanoparticle composite with tris-(2,3-di-t-amylphenoxy)-(8-quinolinolinolyl) copper phthalocyanine (CuPcA(2)), were obtained by capped type and alternated type and characterized by X-ray photoelectron spectroscopy (XPS) and visible spectra. The gas sensitivity of the composite films and the pure ferric oxide and pure CuPcA(2) LB films to ammonia and ethanol were measured at room temperature. The composite films could be used as the C2H5OH sensors in the range of 2-8 or 100-200 ppm. The XPS data suggested that the adduct complex NH3-CuPcA(2) was formed after the capped film was exposed to the detected gas of ammonia. (C) 2000 Elsevier Science B.V. All rights reserved.

Grafting of diaminoalkane on glassy carbon surface and its functionalization

Diaminoalkanes (NH2(CH2)(n)NH2, n = 7,10,12) were grafted onto a glassy carbon electrode (GCE) surface by amino cation radical formed during electrooxidation of amino group. The presence of diamine grafted layer at the GCE is demonstrated by X-ray photoelectron spectroscopy. The effect of the grafted layer at the GCE surface on the redox responses of Ru(NH3)(6)(3+) and Fe(CN)(6)(3-) redox probes has been investigated. Electrochemical impedance experiments indicate that the kinetics of electron transfer are slowed down when the scan rate taken to modify the GCE is low, and that diaminoalkane with longer alkyl-chain used has higher blocking characteristics. The amine-functionalized GCE is versatile not only to further covalently immobilize ferrocene acetic acid via carbodiimide coupling, but also as a charge-rich substrate to successfully adsorb heteropolyanion P2W18 in acidic solution by electrostatic interaction. (C) 2000 Elsevier Science S.A. All rights reserved.

WO_3/ZrO_2固体强酸催化剂上异丁烷/丁烯的烷基化反应Ⅱ.过渡金属的助催化作用

制备了一系列用过渡金属M (M =Pt,Co ,Ni,Mn ,Fe,Cu)活化的WO3 /ZrO2 固体强酸催化剂 ,用XRD ,DTA TG ,H2 TPR ,NH3 TPD等测定了其晶型结构、表面状态和酸量 .结果表明 ,各样品中的ZrO2 主要以T晶相存在 ,但T晶相ZrO2 所占的比例因过渡金属不同而异 ,比表面积比WO3 /ZrO2 稍有下降 ;金属Pt的引入使呈单层分散的WO3 的表面状态发生了改变 .研究了异丁烷 /丁烯烷基化反应 ,其反应活性与酸量的测定结果有对应关系 ;与WO3 /ZrO2 相比 ,M WO3 /ZrO2 上的丁烯转化率均稍有下降 ,但具有更高的i C08选择性 .从反应机理分析了添加过渡金属无显著效果的原因.

WO_3/ZrO_2固体强酸催化剂上异丁烷-丁烯烷基化反应的研究Ⅲ.超细ZrO_2载体对催化剂性能的影响

制备了以超细 Zr O2 为载体的 WO3/ Zr O2 、 SO42 - / Zr O2 、 Mo O3/ Zr O2 固体强酸催化剂 ,并用 XRD、 DTA-TG、 H2 - TPR、 NH3- TPD等方法表征了其晶型结构、表面状态和酸性 .结果表明 ,超细 Zr O2 及其催化剂均主要以 T-晶相存在 ,与通常以 Zr(OH) 4为载体制备的同类催化剂相比 ,Zr O2 中的 T-晶相所占比例虽有所下降 ,但具有更大的比表面积、酸强度和对金属氧化物的负载能力 ,且酸强度随焙烧温度升高而增强 ,表明其表面状态亦有较大变化 .研究了以超细 Zr O2 为载体的固体强酸催化剂上 ,异丁烷 -丁烯的烷基化反应 ,与通常以 Zr(OH) 4为载体制得的催化剂相比 ,其具有更好的烯烃转化率 ,在烷基化产物中 ,C5 ～ C7裂解产物较多 ,使 C80的选择性有所下降

异丁烷-丁烯烷基化反应催化剂的研究Ⅳ.Zr(SO_4)_2和Zr(SO_4)_2/Al_2O_3(SiO_2)

制备了一系列不同焙烧温度的 Zr(SO4) 2 及 Zr(SO4) 2 负载量不同的 Zr(SO4) 2 / Al2 O3(Si O2 )固体强酸催化剂 ,用 XRD、IR、BET、TG- DTA、NH3- TPD、Hamm ett指示剂等方法研究了该催化体系的晶型、结构、比表面、酸量及酸强度随负载量和焙烧温度的变化规律 .将 Zr(SO4) 2 负载在 Al2 O3和 Si O2 两种载体上呈现不同的特性 .在 Al2 O3上明显地延缓了 Zr(SO4) 2 的分解和 Zr O2的晶相转变 .并且使酸量和酸强度有所提高 .研究了异丁烷 -丁烯烷基化反应 ,结果表明 ,对 973和 10 2 3K焙烧的 Zr(SO4) 2 样品 ,活性最好 ,而对 Zr(SO4) 2 / Al2 O3,负载量在 m(Zr(SO4) 2 ) /m(Al2 O3) =0 .5 / 1.0左右时活性最好 .各种样品均具有较高的 C08选择性.

Fabrication of nanometer-sized electrodes and tips for scanning electrochemical microscopy

A novel method for fabrication of nanometer-sized electrodes and tips suitable for scanning electrochemical microscopy (SECM) is reported. A fine etched Pt wire is coated with polyimide, which was produced by polymerization on the Pt surface initiated by heat. This method can prepare electrodes with effective radii varying from a few to hundreds of nanometers. Scanning electron microscopy, cyclic voltammetry, and SECM were used to characterize these electrodes. Well-defined steady-state voltammograms could be obtained in aqueous or in 1,2-dichloroethane solutions. Ibis method produced the nanoelectrodes with exposed Pit on the apex, and they can also be employed as the nanotips for SECM investigations. Different sizes of Pt nanotips made by this method were employed to evaluate the kinetics of the redox reaction of Ru(NH3)6(3+) on the surface of a large Pt electrode by SECM, and the standard rate constant kappa (o) of this system was calculated from the best fit of the SECM approach curve. This result is similar to the values obtained by analysis of the obtained voltammetric data.

Multilayer assemblies of tungstodiphosphate anions on 1,7-diaminoheptane modified glassy carbon electrode and the electrocatalytic reduction to iodate

1,7-Diaminoheptane (DAH) had been covalently grafted on glassy carbon electrode by amino cation radical formation, which resulted in a stable cationic monolayer under proper pH conditions. Dawson-type tungstodiphosphate anion, P2W18O626- and small molecule, Ru(NH3)(6)(3+) were alternately assembled on the DAH modified electrode through layer-by-layer electrostatic interaction. Thus-prepared multilayer film had been characterized by cyclic voltammetry and X-ray photoelectron spectroscopy. The P2W18O626- multilayers exhibit high electrocatalytic response and sensitivity towards the reduction of iodate. With the increase of the number of P2W18O626- the catalytic current was enhanced and the catalytic potential shifted positively. Iodate in table salt was determined at the modified electrode containing three layers of P2W18O626- with satisfactory results. The multilayer electrode is promising as an electrochemical sensor for the detection of trace iodate.

Investigation of the model compounds at 4-aminobenzoic acid modified glassy carbon electrode by scanning electrochemical microscopy

In this paper, we studied the reactions of both potassium ferricyanide and hexaammineruthenium(III) chloride at a 4-aminobenzoic acid (4-ABA) modified glassy carbon electrode (GCE) by scanning electrochemical microscopy (SECM) in different pH solutions. The surface of the modified electrode has carboxyl groups, the dissociation of which are strongly dependent upon the solution pH values. The rate constant kb of the oxidation of ferrocyanide on the modified electrode can be obtained by fitting the experimental tip current-distance (I-T-d) curves with the theoretical values. The surface pK(a) of the 4-ABA modified GCE was estimated from the plot of standard rate constant k(o) versus the solution pH and is equal to 3.2, which is in good agreement with the reported result. The SECM approach curves for Ru(NH3)(6)(3+) both on the bare and the modified electrodes show similar diffusion control processes. These results can be explained by the electrostatic interactions between the modified electrode surface and the model compounds with different charges. (C) 2001 Elsevier Science BN. All rights reserved.