Low-temperature oxidation of CO over Pd/CeO2-TiO2 catalysts with different pretreatments

A comprehensive study of the low-temperature oxidation of CO was conducted over Pd/TiO2, Pd/CeO2, and Pd/CeO2-TiO2 pretreated by a series of calcination and reduction processes. The catalysts were characterized by N-2 adsorption, XRD, H-2 chemisorption, and diffuse-reflectance infrared Fourier transform spectroscopy. The results indicated that Pd/CeO2-TiO2 has the highest activity among these catalysts, whether in the calcined state or in the reduced state. The activity of all of the catalysts can be improved significantly by the pre-reduction, and it seems that the reduction at low temperature (LTR. 150 degrees C) is more effective than that at high temperature (HTR, 500 degrees C), especially for Pd/CeO2 and Pd/TiO2. The catalysts with various supports and pretreatments are also different in the reaction mechanisms for CO oxidation at low temperature. Over Pd/TiO2, the reaction may proceed through a surface reaction between the weakly adsorbed CO and oxygen (Langmuir-Hinshelwood). For Ce-containing catalysts, however, an alteration of reaction mechanism with temperature and the involvement of the oxygen activation at different sites were observed, and the light-off profiles of the calcined Pd/CeO2 and Pd/CeOi-TiO2 show a distortion before CO conversion achieves 100%. At low temperature, CO oxidation proceeds mainly via the reaction between the adsorbed CO on Pd-0 sites and the lattice oxygen of surface CeO2 at the Pd-Ce interface, whereas at high temperature it proceeds via the reaction between the adsorbed CO and oxygen. The high activity of Pd/CeO2-TiO2 for the low-temperature CO oxidation was probably due to the enhancements of both CO activation, caused by the facilitated reduction of Pd2+ to Pd-0, and oxygen activation, through the improvement of the surface oxygen supply and the oxygen vacancies formation. The reduction pretreatment enhances metal-support interactions and oxygen vacancy formation and hence improves the activity of CO oxidation. (c) 2005 Elsevier Inc. All rights reserved.

Electrode catalysts behavior during direct ethanol fuel cell life-time test

In the present paper, a 60 h life-time test of a direct ethanol fuel cell (DEFC) at a current density of 20 mA cm(-2) (the beginning 38 h) and 40 mA cm(-2) (the last 22 h) was carried out. After the life-time test, the MEA could not achieve the former performance. X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray analysis (EDX) were employed to characterize the anode and cathode catalyst before and after the life-time test. The XRD and TEM results showed that the particle size of the anode catalyst increased from 2.3 to 3.3 nm and the cathode from 3.0 to 4.6 nm. The EDX results of PtSn/C anode catalysts before and after the life-time test indicated that the content of the oxygen and tin, especially the content of the platinum, decreased prominently after the life-time test. The results suggest that the agglomeration of electrocatalysts, the destruction of the anode catalyst together with the fuel/water crossover from anode to cathode concurrently contribute to the performance degradation of the DEFC. (C) 2005 Elsevier B.V. All rights reserved.

Improved procedure for preparation of covalently bonded cellulose tris-phenylcarbamate chiral stationary phases

The classical method for preparation of covalently boned cellulose derivative chiral stationary phases (CSP) with diisocyanate as spacer was improved. Diisocyanate was firstly allowed to react with 3-aminopropyltriethoxysilane, and the resulting product was then applied as the spacer reagent to immobilize cellulose derivatives onto silica gel. Influences of the amount and the length of the spacer on the optical resolution ability of the CSP were investigated. Comparing improved procedure to classical diisocyanate method, the cross-linking between the glucose units of the cellulose derivatives was avoided to the most extent. With the improved procedure, regio-nonselective ways could be adopted to prepare covalently bonded CSP, which showed an advantage for the rapid preparation.

Urinary nucleosides as biological markers for patients with colorectal cancer

AIM: Fourteen urinary nucleosides, primary degradation products of tRNA, were evaluated to know the potential as biological markers for patients with colorectal cancer.

Comparison of comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry and gas chromatography-mass spectrometry for the analysis of tobacco essential oils

A sample of tobacco essential oil was analyzed using gas chromatography-mass spectrometry (GUMS)and comprehensive two-dimensional gas chromatography coupled to a time-of-flight mass spectrometry (GC x GC/TOFMS), respectively. In the GUMS analysis, serially coupled columns were used. By comparing the GUMS results with GC x GC/TOFMS result,,, many more components in the essential oil could be found within the two-dimensional separation space of GC x GC. The quantitative determination of components in the essential oil was performed by GC x GC with flame ionization detection (FID), using a method of multiple internal standards calibration, (c) 2005 Elsevier B.V. All rights reserved.

Synthesis of tamarixetin and isorhamnetin 3-O-neohesperidoside

Two isomeric flavonol 3-O-glycosides, tamarixetin and isorhamnetin 3-O-neohesperido side (1 and 2), were synthesized. The natural product from Costus spicatus assigned as the former compound is revised to the latter structure. (c) 2005 Elsevier Ltd. All rights reserved.

On the correlation between microstructural changes of Ag-H-ZSM-5 catalysts and their catalytic performances in the selective catalytic reduction of NOx by methane

The silver catalyzed, selective catalytic reduction (SCR) of nitrogen oxides (NOx) by CH4, is shown to be a structure-sensitive reaction. Pretreatment has a great affect on the catalytic performances. Upon thermal treatment in inert gas stream, thermal induced changes in silver morphology lead to the formation of reduced silver species of clusters and particles. Catalysis over this catalyst indicates an initially higher activity but lower selectivity for the CH4-SCR of NOx Reaction induced restructuring of silver results in the formation of ill-defined silver oxides. This, in turn, impacts the adsorption properties and diffusivity of oxygen over silver catalyst, results in the decrease in activity but increase in selectivity of Ag-H-ZSM-5 catalyst for the CH4-SCR of NO.. (c) 2004 Elsevier B.V. All rights reserved.

Cluster-assisted multiple ionization of xenon and krypton by a nanosecond laser

Multicharged xenon and krypton ions with charge states up to Xe11+ and Kr11+ have been observed in laser ionization of a pulsed xenon or krypton beam by a 25 ns Nd-YAG laser with laser intensity of 10(10)-10(11) W cm(-2) at 532 nm. There is strong evidence to support that those multicharged ions come from cluster-assisted electron recolliding ionizations inside the cluster after multiphoton ionization of atoms in the cluster, the electron can gain its kinetic energy by inverse bremsstrahlung absorption from a laser field quickly.

Purification and characterization of recombinant truncated human interleukin-11 expressed as fusion protein in Escherichia coli

Mature human interleukin-11 (HuIL-11) is a cytokine consisting of 178 amino acid residues that results from scission of the N-terminal signal peptide, consisting of 21 amino acid residaues, from the corresponding nascent polypeptide. A DNA fragment encoding a truncated HuIL-11 (trHuIL-11), with an additional 5 amino acid residues removed from the N-terminus, was cloned into vector pGEX-2T between the BamHI site and the EcoRI site. Upon transformation with Escherichia coli BL21, the construct over-produced a glutathione S-transferase (GST)-fused protein in a soluble form after IPTG induction. The fusion protein was initially fractionated with butyl-Sepharose 4 fast flow column and by affinity chromatography using a GSH-Sepharose 4B column. On-site enzymatic release with thrombin gave the target protein at 96% purity as judged by SDS-PAGE and HPLC. Expression of the interleukin as a GST-fused protein thus greatly improved downstream processing. Subsequent biological activity assay suggested that trHuIL-11 had similar activity profile to the naturally produced sample and may be a promising candidate for further development as biopharmaceutical.

Franck-Condon simulation of the photoelectron spectrum of SO2- including Duschinsky effects

A theoretical method to calculate multidimensional Franck-Condon factors including Duschinsky effects is described and used to simulate the photoelectron spectrum of the anion SO. Geometry optimizations and harmonic vibrational frequency calculations have been performed on the XA(1) state of SO2 and (XB1)-B-2 state of SO2. Franck-Condon analyses and spectral simulation were carried out on the first photoelectron band of SO2. The theoretical spectra obtained by employing CCSD(T)/6-31 I+G(2d,p) values are in excellent agreement with the experiment. In addition, the equilibrium geometric parameters, r(c)(OS) = 0.1508 +/- 0.0005 nm and theta(e)(O-S-0) = 113.5 +/- 0.5 degrees, of the (XB1)-B-2 state of SO2, are derived by employing an iterative Franck-Condon analysis procedure in the spectral simulation. (c) 2005 Elsevier B.V. All rights reserved.