Kinetic study on the photo-catalytic degradation of pyridine in TiO2 suspension systems

It has been generally agreed that pyridine can be effectively mineralized in aerated TiO2 slurries using near-UV irradiation. The knowledge on the kinetics of the system possesses both practical and theoretical values. The present study, on the base of Langmuir-Hinshewood mechanism, illustrates a pseudo first-order kinetic model of the degradation with the limiting rate constant of 3.004 mg l(-1) min(-1) and equilibrium adsorption constant 2.763 x 10(-2) l mg(-1), respectively. The degradation efficiency in alkali is a little higher than that in acid with a minimum at about pH = 5, which is explained by the formation of acid-pyridine in acidic surrounding together with the amphoteric nature of the TiO2 surface. The promotion of H2O2 on the photo-degradation ties in its supplying proper amount of (OH)-O-. radicals for the inducement stage before surface redox reactions. (C) 2004 Elsevier B.V. All rights reserved.

Preparation of highly active Pt/C cathode electrocatalysts for DMFCs by an improved aqueous impregnation method

An improved aqueous impregnation method was used to prepare 40 wt% Pt/C electrocatalysts. TEM analysis of the samples showed that the Pt particles impregnated for a short time have a very narrow size distribution in the range of 1-4 nm with an average size of 2.6 nm. UV-vis spectroscopy measurements verified that the redox reaction between PtCl62- and formaldehyde took place with a slow rate at ambient temperature via a two-step reaction path, where PtCl42- serves as an intermediate. The use of the short-time-impregnated 40 wt% Pt/C as cathode electrocatalysts in direct methanol fuel cells yields better performance than that of commercial 40 wt% Pt/C electrocatalyst. Experimental evidence provides clues for the fundamental understanding of elementary steps of the redox reactions, which helps in guiding the design and preparation of highly dispersed Pt catalyst for fuel cells.

Determination of peptides and amino acids from wool and beer with sensitive fluorescent reagent 2-(9-carbazole)-ethyl chloroformate by reverse phase high-performance liquid chromotography and liquid chromotography mass spectrometry

A new method for the sensitive determination of amino acids and peptides using the tagging reagent 2-(9-carbazole)-ethyl chloroformate (CEOC) with fluorescence (FL) detection has been developed. Identification of derivatives was carried out by liquid chromotography mass spectrometry. The chromophore in the 2-(9-fluorenyl)-ethyl chloroformate (FMOC) reagent was replaced by carbazole, which resulted in a sensitive fluorescence lerivatizing agent CEOC. CEOC can easily and quickly label peptides and amino acids. Derivatives are stable enough to be efficiently analyzed by high-performance liquid chromatography. Studies on derivatization demonstrate excellent derivative yields over the pH range 8.8-10.0. Maximal yields close to 100% are observed with three- to fourfold molar reagent excess. Derivatives exhibit strong fluorescence and allow direct injection of the reaction mixture with no significant disturbance from the major fluorescent reagent degradation by-products, such as 2(9-carbazole)-ethanol and bis-(2-(9-carbazole)-ethyl) carbonate. In addition, the detection responses for CEOC derivatives are compared to those obtained with FMOC. The ratios AC(CEOC)/AC(FMOC) = 1.00-1.82 for fluorescence (FL) response and AC'(CEOC)/AC'(FMOC) = 1.00-1.21 for ultraviolet (UV) response are observed (here, AC and AC' are, respectively, FL and UV F response). Separation of the derivatized peptides and amino acids has been optimized on a Hypersil BDS C18 column. Excellent linear responses are observed. This method was used successfully to analyze protein hydrolysates from wool and from direct-derivatized beer. (C) 2003 Elsevier Science (USA). All rights reserved.

Iron and inorganic carbon in Liaodong Gulf sediments of Bohai Sea in China

Iron in seawater is an essential trace metal for phytoplankton that plays an important role in the marine carbon cycle. But most studies focused on oceanic iron fertilization in high nutrient low chlorophyll (HNLC) seawaters. A study of inorganic carbon (IC) forms and its influencing factors was presented in Liaodong Gulf sediments, and especially the influence of iron was discussed in detail. Inorganic carbon in Liaodong Gulf sediments was divided into five forms: NaCl, NH3·H2O, NaOH, NH2OH·HCl and HCl. The concentration of NaCl and NaOH forms were similar and they only occupied the minority of total inorganic carbon (TIC). However, NH3·H2O, NH2OH·HCl and HCl forms were the principal forms of TIC and accounted for more than 80% of TIC. Especially, the percentage of NH3·H2O form was much higher than that in the Changjiang River Estuary and Jiaozhou Bay sediments. All forms of inorganic carbon were influenced by organic carbon,pore water, iron, pH, redox potential(Eh) and sulfur potential(Es) in sediments, moreover, the influences had different characteristics for different IC forms. However, the redox reactions of iron affected mainly active IC forms. Iron had little effect on NH2OH·HCl and HCl forms of IC which were influenced mainly by pH. Iron had a stronger influence on NaCl, NaOH and NH3·H2O forms of IC; the influence of Fe2+ was higher than Fe3+ and its effect on NH3·H2O form was stronger than on NaCl and NaOH forms.

Tetrahydrothiophenium-based ionic liquids for high efficiency dye-sensitized solar cells

Binary melts of S-ethyltetrahydrothiophenium iodide and dicyanoamide (or tricyanomethide) have been employed for dye-sensitized solar cells with high power conversion efficiencies up to 6.9% under the illumination of AM 1.5G full sunlight. We have further shown that the transport of triiodide in ionic liquids with high iodide concentration is viscosity-dependent in terms of a physical diffusion coupled bond exchange mechanism apart from the simple physical diffusion.

Dye-sensitized solar cells with solvent-free ionic liquid electrolytes

We systematically studied the temperature-dependent physicochemical properties, such as density, conductivity, and fluidity, of 1,3-dialkylimidazolium iodides. In combination with the amphiphilic Z907Na sensitizer, we have found that it is important to use low-viscosity iodide melts with small cations to achieve high-efficiency dye-sensitized solar cells. By employing high-fluidity eutectic-based melts the device efficiencies considerably increased compared to those for cells with the corresponding state of the art ionic liquid electrolytes.

Electrochemical surface plasmon resonance detection of enzymatic reaction in bilayer lipid

In this paper, electrochemical surface plasmon resonance (SPR) method was first used to detect enzymatic reaction in bilayer lipid membrane (BLM) based on immobilizing horseradish peroxidase (HRP) in the BLMs supported by the redox polyaniline (PAn) film. By SPR kinetic curve in situ monitoring the redox transformation of PAn film resulted from the reaction between HRP and PAn, the enzymatic reaction of HRP with H2O2, was successfully analyzed by electrochemical SPR spectroscopy.

Electrochemical characteristics of mediated laccase-catalysis and electrochemical detection of environmental pollutants

Laccase has been immobilized on the carbon nanotubes modified glassy carbon electrode surface by adsorption. As-prepared laccase retains good electrocatalytic activity to oxygen reduction by using 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) as the mediator. It can be used as a biosensor for the determination of catechol with broad linear range.

Bis(2,2 '-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10] phenanthroline)ruthenium: Synthesis and electrochemical and electrochemiluminescence characterization

In this work, an electrochemiluminescence (ECL) reagent bis(2,2'-bipyridine)(5,6-epoxy-5,6-dihydro-[1,10]phenanthroline)ruthenium complex (Ru-1) was synthesized, and its electrochemical and ECL properties were characterized. The synthesis of Ru-1 was confirmed by IR spectra, element analysis, and H-1 NMR spectra. For further study, its UV-vis absorption and fluorescence emission spectra were investigated. Ru-1 also exhibited quasi-reversible Ru-II/Ru-III redox waves in acetonitrile solution. The aqueous ECL behaviors of Ru-1 were also studied in the absence and in the presence of tripropylamine.

Effects of divalent metal ions on electrochemiluminescence sensor with Ru(bPY)(3)(2+) immobilized in Eastman-AQ membrane

Different effects of divalent metal ions on electrochemiluminescence (ECL) sensor with Ru(bPY)(3)(2+) immobilized in Eastman-AQ membrane were investigated. Mg2+,Ca2+ and Fe2+ can elevate the ECL of Ru(bpY)(3)(2+)/proline; while metal ions that underwent redox reactions on the electrode such as Mn2+ and Co2+ presented intensive quenching effects on Ru(bpy)(3)(2+) ECL. Also, the quenching effect of Mn2+ on the ECL sensor with Ru(bpY)(3)(2+) immobilized in Eastman-AQ membrane enhanced to about 30-folds compared with the case that Ru(bpy)(3)(2+) was dissolved in phosphate buffer, and the enhanced quenching effects of Mn2+ were studied.

Direct electrochemistry of horseradish peroxidase immobilized in calcium carbonate microsphere doped with phospholipids

Protein electrochemistry affords a direct method to study the biological electron transfer processes. However, supplying a biocompatible environment to maintain the native state of protein is all-important and challengeable. Here, we chose vaterite, one of the crystalline polymorphs of calcium carbonate, with highly porous nature and large specific surface area, which was doped with phospholipids, as the matrix to immobilize horseradish peroxidase (HRP). The integrity of HRP was kept during the simple immobilization procedure. By virtue of this organic/inorganic complex matrix, the direct electrochemistry of HRP was realized, and the activity of HRP for catalyzing reduction of O-2 and H2O2 was preserved.

The electrochemical behavior of a system with a limited number of molecules

In this paper, based on Einstein relationship between diffusion and random walk, the electrochemical behavior of a system with a limited number of molecules was simulated and explored theoretically. The transition of the current vs time responses from discrete to continuous was clearly obtained as the number of redox molecules increased from 10 to 10(6).

Amperometric glucose biosensor based on single-walled carbon nanohorns

The biosensing application of single-walled carbon nanohorns (SWCNHs) was demonstrated through fabrication of an amperometric glucose biosensor. The biosensor was constructed by encapsulating glucose oxidase in the Nafion-SWCNHs composite film. The cyclic voltammograms for glucose oxidase immobilized on the composite film displayed a pair of well-defined and nearly symmetric redox peaks with a formal potential of -0.453V. The biosensor had good electrocatalytic activity toward oxidation of glucose.

Fabrication and electrochemical characterization of electrostatic assembly of polyelectrolyte-functionalized ionic liquid and Prussian blue ultrathin films

Polyelectrolyte-functionalized ionic liquid (PFIL) and Prussian blue (PB) nanoparticles were used to fabricate ultrathin films on the ITO substrate through electrostatic layer-by-layer assembly method. Multilayer growth was examined by UV-vis spectroscopy and cyclic voltammetry. The resulting ITO/(PFIL/PB)n electrode showed two couples of well-defined redox peaks and good electrocatalytical activity towards the reduction of hydrogen peroxide.

Hydrogen peroxide biosensor based on direct electrochemistry of soybean Peroxidase immobilized on single-walled carbon nanohorn modified electrode

Single-walled carbon nanohorns (SWCNHs) were used as a novel and biocompatible matrix for fabricating biosensing devices. The direct immobilization of acid-stable and thermostable soybean peroxidase (SBP) on SWCNH modified electrode surface can realize the direct electrochemistry of enzyme. Cyclic voltammogram of the adsorbed SBP displays a pair of redox peaks with a formal potential of -0.24V in pH 5 phosphate buffer solution.