The mechanism studies of ethanol oxidation on PdO catalysts by TPSR techniques

The paper studies the direct oxidation of ethanol and CO on PdO/Ce0.75Zr0.25O2 and Ce(0.75)Zr(0.2)5O(2) catalysts. Characterization of catalysts is carried out by temperature-programmed desorption (TPD), temperature-programmed surface reaction (TPSR) techniques to correlate with catalytic properties and the effect of supports on PdO. The simple Ce0.75Zr0.25O2 is in less active for ethanol and CO oxidation. After loaded with PdO, the catalytic activity enhances effectively. Combined the ethanol and CO oxidation activity with CO-TPD and ethanol-TPSR profiles, we can find the more intensive of CO2 desorption peaks, the higher it is for the oxidation of CO and ethanol. Conversion versus yield plot shows the acetaldehyde is the primary product, the secondary products are acetic acid, ethyl acetate and ethylene, and the final product is CO2. A simplified reaction scheme (not surface mechanism) is suggested that ethanol is first oxidized to form intermediate of acetaldehyde, then acetic acid, ethyl acetate and ethylene formed going with the formation of acetaldehyde, acetic acid, ethyl acetate; finally these byproducts are further oxidized to produce CO2. PdO/Ce0.75Zr0.25O2 catalyst has much higher catalytic activity not only for the oxidation of ethanol but also for CO oxidation. Thus the CO poison effect on PdO/Ce0.75Zr0.25O2 catalysts can be decreased and they have the feasibility for application in direct alcohol fuel cell (DAFC) with high efficiency.

Photo-sensitized oxidation in natural water via .OH radicals

A method is presented for determining production and consumption rates of .OH radicals produced photochemically in natural surface waters. It is based on the determination of the kinetics by which the concentration of a specified trace compound decreases during irradiation. In samples from Lake Greifensee (Switzerland) low production rates for .OH limit its possible effects. In addition, fast consumptions by the natural dissolved organic solutes and by the bicarbonate protect organic micropollutants from oxidation by .OH. Neither direct nor indirect H2O2 photolysis was a significant source of .OH in the lakewater studied lacking iron, whereas nitrate photolysis could have been a source. Comparison with reaction kinetic formulations allows generalizations for other types of waters.

Macroporous Pt modified glassy carbon electrode: preparation and electrocatalytic activity for methanol oxidation

Three-dimensional (3D) macroporous Pt (MPPt) with highly open porous walls has been successfully synthesized using the hydrogen bubble dynamic template synthesis and galvanic replacement reaction. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and electrochemical methods were adopted to characterize their structures and properties.

Platinum-coated gold nanoporous film surface: Electrodeposition and enhanced electrocatalytic activity for methanol oxidation

This report describes the preparation of Pt-nanoparticle-coated gold-nanoporous film (PGNF) on a gold substrate via a simple "green" approach. The gold electrode that has been anodized under a high potential of 5 V is reduced by freshly prepared ascorbic acid (AA) solution to obtain gold nanoporous film electrode. Then the Pt nanoparticle is grown on the electrode by cyclic voltammetry (CV).

A new oxidation state of aniline pentamer observed in water-soluble electroactive oligoaniline-chitosan polymer

A novel water-soluble electroactive polymer, aniline pentamer crosslinked chitosan (Pentamer-c-Chi), was prepared by condensation polymerization of the terminal carboxyl groups in aniline pentamer with the amino side groups in chitosan in aqueous solution. The carboxyl groups were activated by N-hydroxysuccinimide (NHS) and N,N'-dicyclohexylcarbodiimide (I)CC). The electrochemical behavior of aniline pentamer in this kind of crosslinked polymer was studied in acidic aqueous solution by means of cyclic voltammetry (CV), UV-vis, and electron spin resonance (ESR) spectroscopy.

Electrostatic layer-by-layer a of platinum-loaded multiwall carbon nanotube multilayer: A tunable catalyst film for anodic methanol oxidation

A simple layer-by-layer (LBL) electrostatic adsorption technique was developed for deposition of films composed of alternating layers of positively charged poly(diallyldimethylammonium chloride) (PDDA) and negatively charged multiwall carbon nanotubes bearing platinum nanoparticles (Pt-CNTs). PDDA/Pt-CNT film structure and morphology up to six layers were characterized by scanning electron microscopy and ultraviolet-visible spectroscopy, showing the Pt-CNT layers to be porous and uniformly deposited within the multilayer films.

Effect of diffusion barrier on the high-temperature oxidation behavior of thermal barrier coatings

A selective oxidation technique has been applied to form a diffusion barrier on the Ni-based superalloy substrate by heating the substrate with electron beam of the electron beam-physical vapor deposition (EB-PVD) facility. The interdiffusion behavior, cross-sectional morphology, isothermal and cyclic oxidations were studied for thermal barrier coatings (TBCs) with and without diffusion barrier.

Platinum-macrocycle co-catalysts for electro-oxidation of formic acid

In this paper, it was found that the electrocatalytic activity of a Pt electrode for the electro-oxidation of formic acid could be dramatically enhanced with the modification of macrocycle compounds, such as iron-tetrasulfophthalocyanine (FeTSPc). The electro-oxidation of formic acid on a modified Pt electrode with FeTSPc occurs mainly through a direct pathway. A series of macrocycle compounds were also investigated as modifiers and exhibited a promotion effect similar to the Pt electrode.

The mechanism of formic acid electro oxidation on iron tetrasulfophthalocyanine-modified platinum electrode

The mechanism of formic acid electrooxidation on iron tetrasulfophthalocyanine (FeTSPc) modified Pt electrode was investigated with electrochemical methods. It was found that a "third-body" effect of FeTSPc on Pt electrode predominates during the electrooxidation process based on unusual electrochemical results. The modification leads formic acid electrooxidation to take place through a desired direct pathway, in which the mechanism is proposed to be the gradual dehydrogenation of formic acid and the reaction of formate with hydroxyl species.

Preparation of Pd/C catalyst for formic acid oxidation using a novel colloid method

A novel colloid method using (WO3)(n)center dot xH(2)O as colloidal source was developed to prepare Pd/C catalyst for formic acid oxidation. Transmission electron microscopy image shows that the Pd/C nanoparticles have an average size of 3.3 nm and a narrow size distribution. Electrochemical measurements indicate that the Pd/C catalyst exhibits significantly high electrochemical active surface area and high catalytic activity with good stability for formic acid oxidation compared with that prepared by common method.

Highly active PtRu catalysts supported on carbon nanotubes prepared by modified impregnation method for methanol electro-oxidation

A simple and rapid synthesis method (denoted as modified impregnation method, MI) for PtRu/CNTs (MI) and PtRu/C (MI) was presented. PtRu/CNTs (MI) and PtRu/C (MI) catalysts were characterized by transmission electron microscopy (TEM) and X-ray diffractometry. It was shown that Pt-Ru particles with small average size (2.7 nm) were uniformly dispersed on carbon supports (carbon nanotubes and carbon black) and displayed the characteristic diffraction peaks of Pt face-centered cubic structure.

Synthesis of Pd/C catalysts with designed lattice constants for the electro-oxidation of formic acid

Pd/C catalysts with designed lattice constants were synthesized for the electro-oxidation of formic acid. By changing the solvents in the preparation procedure, it was demonstrated that the different lattice constants of Pd crystallites could be controlled as desired. The varied lattice constants may be attributed to the difference in the interactions between solvents and PdCl2. it was found that the lattice constant had an obvious effect on the electro-catalytic performance of Pd.