Electrochemical reactors for NO decomposition. Basic aspects and a future

The electrochemical reduction of nitric oxide in the presence of the excess oxygen was reviewed. It was shown that the selectivity and activity of the cathodes is strongly dependent on the composition and on the microstructure of the cathode material. A concept of electrochemical reactor with multilayer electro-catalytic electrode was proposed and successfully designed in Advanced Manufacturing Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), Nagoya, Japan. The typical values of current efficiency in such electrochemical reactors are of the order of 10–20% at gas composition: 1,000 ppm NO and 2% O₂ balanced in He and at gas flow rate 50 ml/min. The value of current efficiency depends on the functional multi-layer electrode composition, structure, and operating temperature. Such electrochemical reactors show the value of NO/O₂ selectivity (ν _sel) higher than 5 (ν _sel > 5) at intermediate temperature and up to ν _sel = 25 at low temperature operation. It was shown that multilayer electro-catalytic electrode should consist at list from three main functional layers: cathode, electro-catalytic electrode, covering layer, in order to operate as an electrode with high selectivity.     

Complexed sol-gel synthesis of improved Pt-Ru-Os-based anode electro-catalysts for direct methanol fuel cells

A high specific surface area (SSA) Pt-Ru-Os-based anode catalyst synthesized by a novel complexed sol-gel (CSG) process shows better catalytic activity in comparison to pure equi-atomic compositions of Pt-Ru anode catalysts synthesized by similar sol-gel processes. A homogeneous amorphous gel was successfully synthesized by complexing platinum(II) acetylacetonate, ruthenium(III) acetylacetonate and osmium(III) chloride with tetramethylammonium hydroxide (TMAH) used as a complexing agent. Phase-pure Pt(Ru,Os) and Pt(Ru) solid solutions possessing high specific surface area (∼110-120 m²/g) were successfully synthesized by controlled removal of carbonaceous species present in the as-prepared precursor generated from the CSG process. This has been successfully achieved by precise thermal treatments of the precursor using controlled oxidizing atmospheres. Results indicate that the nano-crystalline Pt(Ru,Os) solid solution of nominal composition 50 at%-Pt-40 at% Ru-10 at% Os possesses good chemical homogeneity, and reveals excellent catalytic activity, thus demonstrating the potential of the novel CSG process for synthesizing high-performance Pt-Ru-Os-based catalysts for direct methanol fuel cells.     

Selective surface chemistry of allyl alcohol and allyl aldehyde on Si(1 0 0)2×1: Competition of [2 + 2] CC cycloaddition with O-H dissociation and with [2 + 2] CO cycloaddition in bifunctional molecules

Competition between the CC functional group with the OH group in allyl alcohol and with the CO group in allyl aldehyde in the adsorption and thermal chemistry on Si(1 0 0)2×1 has been studied by X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption (TPD), as well as density-functional theory (DFT) calculations. The similarities found in the C 1s and O 1s spectra for both molecules indicate that the O-H dissociation product for allyl alcohol and [2 + 2] CO cycloaddition product for allyl aldehyde are preferred over the corresponding [2 + 2] CC cycloaddition products. Temperature-dependent XPS and TPD studies further show that thermal evolution of these molecules gives rise to the formation of ethylene, acetylene, and propene on Si(1 0 0)2×1, with additional CO evolution only from allyl alcohol. The formation of these desorption products also supports that the [2 + 2] CC cycloaddition reaction does not occur. In addition, the formation of SiC at 1090 K is observed for both allyl alcohol and allyl aldehyde. We propose plausible surface-mediated reaction pathways for the formation of these thermal evolution products. The present work illustrates the crucial role of the Si(1 0 0)2×1 surface in selective reactions of the Si dimers with the O−H group in allyl alcohol and with the CO group in allyl aldehyde over the CC functional group common to both molecules.     

Stripping voltammetry of Pb and Cu using a microcantilever electrode

Microfabricated silicon microcantilevers coated with gold on one side have been used as working electrode in a three-electrode electrochemical arrangement. In addition to electrochemical current, cantilever bending has been used as a signal for monitoring electrode reactions on the cantilever surface. The microcantilever bending was measured by an optical beam deflection method as the surface potential was scanned and electrochemical reactions occurred on the surface. The microcantilever bending due to differential surface stress was used to sense Pb and Cu using cyclic voltammetry (CV) and linear sweep stripping voltammetry (LSSV).     

Spin-peierls transition in dimerized stacks of anion-radical salt (N-Me-2,5-di-Me-Pz)(TCNQ)2, (Pz is pyrazine)

An anion-radical salt (ARS) (N-Me-2,5-di-Me-Pz)(TCNQ)₂, where Pz is pyrazine, was synthesized and its crystal structure was resolved. X-ray diffraction experiments on single crystals were performed. Heat capacity was measured in the temperature range from 2 to 300 K. Magnetisation and magnetic susceptibility were measured in the temperature range from 2 to 300 K and the low-temperature part was measured in magnetic fields from 5 mT to 5 T. The experimental results were explained in terms of dimerized Heisenberg spin chain model. Numerical calculations were performed and compared with experimental data.     

Improvement of corrosion resistance of AA6061 alloy by tapioca starch in seawater

This study examines the use of tapioca starch for improvement of corrosion resistance of AA6061 alloy in seawater. Gravimetric, potentiodynamic polarization, linear polarization resistance and electrochemical impedance measurements were employed to study the corrosion behavior of AA6061 alloy in seawater. The electrochemical measurements for AA6061 alloy in seawater showed that the presence of tapioca starch significantly decreases the corrosion rates, corrosion current densities (i_corr), and double layer capacitance (C_dl), simultaneously increases the values of polarization resistance (R_p). The inhibition efficiencies increase with increasing of tapioca starch concentration. The Langmuir adsorption isotherm fits well with the experimental data. The nature of adsorption of tapioca starch on the metal surface has also been examined. The analysis of SEM and EDS confirmed the formation of precipitates of tapioca starch on the metal surface, which reduced the overall corrosion reaction.     

Enhanced gas-sensing behaviour of Ru-doped SnO2 surface: A periodic density functional approach

A theoretical study on Ru-doped rutile SnO₂(1 1 0) surface has been carried out by means of periodic density functional theory (DFT) at generalized gradient approximation (GGA-RPBE) level with a periodic supercell approach. Electronic structure analysis was performed based on the band structure and partial density of states. The results provide evidence that the electronic structures of SnO₂(1 1 0) surface are modified by the surface Ru dopant, in which Ru 4d orbital are located at the edge of the band gap region. It is demonstrated that molecular oxygen adsorption characteristics on stoichiometric SnO₂(1 1 0) surface are changed from endothermic to exothermic due to the existence of surface Ru dopant. The dissociative adsorption of molecular oxygen on the Ru_5c/SnO₂(1 1 0) surface is exothermic, which indicates that Ru could act as an active site to increase the oxygen atom species on SnO₂(1 1 0) surface. Our present study reveals that the Ru dopant on surface is playing both electronic and chemical role in promoting the SnO₂ gas-sensing property.     

Energy dependence of electron mobility in metallic nanowires

We study the electron drift mobility in a metallic nanowire (at low temperature) as a function of both electron energy and electrochemical potential from considerations relative to energy-dependent conductance and carrier spatial density. In fact, a mathematical expression for the electron mobility, when electronic energy equals Fermi energy (resonant states), valid for negative values of the electrochemical potential is derived.     

Corrosion behavior of Nd9.4Pr0.6Febal.Co6B6Ga0.5TixCx (x=0, 1.5, 3, 6) nanocomposites annealed melt-spun ribbons

The effect of Ti and C additions on the corrosion behavior of Nd_9.4Pr_0.6Fe_bal.Co₆B₆Ga_0.5Ti_xC_x (x=0, 1.5, 3, 6) isotropic nanocomposite melt-spun ribbons in 3.5 wt% sodium chloride solution was studied. The melt-spun ribbons were annealed at 750 °C for 10 min in argon-filled quartz capsules. The microstructure of multiphase nanocrystalline samples and corrosion products was characterized using the X-ray diffraction and electron microscopy techniques. The electrochemical behavior was assessed using potentiodynamic polarization and electrochemical impedance spectroscopy. The results show that the addition of Ti and C increases the corrosion resistance of NdFeB ribbons; the best corrosion resistance was obtained for 1.5 wt% Ti and C content.     

A Monte Carlo study of the thermodynamic properties of a quasi-one-dimensional organic polymer ferromagnet

The thermodynamic properties of a quasi-one-dimensional organic ferromagnet at different temperatures and in different applied magnetic fields have been investigated by means of the Heisenberg model combined with the Monte Carlo method. The results indicate that a peak in the magnetic susceptibility is obtained at low temperatures. Furthermore, the effect of dimerization on the magnetic properties has also been studied. We find that the dimerization suppresses the magnetization in this model. The ferromagnetic couplings between the side-free radicals stabilize the ferromagnetism and increase the apparent Curie temperature.