Transient analysis of the release and reduction of NOx using a Pt/Ba/Al2O3 catalyst

The release and reduction of NO_x in a NO_x storage-reduction (NSR) catalyst were studied with a transient reaction analysis in the millisecond range, which was made possible by the combination of pulsed injection of gases and time resolved time-of-flight mass spectrometry. After an O₂ pulse and a subsequent NO pulse were injected into a pellet of the Pt/Ba/Al₂O₃ catalyst, the time profiles of several gas products, NO, N₂, NH₃ and H₂O, were obtained as a result of the release and reduction of NO_x caused by H₂ injection. Comparing the time profiles in another analysis, which were obtained using a model catalyst consisting of a flat 5 nmPt/Ba(NO₃)₂/cordierite plate, the release and reduction of NO_x on Pt/Ba/Al₂O₃ catalyst that stored NO_x took the following two steps; in the first step NO molecules were released from Ba and in the second step the released NO was reduced into N₂ by H₂ pulse injection. When this H₂ pulse was injected in a large amount, NO was reduced to NH₃ instead of N₂.

A only small amount of H₂O was detected because of the strong affinity for alumina support. We can analyze the NO_x regeneration process to separate two steps of the NO_x release and reduction by a detailed analysis of the time profiles using a two-step reaction model. From the result of the analysis, it is found that the rate constant for NO_x release increased as temperature increase.     

Preparation of avidin-containing polyelectrolyte microcapsules and their uptake and release properties

Avidin-containing polyelectrolyte microcapsules were prepared by a layer-by-layer deposition technique and uptake and release of biotin-labelled fluorescein (b-FITC) was studied. The polyelectrolyte microcapsules were prepared by coating the surface of calcium carbonate (CaCO₃) microparticles containing avidin-poly(styrene sulfonate) (PSS) conjugate, followed by dissolution of CaCO₃ core in an ethylenediaminetetraacetic acid solution. Release of avidin from the microcapsules was markedly suppressed due to formation of a high molecular weight of avidin-PSS conjugate in the microcapsules. The uptake of b-FITC into the microcapsules was highly enhanced through a strong binding of b-FITC to avidin, as compared to the uptake into avidin-free microcapsules. Release of b-FITC from the microcapsules was accelerated upon addition of biotin, 2-iminobiotin, or lipoic acid in the solution due to the competitive binding of the additives to the binding site of avidin.     

Gas-Wall Partitioning of Organic Compounds in a Teflon Film Chamber and Potential Effects on Reaction Product and Aerosol Yield Measurements

Gas-wall partitioning of organic compounds (OC) that included C ₈ –C ₁₆ n-alkanes and 1-alkenes and C ₈ –C ₁₃ 2-alcohols and 2-ketones was investigated in two Teflon FEP chambers whose walls were either untreated, oxidized in sunlight, or previously exposed to secondary organic aerosol (SOA). Partitioning was nearly independent of chamber treatment, reversible, and obeyed Henry's law. The fraction of an OC that partitioned to the walls at equilibrium ranged from 0 to ～ 65%. Values increased with increasing carbon number within an OC class and for OC with similar vapor pressures increased in the order n-alkanes <1-alkenes <2-alcohols <2-ketones. Estimated time constants for achieving partitioning equilibrium ranged from ～ 60 min for n -alkanes to ? 8 min for 2-ketones. The observations are consistent with a sorption mechanism in which OC dissolve into the film but are restricted to the near-surface region by a sharp permeability gradient that develops in response to OC-induced stresses in polymer chains. When the results were analyzed using a model analogous to one commonly employed for gas-particle partitioning, it was estimated that the sorption properties of the chamber walls were equivalent to organic aerosol mass concentrations of 2, 4, 10, and 24 mg m^{– 3} with respect to the partitioning of n -alkanes, 1-alkenes, 2-alcohols, and 2-ketones. These values are up to ～ 4 orders of magnitude larger than concentrations used in most laboratory studies of SOA, which are typically 1–10 ³ μ g m^{– 3} , meaning that if full partitioning equilibrium is established in the chamber then semi-volatile OC will reside overwhelmingly in the chamber walls. Model simulations of gas-particle-wall partitioning were also carried out using the experimental data, and demonstrate quantitatively the large potential effects of Teflon walls on measured yields of gas-phase OC products and SOA.     

An electrochemical ionic liquid membrane reactor for NO x selective separation under excess oxygen conditions

A novel electrochemical ionic liquid membrane reactor capable of separating NO from a mixture of NO and oxygen with high current efficiency at low temperatures was designed and tested. This reactor consists of a combination of an ionic liquid and a thin film of anodised alumina with two platinum electrodes. During operation of the reactor, NO is electrically transported from the cathode side to the anode side.     

A quick and simple method for the identification of meat species and meat products by PCR assay

The polymerase chain reaction (PCR) was applied to identify six meats (cattle, pig, chicken, sheep, goat and horse) as raw materials for products. By mixing seven primers in appropriate ratios, species-specific DNA fragments could be identified by only one multiplex PCR. A forward primer was designed on a conserved DNA sequence in the mitochondrial cytochrome b gene, and reverse primers on species-specific DNA sequences for each species. PCR primers were designed to give different length fragments from the six meats. The products showed species-specific DNA fragments of 157, 227, 274, 331, 398 and 439 bp from goat, chicken, cattle, sheep, pig and horse meats, respectively. Identification is possible by electrophoresis of PCR products. Cattle, pig, chicken, sheep and goat fragments were amplified from cooked meat heated at 100 or 120°C for 30 min, but horse DNA fragments could not be detected from the 120°C sample. Detection limits of the DNA samples were 0.25 ng for all meats.     

Characteristic behavior of aluminum-stainless laminated sheet in redrawing

Using a rigid-plastic finite element program deep drawing, direct and reverse redrawing of two layer aluminum-austenitic stainless steel (AL-ASS) laminated sheets have been simulated. The results of simulations as the variation of drawing ratios with thickness ratio and setting condition are presented. They show that to access the highest drawing ratios in direct and reverse redrawing, thickness ratio should be about 1/3 (one layer aluminum and three layer stainless steel) and the setting conditions are opposite to each other. In another word, while in direct redrawing contact of austenitic stainless steel with punch leads to the maximum drawing ratio, in reverse redrawing, aluminum should contact the punch in order to access highest drawing ratio. An explanation for this finding is offered through the thickness strain distribution.     

Hydrogen production through dry reforming of biogas using a porous electrochemical cell: Effects of a cobalt catalyst in the electrode and mixing of air with biogas

This paper reports the performance of porous Gd-doped ceria (GDC) electrochemical cells with Co metal in both electrodes (cell No. 1) and with Ni metal in the cathode and Co metal in the anode (cell No. 2) for CO₂ decomposition, CH₄ decomposition, and the dry reforming reaction of a biogas with CO₂ gas (CH₄ + CO₂ → 2H₂ + 2CO) or with O₂ gas in air (3CH₄ +?1.875CO₂ +?1.314O₂ → 6H₂ +?4.875CO +?0.7515O₂). GDC cell No. 1 produced H₂ gas at formation rates of 0.055 and 0.33?mL-H₂/(min?m²-electrode) per 1?mL-supplied gas/(min?m²-electrode) at 600?°C and 800?°C, respectively, by the reforming of the biogas with CO₂ gas. Similarly, cell No. 2 produced H₂ gas at formation rates of 0.40?mL-H₂/(min?m²) per 1?mL-supplied gas/(min?m²) at 800?°C from a mixture of biogas and CO₂ gas. The dry reforming of a real biogas with CO₂ or O₂ gas at 800?°C proceeded thermodynamically over the Co or Ni metal catalyst in the cathode of the porous GDC cell. Faraday's law controlled the dry reforming rate of the biogas at 600?°C in cell No. 2. This paper also clarifies the influence of carbon deposition, which originates from CH₄ pyrolysis (CH₄ → C + 2H₂) and disproportionation of CO gas (2CO → C + CO₂), on the cell performance during dry reforming. The dry reforming of a biogas with O₂ molecules from air exhibits high durability because of the oxidation of the deposited carbon by supplied air.     

Preparation method for supported metal catalysts using w/o microemulsion: Study on immobilization conditions of metal particles by hydrolysis of alkoxide

It was previously found that the silica-supported rhodium catalyst prepared using water-in-oil microemulsion had rhodium particles partly, or wholly, embedded in silica. In this work, consequently, we investigated the effect of hydrolysis conditions of tetraethylorthosilicate, employed as the source of silica, on the atomic ratio of surface rhodium in contact with the gas phase, to total surface rhodium of nanoparticles. This ratio is denoted as R in this paper. R became higher when the catalyst was prepared under the following hydrolysis conditions: a shorter hydrolysis time and a smaller amount of tetraethylorthosilicate. On the other hand, R showed the minimum value when the water content in the preparation solution was 33 vol%. From these results, it is demonstrated that it was important to form silica as early as possible in hydrolysis of TEOS in order to increase R values. In addition, the effect of R on the catalytic behavior in CO hydrogenation was investigated. At R values below 30%, the turnover frequencies increased with a decrease in R.     

Photoreaction of Titanium-Based Metal-organic Compounds for Ceramic Fine Patterning

The photoreaction of metal-organic compounds prepared by the chemical modification of metal alkoxides was investigated for the patterning of ceramic films. The chemical stability and photoreactivity of these compounds were found to be greatly influenced by the kind of chemical additive applied during the syntheses of the precursor solutions. In this study, the photoreaction of the precursor thin films prepared by the addition of alkanolamines was achieved by tuning the wavelength of the incident UV light. The decomposition of the organic moieties of the percursors was clearly observed in IR spectra during UV irradiation. Furthermore, the spectrum of the titania precursor film in the visible and ultraviolet regions (UV-vis) changed in accordance with the irradiation time. The photolithography of the titanium precursor pattern was successfully achieved by means of these techniques.