Construction of sensitive and selective zirconia-based CO sensors using ZnCr2O(4)-based sensing electrodes

The carbon monoxide (CO) sensitivity of a mixed-potential-type yttria-stabilized zirconia (YSZ)-based tubular-type sensor utilizing a ZnCr(2)O(4) sensing electrode (SE) was tuned by the addition of different precious metal nanoparticles (Ag, Au, Ir, Pd, Pt, Ru and Rh; 1 wt % each) into the sensing layer. After measuring the electromotive force (emf) response of the fabricated SEs to 100 ppm of CO against a Pt/air-reference electrode (RE), the ZnCr(2)O(4)-Au nanoparticle composite electrode (ZnCr(2)O(4)(+Au)-SE) was found to give the highest response to CO. A linear dependence on the logarithm of CO concentration in the range of 20-800 ppm at an operational temperature of 550 °C under humid conditions (5 vol % water vapor) was observed. From the characterization of the ZnCr(2)O(4)(+Au)-SE, we can conclude that the engineered high response toward CO originated from the specific properties of submicrometer sized Au particles, formed via the coalescence of nanosized Au particles located on ZnCr(2)O(4) grains, during the calcining process at 1100 °C for 2 h. These particles augmented the catalytic activities of the gas-phase CO oxidation reaction in the SE layer, as well as to the anodic reaction of CO at the interface; while suppressing the cathodic reaction of O(2) at the interface. In addition, the response of the ZnCr(2)O(4)(+Au)-SE sensor toward 100 ppm of CO gradually increased throughout the 10 days of operation, and plateaued for the remainder of the month that the sensor was examined. Correlations between SEM observations and the CO sensing characteristics of the present sensor were suggestive that the sensitivity was mostly affected by the morphology of the Au particles and their catalytic activities, which were in close proximity to the ZnCr(2)O(4) grains. Furthermore, by measuring the potential difference (emf) between the ZnCr(2)O(4)(+Au) and a ZnCr(2)O(4) electrode, sensitivities to typical exhaust component gases other than CO were found to be negligible at 550 °C.     

Amperometric determination of choline with enzyme immobilized in a hybrid mesoporous membrane

Choline sensor is successfully prepared by using immobilized enzyme, i.e., choline oxidase (ChOx) within a hybrid mesoporous membrane with 12 nm pore diameter (F127M). The measurement was based on the detection of hydrogen peroxide, which is the co-product of the enzymatic choline oxidation. The determination range and the response time are 5.0-800 μM and approximately 2 min, respectively. The sensor is very stable compared to the native enzyme sensor and 85% of the initial response was maintained even after storage for 80 days. These results indicate that ChOx is successfully immobilized and well stabilized, and at the same time, enzyme reaction proceeds efficiently. Such ability of hybrid mesoporous membrane F127M suggests great promise for effective immobilization of enzyme useful for electrochemical biosensors.     

The β‐silicon effect. 4: substituent effects on the solvolysis of 1‐alkyl‐2‐(aryldimethylsilyl)ethyl trifluoroacetates

Solvolysis rates of 2‐(aryldimethylsilyl)‐1‐methylethyl and 2‐(aryldimethylsilyl)‐1‐tert‐butylethyl trifluoroacetates were determined conductimetrically in 60% (v/v) aqueous ethanol. The effects of aryl substituents at the silicon atom on the solvolysis rates at 50 °C were correlated with parameters of r⁺ = 0.15 with the Yukawa–Tsuno equation, giving ρ values of ?1.5 for both secondary α‐Me and α‐tert‐Bu systems. The ρ values for those secondary systems are less negative than ?1.75 for the 2‐(aryldimethylsilyl)ethyl system that proceeds by the Eaborn (non‐vertical) mechanism, while they are distinctly more negative than ?0.99 for 2‐(aryldimethylsilyl)‐1‐phenylethyl system that should proceed by the Lambert (vertical) mechanism. There was a fairly linear relationship between the reaction constants (ρ) for the β‐silyl substituent effects and the solvolysis reactivities for a series of β‐silyl substrates. The solvolyses of the α‐Me and tert‐Bu substrates proceed through the transition state (TS) with an appreciable degree of the β‐silyl participation, close to the Eaborn (non‐vertical) TS rather than to the Lambert (vertical) TS. Copyright © 2010 John Wiley & Sons, Ltd.     

Unsteady PTV velocity field past an airfoil solved with DNS: Part 2. Validation and application at Reynolds numbers up to <Emphasis Type="Italic">Re</Emphasis> ≤ 10<Superscript>4</Superscript>

Hybrid unsteady-flow simulation combining particle tracking velocimetry (PTV) and direct numerical simulation (DNS) is introduced in the series of two papers. Particle velocities on a laser-light sheet acquired with time-resolved PTV in a water tunnel are supplied to two-dimensional DNS with time intervals corresponding to the frame rate of the PTV. Hybrid velocity fields then approach those representing the PTV data in the course of time, and the reconstructed velocity fields satisfy the governing equations with the resolution comparable to numerical simulation. In part 2, by extending the capabilities of the hybrid simulation to higher Reynolds numbers, we simulate flows past the NACA0012 airfoil over ranges of Reynolds numbers (Re ≤ 10⁴) and angles of attack (−5° ≤ α ≤ 20°) and validate the proposed technique by comparing with experimental results in terms of the lift and drag coefficients. We also compare the results with unsteady Reynolds-averaged Navier–Stokes (URANS) simulation in two-dimensions and show the advantages of the hybrid simulation against two-dimensional URANS.     

A Novel Layered Silicate with a Helical Morphology

Helices composed of stacked layers are present in the novel silicate obtained from a silica sol and NaOH by hydrothermal synthesis in the presence of tetramethylammonium (TMA) hydroxide and 1,4-dioxane. The helical morphology is evident in scanning electron micrographs (see picture). The TMA and sodium ions of the silicate are readily replaced by protons, and on heating to 200°C a reversible phase transition occurs in which water molecules are lost from between the layers.     

Preparation of Titania Containing Mixed Oxides and Their Catalytic Activities

Titania containing catalysts were prepared by conventional procedures (coprecipitation, hydrogel kneading and titania precipitation) and a complexing-agent assisted sol-gel method. The effect of preparation methods on their properties and catalytic activities in the oxidation of olefins and decomposition of cumene hydroperoxide were examined. The sol-gel method gave the best dispersion of titania. In contrast, with the kneading and titania precipitation method, titania formed crystalline particles. The sol-gel catalysts are more effective for epoxydation of olefins because of the high dispersibility of Ti in them. However, the most active catalysts in the decomposition of cumene hydroperoxide are kneading ones.     

Molecular Weight Development in Free‐Radical Polymerization with Polyfunctional Chain‐Transfer Agents, 1. Equal Reactivity Model

The analytic expression for the weight‐average molecular weight development in free‐radical polymerization that involves a polyfunctional chain‐transfer agent is proposed. Free‐radical polymerization is kinetically controlled; therefore, the probability of chain connection with a polyfunctional chain‐transfer agent as well as the primary chain‐length distribution changes during the course of polymerization. We consider the primary chains formed at different times as different types of chains, and the heterochain branching model is used to obtain the weight‐average chain length at a given conversion level in a matrix formula, described as P_w = W { D _w + ( I + T ) SP ( I – TSP )^–1 D_f }. Because the primary chains are formed consecutively, the number of chain types N is extrapolated to infinity, but such extrapolation can be conducted with the calculated values for only three different N values. The criterion for the onset of gelation is simply described as a point at which the largest eigenvalue of the product of matrixes, TSP reaches unity, i. e., det  ( I – TSP ) = 0. The present model can readily be extended for the star‐shaped polyfunctional initiators, and the relationships between the model parameters and kinetic rate expression for such reaction systems are also shown.