High Throughput Screening of Low Temperature SCR and SCD De-NOx Catalysts in Scanning Mass Spectrometer

High-throughput synthesis and screening methods have been developed for the discovery of highly active lead compounds for the selective catalytic reduction as well as direct decomposition of NO in the temperature range 200–300 °C. The discovery libraries for primary screening consisted of 16 × 16 catalyst arrays on 4in. square quartz wafers. Catalysts were prepared by robotic liquid dispensing techniques and screened for catalytic activity in Symyx' scanning mass spectrometer. The scanning mass spectrometer is a fast serial screening tool that uses flat wafer catalyst surfaces, local laser heating, a scanning/sniffing nozzle and a quadrupolar mass spectrometer to compare relative catalytic activities. The feed consisted of NO/NH₃ mixtures with optional O₂ cofeed and Kr as the internal standard in Ar carrier gas. QMS detection allowed for tracking of H₂O, N₂, NO, O₂, N₂O and Kr. Screening protocols for catalytic materials encompassed metal precursors and carriers for supported vanadia systems, extensive doping of V₂O₅/TiO₂, and broad screening of mixed redox metal oxides and supported base and noble metal systems. More than 500 samples could be screened in a single day. Active hits (high NO consumption accompanied by corresponding N₂ production) identified in discovery libraries were re-synthesized as focus libraries for lead confirmation and further optimization. These libraries used shallower compositional gradients, for example 56 points (compositions) per ternary, with four 56-point ternaries per 4in. wafer. Broad screening ternaries were generally 8 or 15 points. The focus libraries more clearly reveal the trends and provide guidelines for secondary screening and scale-up. High conversions were achieved in scanning mass spectrometer so the scalability risk is small for the short contact time reactions.     

Electrochemical promotion of Rh catalyst in gas-phase reduction of NO by propylene

The concept of non-faradaic electrochemical modification of catalytic activity (NEMCA) has been applied for the in situ control of catalytic activity of a rhodium film deposited on YSZ (yttria stabilized zirconia) solid electrolyte towards reduction of 1000 ppm NO by 1000 ppm C₃H₆ in presence of excess (5000 ppm) O₂ at 300 °C. A temporary heating at this feed composition results in a long-lasting deactivation of the catalyst under open circuit conditions due to partial oxidation of the rhodium surface. Positive current application (5 A) over both the active and the deactivated catalysts gives rise to an enhancement of N₂ and CO₂ production, the latter exceeding several hundred times the faradaic rate. While active rhodium exhibits a reversible behaviour, electrochemical promotion on the deactivated catalyst is composed of a reversible and an irreversible part. The reversible promotion results from the steady-state accumulation of current-generated active species at the gas exposed catalyst surface whereas the irreversible effect is due to the progressive reduction of the catalyst resulting in an increased recovery rate of lost catalytic activity. The results are encouraging with respect to application of rhodium for the catalytic removal of NO from auto-exhaust gases under lean-burn conditions.     

X-ray photoelectron spectroscopic study of the oxidation and reduction of a cerium(III) oxide/cerium foil substrate

X-ray photoelectron spectroscopy has been used to examine the nature of the oxide overlayers on a passivated cerium metal foil as a function of a variety of oxidation and reduction treatments. Oxidation of a clean uncontaminated cerium(III) oxide surface is facile at room temperature and produces non-stoichiometric ceria (CeO_2–x) at oxygen doses as low as 10 L. At higher doses the overlayer thickens, and after a dose of 160 L the layer depth exceeds the Ce 3d photoelectron attenuation distance of about 20 Å. High pressure treatment of the foil in oxygen (0.5 bar at RT and 473 K) produces CeO₂ in a high degree of crystallographic order such that O 1s photoelectron intensities are increased above that expected from a randomly oriented powder. An attempt to reduce the CeO₂ layer formed by controlled oxidation with CO (633 K, 14 h, 0.6 bar) results in the formation of a carbonated surface layer. Results following attempts to reoxidise this layer are discussed.     

Activation of plant foliar oxidases by insect feeding reduces nutritive quality of foliage for noctuid herbivores

The foliage and fruit of the tomato plantLycopersicon esculentum contains polyphenol oxidases (PPO) and peroxidases (POD) that are compartmentally separated from orthodihydroxyphenolic substrates in situ. However, when leaf tissue is damaged by insect feeding, the enzyme and phenolic substrates come in contact, resulting in the rapid oxidation of phenolics to orthoquinones. When the tomato fruitwormHeliothis zea or the beet army-wormSpodoptera exigua feed on tomato foliage, a substantial amount of the ingested chlorogenic acid is oxidized to chlorogenoquinone by PPO in the insect gut. Additionally, the digestive enzymes of the fruitworm have the potential to further activate foliar oxidase activity in the gut. Chlorogenoquinone is a highly reactive electrophilic molecule that readily binds cova-lently to nucleophilic groups of amino acids and proteins. In particular, the —SH and —NH₂ groups of amino acids are susceptible to binding or alkylation. In experiments with tomato foliage, the relative growth rate of the fruitworm was negatively correlated with PPO activity. As the tomato plant matures, foliar PPO activity may increase nearly 10-fold while the growth rate of the fruitworm is severely depressed. In tomato fruit, the levels of PPO are highest in small immature fruit but are essentially negligible in mature fruit. The growth rate of larvae on fruit was also negatively correlated with PPO activity, with the fastest larval growth rate occurring when larvae fed on mature fruit. The reduction in larval growth is proposed to result from the alkylation of amino acids/protein byo-quinones, and the subsequent reduction in the nutritive quality of foliage. This alkylation reduces the digestibility of dietary protein and the bioavailability of amino acids. We believe that this mechanism of digestibility reduction may be extrapolatable to other plant-insect systems because of the ubiquitous cooccurrence of PPO and phenolic substrates among vascular plant species.     

Application of an improved control-variate scheme to local neoclassical transport simulations

A new radially local neoclassical transport code is developed based on the radially global two-weight δf$\delta f$ Monte Carlo code, FORTEC-3D (Satake et al., 2008). In the collisional two-weight δf$\delta f$ method, the variance of weight increases in time due to the so-called weight spreading, which leads to an increasing numerical noise in long time simulations. A new improved control-variate scheme was proposed by Kleiber et al. (2011) to reduce the variance. We investigate the effectiveness and validity of the new control-variate scheme for a practical collisional transport problem in a plasma described by the drift kinetic equation. It is demonstrated that the new scheme reduces the variance of weight by approximately 75% in an axisymmetric magnetic field configuration. The burst-like behavior of a transport observable caused by a large numerical noise can be avoided. As a result, the time evolution of a transport observable can be successfully smoothed.     

高岭土在碳热还原氮化过程中的相变

系统研究了苏州高岭土碳热还原氮化合成SiAlON过程在不同温度下的相变。对试样的XRD、SEM以及EDXA分析结果表明 ,1 30 0℃之前 ,试样中没有氮化物生成 ,物相为莫来石、石英和方石英 ;1 30 0℃时 ,高岭土开始发生氮化反应 ,生成过渡型SiAlON和β SiAlON。此时 ,石英和方石英相基本消失 ;1 4 0 0℃时 ,过渡型SiAlON、β SiAlON和X SiAlON三相共存 ,β SiAlON有所增多并有少量刚玉相生成 ;从 1 4 50℃到 1 550℃ ,Z值为 3的β SiAlON成为惟一的氮化产物 ,与少量SiC和刚玉相并存。莫来石在 1 50 0℃时完全消失     

Electrochemical reduction of nitrate on Pt(S)[n(1 1 1) × (1 1 1)] electrodes in perchloric acid solution

The electrochemical reduction of nitrate ion was studied by cyclic voltammetry on Pt(1 1 1) and [n(1 1 1) × (1 1 1)] stepped Pt surfaces, where n (=14, 10, 7, 6, 5, 4, 3, 2) is the number of terrace atoms, in 0.1 M HClO₄ + 10 mM KNO₃. The electrocatalytic nitrate reduction was found to hardly proceed on Pt(1 1 1) in the hydrogen adsorption region, while the electrocatalytic activity was improved with the increase in the step density. Inactivation was observed in the presence of adsorbed hydrogen or nitrate-derived reduced adsorbate, i.e. adsorbed NO, on (1 1 1) step sites. It was, therefore, concluded that the electrocatalytically active NO₃⁻ species does not adsorb on the (1 1 1) terraces but on the (1 1 1) monoatomic steps. The nitrate reduction current increased with the step density in a non-linear relationship. The overall current density at 0.21 V (RHE) corresponding to the peak potential of the main electrocatalytic nitrate reduction wave which was maximum at n = 2, abruptly increased with short terraces, i.e. n < 5, where the current wave of adsorbed hydrogen on the Pt stepped surface with comparatively narrow (1 1 1) terraces, denoted as H_nt, also appeared unmodified for n < 5 on voltammograms recorded in 0.1 M HClO₄ in the absence of nitrate.     

Reactive rock phosphate fertilizers and soil testing for phosphorus: The effect of particle size of the rock phosphate

North Carolina rock phosphate (NCRP) (highly carbonate—substituted apatite) was ground to produce three samples with different particle size distributions. The effectiveness of these fertilizers was compared with the effectiveness of superphosphate in a field experiment and three glasshouse experiments using lateritic soils from south-western Australia. Non-reactive Queensland rock phosphate (low carbonate-substituted apatite from the Duchess deposit) was also used in the pot experiments. Bicarbonate-soluble phosphorus extracted from the soil is widely used in Western Australia to predict plant yields from previously-applied fertilizer dressings. For both field and pot experiments bicarbonate-extractable phosphorus (soil test value) was measured and related to subsequent plant yields.As calculated from the initial slope of the relationship between yield and the level of P applied, finely powdered NCRP was about 5–32% as effective as freshly-applied superphosphate in the year of application and also for two years after application in the field experiment, and for two successive crops in the three pot experiments. For both field and pot experiments, finely powdered NCRP, was at best, 1.5–2.0 times as effective as granular NCRP. Relative to freshly-applied superphosphate, the effectiveness of rock phosphates usually decreased with increasing level of application.For each of the crops in the field experiment, the relationships between yield and phosphorus content of plants (i.e. internal efficiency curves) were similar for all fertilizers. Thus the low effectiveness of the rock phosphates relative to superphosphate was solely due to much less phosphorus being taken up by plants. By contrast, in the pot experiments internal efficiency curves differed for different fertilizers. This is attributed to differences in the rate of phosphorus uptake by plant roots during the early stages of plant growth.For both field and pot experiments, soil test calibrations (the relationship between yield and soil test value) differed for rock phosphates and superphosphate. For superphosphate, soil test calibrations also differed for the three different years after the initial application of this fertilizer in the field experiment. For the second crop in the pot experiment, soil test calibrations differed for superphosphate applied at different times (before the first and the second crop). These results point out the difficulty of applying soil testing procedures to soils that have experienced different histories of fertilizer application.     

基于多步迭代算法的数字预失真技术

为了更好地补偿功率放大器的非线性,提出一种新型多步迭代算法来求取数字预失真器。新算法结合了多步迭代算法与频域削峰技术,使功放在保证工作效率的同时更大程度提高其线性度。实验结果显示,该方法较传统的线性化技术有明显优势,功放输出信号的ACPR可改善20.66 dB。     

Electrosynthesis of 2,3-dimethyltartaric acid from pyruvic acid in acid medium

This study reports the electrohydrodimerization of pyruvic acid to 2,3-dimethyltartaric acid in sulphuric acid medium (0.5 M H₂SO₄) on a lead cathode. The main products detected were lactic acid and 2,3-dimethyltartaric acid. The selectivity towards the formation of 2,3-dimethyltartaric acid was studied vs. pyruvic acid concentration in sulphuric acid solution, at −1.1 V vs. MSE. The best selectivity of 2,3-dimethyltartaric acid reached 69% for an initial concentration of 1.7 M pyruvic acid. The yield of pyruvic acid was 84%.