The kinetics of hydrogen transport through amorphous Pd82−yNiySi18 alloys (y=0-32) by analysis of anodic current transient

Hydrogen transport through amorphous Pd_82−yNi_ySi₁₈ alloys (y=0-32) was investigated in 0.1 M NaOH solution by analysis of the anodic current transient. It was found that the anodic current transient shows the non-Cottrell behaviour, but its shape and value remain nearly constant regardless of the hydrogen discharging potential. From the coincidence of the anodic current transient theoretically calculated with that experimentally measured, it is suggested that the change in surface concentration of hydrogen with time is uniquely given by the rate of hydrogen transfer from absorbed state at the electrode sub-surface to adsorbed state on the electrode surface. This means that neither the ‘constraint of constant concentration’ nor the ‘constraint by Butler-Volmer behaviour’ is effective at the electrode surface during hydrogen extraction. On the basis of the theoretical current-time relation under the ‘constraint by hydrogen transfer of absorbed state to adsorbed state’, the hydrogen diffusivity was determined to have an almost constant value of (1.3±0.4)×10⁻⁸ cm² s⁻¹, irrespective of the Ni content and in the absence of Ni. On the other hand, it is inferred that the rate constant of hydrogen transfer decreases markedly with increasing Ni content due to the Ni(OH)₂ layer formed on the electrode surface.     

Etude de l'oxydation du pentachlorophénol dans différentes géométries de réacteurs à ultrasons de haute fréquence

The determination of the key geometric parameters used for high-frequency sonoreactor modeling has been studied. The methodology allowing the characterization of the different reactors built in our laboratory has been defined. The methods are: calorimetry, determination of the residence time distributions, the observation of the chemiluminescence of luminol and the degradations of a prototype molecule: pentachlorophenol. After characterization of the studied reactors, it seems that volumetric power, with equivalent emitting system, is the major parameter of the reactor's performance.     

Activation of Ni/A12O3 catalysts through modification of the Al2O3 support

The effect of alumina pretreatment on the performance of alumina supported nickel catalysts was demonstrated in gas phase hydrogenation of toluene to methylcyclohexane. The state of the alumina was changed from pure to pure phase through various heat treatments in air. The catalysts were prepared from vapor phase by saturating the accessible binding sites on the pretreated alumina with the nickel precursor. The highest number of active sites for hydrogenation was observed for catalysts prepared on alumina having an incomplete phase transition and a / alumina phase ratio between 0.5 and 10. Results from temperature programmed desorption (TPD) studies revealed that a maximum in weakly chemisorbed hydrogen as well as in total amount of desorbed hydrogen was found for the same catalysts. By hydrogen chemisorption studies the total hydrogen uptake was found to correlate with the observed hydrogenation maximum. It is suggested that both the chemical and physical properties of the alumina influence the activity. An optimal metal-support interaction and structural defects on the alumina due to the phase transition can explain the observed maximum in the number of active sites and in hydrogen uptake.     

Catalytic Combustion of Model Carbon Particles (CPs) over Pt/β-SiC Catalyst

Platinum catalyst supported on a medium surface area -SiC was successfully used for the catalytic combustion of model carbon particles and compared to a catalyst supported on a low surface area -SiC. The -SiC-based catalyst showed no deactivation as a function of cycling tests while a strong deactivation was observed on the -SiC-based catalyst. This deactivation was attributed to the progressive encapsulation of the platinum particles by a layer of silica which built up during the combustion cycle. These results render possible the use of Pt/-SiC catalyst as a diesel carbon particle catalytic filter with continuous regeneration.     

New sesquiterpenes fromMaytenus species (Celastraceae). Taxonomic and chemotaxonomic considerations concerning chileanMaytenus

Three new dihydro--agarofuran sesquiterpenes from two species ofMaytenus were isolated and their structures were elucidated by means of¹H and¹³C NMR studies. The differences and similarities noted in the chemical content of the dihydro--agarofuran sesquiterpenes from the fourMaytenus species from Chile are in line with the taxonomic characterization of these species; their geographical distribution is also given.     

β-Phellandrene: kairomone for pine engraver,Ips pini (Say) (Coleoptera: Scolytidae)

The responses ofIps pini (Scolytidae) to multiple-funnel traps baited with the pheromone, ipsdienol, and various monoterpenes were determined in stands of lodgepole pine in southern and central British Columbia.Ips pini was attracted to both ipsdienol and -phellandrene, demonstrating that -phellandrene is a kairomone for this species.Lasconotus complex (Colydiidae) and aCorticeus sp. (Tenebrionidae) were attracted to both ipsdienol and -phellandrene. TheCorticeus sp. exhibited a synergistic response to the combination of ipsdienol and -phellandrene; the responses of the other two species to the combination were additive. The predators,Thanasimus undatulus, Enoclerus sphegeus, andE. lecontei (Cleridae), were attracted to ipsdienol-baited traps, whileMonochamus clamator (Cerambycidae) andDendroctonus ponderosae (Scolytidae) were attracted to -phellandrene. Attraction of all eight species increased with increasing release rates of ipsdienol and/or -phellandrene.     

改进的细菌觅食优化算法求解0-1背包问题

细菌觅食优化算法作为一种新兴的智能优化算法,一般用来解决连续域的问题。为了解决离散域问题,提出了一种改进的细菌觅食优化算法。采用线性递减的思想和随机的游动长度代替固定步长和随机游动方向,改进了趋向性操作方案,并将其应用于解决0-1背包问题。将改进的细菌觅食优化算法与遗传算法、离散粒子群优化算法及基本的离散化细菌觅食优化算法分别在小规模和大规模的0-1背包问题上进行了仿真比较,表明了改进的细菌觅食优化算法能取得较好的效果,寻优能力强。     

Sintering behaviour of La1−xSrxFeO3−δ mixed conductors

The sintering properties of La_1−xSr_xFeO_3−δ (x = 0.1, 0.25) mixed conductors have been investigated with particular emphasis on the effect of secondary phases due to cation non-stoichiometry (±5 mol% La excess and deficiency). Secondary phases, located at grain boundaries in cation non-stoichiometric materials, increased the sintering temperature compared to single-phase materials. Extensive swelling in final stage of sintering was observed in all materials, which resulted in micro-porous materials. The swelling was most pronounced in the phase pure and two-phase materials due to La-deficiency, while refractory secondary phases in La-excess materials inhibited both sintering, grain growth and swelling. In La-deficient materials, formation of molten secondary phases resulted in rapid swelling due to viscous flow. The present findings demonstrated the importance of controlling sintering temperature and time, as well as careful control of the cation stoichiometry of La_1−xSr_xFeO_3−δ in order to achieve fully dense and homogenous La_1−xSr_xFeO_3−δ ceramics.     

Fluorescence of poly(di-n-alkylsilane)s in room-temperature solution

A comprehensive study of the electronic absorption and emission spectra and the fluorescence quantum yield and lifetime of seven poly(di-n-alkylsilane)s and of three isotopically labelled poly(di-n-hexylsilane)s in hydrocarbon solution at room temperature is reported. Also reported are fluorescence polarization and carbon tetrachloride quenching of fluorescence of poly(di-n-hexylsilane). The observed fluorescence spectra, quantum yield, and polarization depend on the selected excitation energy in a very characteristic fashion, whereas the fluorescence lifetime does not; however, it depends on the selected emission energy. These characteristic dependencies are qualitatively accounted for by the previously proposed segment distribution model if one assumes that the photophysical behavior at higher excitation energies is strongly affected by the presence of a low-lying weakly allowed state in short-segment chromophores and the behavior at lower excitation energies is dictated by the selective excitation of emitting long-segment chromophores.     

An EXAFS study of the Mo/TiO2 hydrodesulphurization catalysis

In-situ EXAFS studies of sulphided Mo/TiO₂ catalysts have shown that at low Mo loadings (2–4 wt%), an active species with a short Mo-S distance of 2.25 Å is formed, while on Mo/TiO₂ with high Mo loadings as well as on Mo/-Al₂O₃, bulk MoS₂ (Mo-S, 2.42 Å) is formed. The species with the short Mo-S distance has Mo in an oxidation state close to 6 + and is likely to result from the sulphidation of the tetrahedral molybdate species present in the oxidic precursor at low Mo loadings. The calcination temperature of the oxidic precursor appears crucial, a high calcination temperature of 973 K favouring the formation of MoS₃ on sulphidation, and a low calcination temperature of 623 K favouring MoS₂.Contribution No. 790 from the Solid State and Structural Chemistry Unit.