几种光敏剂光敏氧化效率的比较

<正> 光敏氧化效率是由敏化剂分子吸收光量子数及其产生单重态氧的量子产率决定的,这要求敏化剂的吸收光谱同光源的发射光谱很好地匹配。本文报道竹红菌甲素匹配高压钠灯有效地产生单重态氧,高效光敏氧化一系列具有不同反应活性的底物,成为单重态氧化学中一个新的光敏氧化体系。     

Energetics of magnesium, strontium, and barium doped lanthanum gallate perovskites

LaGaO₃ perovskites doped with Sr or Ba at the La site and Mg at the Ga site were prepared by solid-state reaction or sol-gel method and characterized. Enthalpies of formation from constituent oxides at 298 K were determined by high-temperature oxide melt solution calorimetry. Energetic trends are discussed in terms of defect chemistry. As oxygen deficiency increases, formation enthalpies define three trends, LaGa_1−yMg_yO_3−δ (LGM), La_1−xSr_xGa_1−yMg_yO_3−δ (LSGM), and La_1−xBa_xGa_1−yMg_yO_3−δ (LBGM). They become less exothermic with increasing doping, suggesting a dominant destabilization effect from oxygen vacancies. The endothermic enthalpy of vacancy formation is 275±37, 166±18 and 138±12 kJ/mol of V_O^·· for LGM, LBGM and LSGM, respectively. Tolerance factor and ion size mismatch also affect enthalpies. In terms of energetics, Sr is the best dopant for the La site and Mg for the Ga site, supporting earlier studies, including oxygen ion conductivity and computer modeling.     

TDS and XPS study of oxygen diffusion into subsurface layers of Pd(110)

Summary The interaction of O₂with Pd(110) has been studied by TDS and XPS at T = 400 K and at pressures P_{O2 from 2.6x10}^-6to 10 Pa. At low exposures in O₂(e￡1-5 L), an adsorption layer withqof ca.0.5 and with the O1s peak at BE = 529.3 eV has been found to form on the surface. Whenegrows from 5 to 10⁸L, the position and intensity of the oxygen O1s peak remain practically constant. At the same time, as much as 5 mL of oxygen is absorbed according to the TDS data. The results obtained by TDS and XPS indicate that oxygen penetrates deep into the subsurface layers of palladium (315-20 ?) and is distributed in its bulk in a low concentration.     

Chemical diffusion of oxygen in tin dioxide: Effects of dopants and oxygen partial pressure

Tin dioxide SnO_2−δ is a pronounced n-type electron conductor due to its oxygen deficiency. This study investigates the rate of chemical diffusion of oxygen in SnO_2−δ single crystals, which is a crucial step in the overall stoichiometry change of the material. The chemical diffusion coefficient D^δ was determined from conductivity- and EPR-relaxation methods. The temperature dependence was found to be . The dependence on crystal orientation, dopant content and oxygen partial pressure was below experimental error. The latter observation leads to the conclusion that the chemical diffusion coefficient is close to the diffusion coefficient of oxygen vacancies. Along with the relaxation process resulting from the chemical diffusion of oxygen, additional processes were observed. One of these was attributed to complications in the defect chemistry of the material. The relevance of the results for the kinetics of drift processes of Taguchi sensors is discussed.     

Nonstationary Markov chains and convergence of the annealing algorithm

We study the asymptotic behavior as timet + of certain nonstationary Markov chains, and prove the convergence of the annealing algorithm in Monte Carlo simulations. We find that in the limitt + , a nonstationary Markov chain may exhibit phase transitions. Nonstationary Markov chains in general, and the annealing algorithm in particular, lead to biased estimators for the expectation values of the process. We compute the leading terms in the bias and the variance of the sample-means estimator. We find that the annealing algorithm converges if the temperatureT(t) goes to zero no faster thanC/log(t/t ₀) ast+, with a computable constantC andt ₀ the initial time. The bias and the variance of the sample-means estimator in the annealing algorithm go to zero likeO(t^–1+) for some 0<1, with =0 only in very special circumstances. Our results concerning the convergence of the annealing algorithm, and the rate of convergence to zero of the bias and the variance of the sample-means estimator, provide a rigorous procedure for choosing the optimal annealing schedule. This optimal choice reflects the competition between two physical effects: (a) The adiabatic effect, whereby if the temperature is loweredtoo abruptly the system may end up not in a ground state but in a nearby metastable state, and (b) the super-cooling effect, whereby if the temperature is loweredtoo slowly the system will indeed approach the ground state(s) but may do so extremely slowly.     

锡铅银等低熔点合金中氧的测定方法研究

研究了锡铅银等低熔点合金中杂质氧的测定方法。针对这些金属高温下易挥发、分解的特点，选择适宜的加热温度，使用铜和石墨粉作为浴料，选择标准坩埚，以电流920A加热进行试验。对氧的质量分数为0.017%的试样，分析精密度为5.9%，加标回收率为91％－108％。     

Effects of Oxygen and Water Vapor on Volatile Organic Compounds Decomposition Using Gliding Arc Gas Discharge

The combined effects of oxygen and water vapor on three typical volatile organic compounds, i.e. tetrachloromethane, n-butane and toluene, decomposition efficiency under gliding arc gas discharge conditions are studied. The electron density and the density of the reactive radicals such as O and OH are modified by addition of oxygen and water vapor. Consequently, the decomposition process can be enhanced or suppressed, depending on the involved chemical structures and reaction channels. The addition of oxygen and water vapor suppresses the tetrachloromethane decomposition which indicates that this process is mainly controlled by the electron dissociation reactions. By contrast, the n-butane and toluene decompositions are enhanced, which shows that they can be mainly ascribed to the radical induced reactions. Especially, in a moist atmosphere the OH radicals are supposed to play the most important role in the n-butane decomposition process.     

Low volume sampling device for mass spectrometry analysis of gas formation in nickel-metalhydride (NiMH) batteries

Rechargeable nickel-metalhydride (NiMH) batteries have major advantages with respect to environmental friendliness and energy density compared to other battery systems. Research on thermodynamics and reaction kinetics is required to study the behaviour of these batteries, especially under severe operating conditions such as overcharging and (over)discharging. During these processes several reactions take place resulting in the formation of oxygen and hydrogen gas. Hence, the recombination processes should be well controlled to guarantee that the partial oxygen and hydrogen pressure inside the battery are kept low.Mass spectrometry is one of the analytical techniques capable of measuring the composition of gases released inside the battery during the charge and discharge processes. However, the sample gas needs to be withdrawn from the battery during the experiment. The gas consumption must be kept to a minimum otherwise the equilibrium inside the battery will be disturbed. A bench-top quadrupole mass spectrometer with a standard capillary by-pass inlet cannot be used for this purpose as its gas consumption is in the 1-10 ml/min range. In this paper, a new gas inlet device is presented that reduces gas consumption to a value <50 μl/h. The use of a capillary by-pass splitter and a discontinuous sampling procedure allow mass spectrometry to be used as a gas analysis tool in many applications in which small amounts of sample gas are involved.Experiments with standard AA-size NiMH batteries show that hydrogen release dominates during (over)charging at increased charging rates. Beside mass spectrometry, evolved gases are also analysed using Raman spectroscopy. Although some differences are observed, the results of similar experiments show a good agreement.     

The systems Zr(Nb,Ti)(R)O2−δ, R=Yb, Ca—optimization of mixed conductivity and comparison with results of other systems (R=Y and Gd)

In this work we address the optimization of mixed conductivity in fluorite compounds based on zirconia. Phase relations of the new systems YbO_1.5-NbO_2.5-ZrO₂, and CaO-NbO_2.5-ZrO₂ are presented. The limit of the cubic defect fluorite phase in YbO_1.5-NbO_2.5-ZrO₂ closely resembles that of the system YO_1.5-NbO_2.5-ZrO₂, whilst in CaO-NbO_2.5-ZrO₂ is narrow extending to include composition Ca_0.255Nb_0.15Zr_0.595O_1.82 at 1500°C. The influence of dopant ion size, charge and composition on ionic conduction is assessed and parallels are drawn with the systems YO_1.5-NbO_2.5-ZrO₂ and YO_1.5-TiO₂-ZrO₂. Comparison of these results with published data on the Ti containing systems CaO-TiO₂-ZrO₂, GdO_1.5-TiO₂-ZrO₂ shows that the highest mixed conducting compositions can only be offered in the system YO_1.5-TiO₂-ZrO₂ out of all the systems here studied.     

Xyloccensin L, a novel limonoid from Xylocarpus granatum

The isolation and structure elucidation of xyloccensin L from the stem bark of Xylocarpus granatum is described. Xyloccensin L is a highly oxidized heptacyclic A, B, D-seco limonoid with an α-8, 30-epoxy ring and a rare 1, 29 oxygen bridge.