Dynamic and kinetic modeling of isotopic transient responses for CO insertion on Rh and Mn–Rh catalysts

Isotopic transient tracer techniques have been employed to study heterogeneous hydroformylation on Rh/SiO₂ and Mn–Rh/SiO₂. Pulse injection of D₂ and allowed tracing of the deuterium and CO incorporation pathway into the aldehyde product. The d₁- and d₂-propionaldehyde responses showed a double-peak, or two-hump, response to the D₂ pulse, while showed a single-hump response to the pulse. Analysis of the product responses to the D₂ pulse in CO/H₂/C₂H₄ and CO/H₂/C₂H₄/C₂H₅CHO suggests that the first hump of the d₁- and d₂-propionaldehyde responses was due to rapid H/D exchange with adsorbed propionaldehyde via enol intermediates. The decay of the second hump was due to reaction of adsorbed acyl with spillover hydrogen/deuterium. The response was due to CO insertion followed by acyl hydrogenation. Compartment modeling of the product responses from the and D₂ pulse inputs allowed determination of residence times of adsorbed intermediates, surface coverages of adsorbed intermediates, and the elementary rate constants for acyl hydrogenation and CO insertion. Elementary rate constants for acyl hydrogenation determined from this study were consistent with the value calculated by transition state theory (TST). The addition of Mn promoter to Rh/SiO₂ increased coverages of , , and and shifted the rate-limiting step for propionaldehyde formation. Acyl hydrogenation is the rate-limiting step on Rh/SiO₂ while CO insertion and acyl hydrogenation are both kinetically significant on Mn–Rh/SiO₂.     

Characterization and modeling of diffusion process for mass transport through the Tournemire argillites (Aveyron, France)

Argillites are one of the geological formations studied by IRSN for their confining properties for isolation of radioactive wastes. One of the main objectives is the study of water transport through rocks with very low water content and very low hydraulic conductivity by modeling of natural tracer profiles. This paper presents the protocol developed for and applied to the acquisition of data for chloride content in interstitial water of the Toarcian argillites at the Tournemire site (Southern France). This protocol is based on laboratory diffusion experiments and on modeling. Experimental data obtained during the transient and steady-state parts of diffusion experiments enable, respectively, the assessment of the diffusion coefficient and the determination of Cl concentration in pore water. Using this protocol, profiles with depth for both of these data sets have been acquired along the geological sequence. Taking into account the present knowledge of the geological and hydrogeological history of the Tournemire massif, a conceptual model granting the main role for mass transport to diffusion has been proposed. According to this conceptual model, a one-dimensional numerical model was built for simulating the mass transport of chloride through the sedimentary column, over 53 Ma. The good agreement between experimental data and calculated values for both diffusion coefficients and concentrations of chloride confirms that diffusion is likely the main process for mass transport in the massif. This model was also tested with the deuterium content of interstitial water, applying variable concentrations at the aquifer system boundaries for reflecting the thermal dependency of isotopic composition in precipitation. These simulations also reveal the likely important role of heterogeneities, such as fractures, in the variability of tracer concentrations with regards to a simple diffusion profile.     

Recovery of deuterium from water-isotopes mixture by thermal diffusion

Methods for theoretical prediction of deuterium recovery from the separation of water-isotope mixtures in a batch-type thermal diffusion column have been introduced. Theoretical predictions are found in fair agreement with the experimental results. Most of the predictions give higher values of separation than experiments. Predictions based on the constant and linear approximations for the pseudo product form of concentration are very similar and have better agreement with experiments than those based on the third type of approximation.     

Studies on the Dynamics of D–T Fusion Reaction Based on the Relativistic Equilibrium Velocity Distribution

The Coulomb barrier is in general much higher than thermal energy. Nuclear fusion reactions occur only among few protons and nuclei (i.e., deuterium and tritium) with higher relative energies than Coulomb barrier. It is the equilibrium velocity distribution of these high-energy protons and nuclei that participates in determining the rate of nuclear fusion reactions. In the circumstance it is inappropriate to use the Maxwellian velocity distribution for calculating the nuclear fusion reaction rate. We use the relativistic equilibrium has a reduction factor with respect to that based on the Maxwellian distribution, which factor depends on the temperature, reduced mass and atomic numbers of the studied nuclear fusion reactions. In this paper, we concluded at energy range 10⁵ (keV) ≤ E ≤ 10⁶ (keV), that is smaller than reduced mass energy of deuterium–tritium, m _r c ², the numerical values of R and R _M are not different from each other very much, but by increasing energy near the region of m _r c ² the difference between them are visible, also by increasing energy for example 9 × 10⁶ (keV) ≤ E ≤ 10 × 10⁶ (keV) the difference is obviously more visible. Therefore, we have to use relativistic equilibrium velocity distribution instead of Maxwellian velocity distribution.     

Stable isotope characterization of olive oils: II-deuterium distribution in fatty acids studied by nuclear magnetic resonance (SNIF-NMR)

Site-specific isotope fractionation of hydrogen was investigated, at natural abundance, by deuterium nuclear magnetic resonance (SNIF-NMR) on nearly two hundred olive oil samples. Owing to the complexity of the ²H-NMR spectra of the mixtures of fatty acids obtained after hydrolysis of the oils, the different signals were gathered into six clusters. Knowing the contribution to the clusters of each of the four fatty acids considered (C_16:0, C_18:0, C_18:1, and C_18:2) and the composition of the fatty acids in the mixture, it is possible to compute the site-specific isotope ratios of the clusters from the molar fractions obtained from the ²H-NMR-spectra and from the total isotope ratio of the mixture, determined by isotope ratio mass spectrometry (IRMS). The results are discussed in terms of geographical (country, region and elevation) and temporal (year) parameters and they are tentatively explained on a climatic basis.     

Isotope effects H/D in a PEFC with PtRu/anode at low and high current density

This paper reports a study on the use of a polymer electrolyte fuel cell (PEFC) with a PtRu/C anode for isotopic separation of hydrogen (H) and deuterium (D). The performance of a PEFC, fed with pure hydrogen, deuterium or a their mix is depicted. In order to investigate the effect of the two isotopes, electrochemical impedance spectroscopy (EIS) tests have been carried out together with galvanostatic polarization and IR analysis. Results evidenced an isotope effect on the thermodynamics, conductivity, ionic mobility and cathode mass transfer. IR analysis at the cathode side indicated that the isotopic separation efficiency was dependent on the current density with a maximum at intermediate values.     

Feasibility study of an intense D–T fusion source: “The New Sorgentina”

The international community agrees on the importance to build a large facility devoted to test and validate materials to be used in harsh neutron environments. Such a facility, proposed by ENEA, reconsiders a previous study known as “Sorgentina” but takes into account new technological development so far attained. The “New Sorgentina” Fusion Source (NSFS) project is based upon an intense D–T 14 MeV neutron source achievable with T and D ion beams impinging on 2 m radius rotating targets. NSFS produces about 1 × 10¹³ n cm⁻² s⁻¹ over about 50 cm³. Larger volumes of lower neutron flux will be available (e.g. for TBM experiments) as well as collimated channels to study some features of the ITER neutron camera. The NSFS facility will overcome problems related to the ion source and accelerating system, by means of an upgraded version of the JET–PINI ion beams. NSFS has to be intended as an European facility that may be realized in a few years, once provided a preliminary technological program devoted to the operation of the ion source in continuous mode, target heat loading/removal, target and tritium handling, inventory as well as site licensing. In this contribution, the main characteristics of NSFS project will be presented.     

Ti/AlN/Ti/AlN复合涂层的制备和阻氘性能研究

为提高AlN涂层的稳定性和阻氚性能,提出“Ti-AlN”复合结构涂层。采用磁控溅射法在316L不锈钢基体表面制备了结构致密、总厚度约500 nm的Ti/AlN/Ti/AlN复合涂层。对涂层样品进行不同的真空热处理后,采用SEM、XRD、AES等手段分析涂层样品在热处理前后的微观形貌和结构变化,并对样品在200-600 ℃的阻氘性能进行测试和分析。结果表明,仅热处理温度为760 ℃时,Ti-AlN界面反应生成少量的Al3Ti相。在所有涂层样品中,热处理温度为700 ℃、升温速率为1.5 ℃/min的复合涂层表现出最优的阻氘性能,其600 ℃的PRF（Permeation Reduction Factor）高达536。当热处理温度升高至760 ℃或升温速率达到2.5 ℃/min时,表层AlN层的开裂程度更为严重,并导致涂层的阻氘性能显著降低。另外,所有涂层样品的PRF（阻氘性能）均随渗透温度的降低而急剧减小,表明氘气渗透过程中的温度变化会导致复合涂层阻氘性能失效。     

氮杂环苯基吡啶类铱配合物合成及器件性能

通过对2-甲基-8-(2-吡啶基)苯并呋喃[2,3-B]吡啶辅助配体进行修饰,在吡啶的4号位引入吸电子基团苯基,并对其进行全氘代,同时对5-甲基-2-对甲苯基吡啶主配体的两个甲基进行全氘代,分别合成了两种铱磷光配合物Ⅳ和Ⅳ-d₂₀,采用元素分析、质谱和核磁共振氢谱对其结构进行了表征与确认。利用UV-Vis 光谱、荧光发射光谱(PL)和循环伏安法对其光物理性质及能级结构进行了研究。结果表明：铱配合物的Ⅳ和Ⅳ-d₂₀光致发光光谱发射波长分别为546.85nm和548nm;它们的HOMO和LUMO能级分别为-5.237ev和-2.645ev、-5.082ev和-2.50ev,都是潜在的黄绿色磷光材料。以铱配合物Ⅳ和Ⅳ-d₂₀为客体,制备了结构为ITO/HT:NDP-9(100nm,2%)/HT(130nm)/EB(10nm)/GH:化合物Ⅳ或Ⅳ-d₂₀(40nm,5%)/HB(10nm)/ ET:Liq(35nm,50%)/Liq(10nm)/Al(150nm)的OLED器件,并研究了它们的器件性能。结果表明：铱配合物Ⅳ-d₂₀表现出更优异的器件性能。电流密度为20mA/cm₂^时,铱配合物Ⅳ-d₂₀的器件发射波长为552nm,CIE 坐标为 (0.422,0.569),电流效率为 87.00cd/A,外量子效率(EQE)高达23.82%。     

POSITRON LIFETIME STUDIES ON SYSTEMS OF PALLADIUM FILLED GALVANOSTATICALLY WITH HYDROGEN OR DEUTERIUM

The positron lifetime spectroscopy was used to investigate the electron structures of crystal lattice and its defects in palladium samples filled galvanostatically with hydrogen and deuterium, respectively. The results have indicated that the positron lifetime were all the same between hydrogen and deuterium filled samples in which the positron lifetime τ(?) increased about 10%, corresponding to the volume expansibility after the formation of hydrides PdH or PdD phases during electrolyzing commom water or heavy water with Pd cathode; and Will not change with time in 3 weeks after stopping electrolysis; but could be recovered to 116±1ps, the value in polycrystalline pure palladium, after annealing at high temperature.