Nickel/Chromium oxide/Zirconium oxide Catalysts for Hydrogen/Deuterium Isotopic Exchange

Catalysts composed of nickel and promoted with different metal oxides proved to be suitable for H/D isotropic exchange between hydrogen and water vapour. They loss their activity due to water condensation on their surfaces. Several nickel/chromium oxide/zirconium oxide catalysts of different composition were prepared by the coprecipitation technique. The liquid phase activity of these catalysts were followed using the hydrogen peroxide decomposition on their surfaces at different temperatures. The surface characteristics of the examined catalysts were followed by applying the BET method. The results were discussed and lead to the required catalyst composition which resists the water condensation on its surface during operation and has relatively high activity in the vapour phase H/D isotopic exchange reaction between hydrogen and water.     

Hydrogen isotope exchange in proton-conducting oxides during proton and deuteron irradiation

It has been found that during accelerator beam deuteron irradiation of a proton-conducting oxide containing protium H/D isotope exchange between beam ions and dissolved ions takes place. This isotope exchange was also observed during high-energy proton irradiation of the oxide containing dissolved deuterium atoms. These results provide evidence to a new type of hydrogen isotope exchange. Any appreciable effects of conjugate diffusion of hydrogen and oxygen ions and of the interface processes on the isotope exchange rate were eliminated. In this type of exchange the rate of replacement of H⁺ by D⁺ and of D⁺ by H⁺ was determined only by the properties of the crystal. The discovered effect was used in our study to obtain experimental data characterizing the dynamic and equilibrium behavior of hydrogen isotopes in the oxide BaZr_0.9Y_0.1O_{3 ? δ}.     

金刚石压腔结合拉曼光谱技术进行氢同位素分馏的实验研究

应用水热金刚石压腔结合拉曼光谱技术来进行石膏和重水间稳定同位素分馏的实验研究.氢同位素 D 与 H 的质量差百分比是所有稳定同位素里最大的,由质量引起的分馏更容易发生,更容易在实验中观测;石膏是浅部地壳重要的含水矿物,它与重水之间的同位素分馏效应对矿物-水体系的同位素平衡分馏研究具有重要意义.常用分馏系数是指两矿物或两...     

环丙烷衍生物在D2O离子体系中的H/D交换反应

在Ｄ２Ｏ化学反应气条件下环丙烷衍生物的Ｈ／Ｄ交换反应特性,发现了三种新的产物离子（Ｍ＋１）＾＋、（Ｍ＋２）＾＋和（Ｍ＋３）＾＋。应用碰撞诱导碎裂（ＣＩＤ）技术研究了这些离子的碎裂反应特性。实验结果表明三种新的产物离子是由反应物与试剂离子间发生Ｈ／Ｄ交换反应生成的。并获得了环丙烷衍生物结构中活泼氢位置及其数量的信息。     

1HNMR测定含氢硅油含氢量及分子量

以高含氢硅油、八甲基环四硅氧烷和六甲基二硅氧烷为原料,在浓硫酸催化作用下通过调聚反应制备了一系列不同规格的低含氢硅油。并通过1H NMR（以二氧六环为内标物,以氘代氯仿为溶剂）表征了该含氢硅油,由特征峰的面积比计算出了其含氢量,并与化学方法测定的含氢量进行了对比,结果表明两者间相对偏差均小于±1.9%。同时,此方法还可以求得含氢硅油链段中不同结构的链段比,从而求得含氢硅油的分子量;结合特性粘度的测定,求得含氢硅油的K值为4.21×10-5L/g,α值为0.83。K,α值不受含氢量的影响,且与文献中的值一致,表明用1H NMR测定含氢硅油分子量是可行的。该方法具有操作简单、省时、准确、可靠、所需样品量少等优点。     

Mechanism of protonic conductivity in an NH4HSeO4 crystal

The chemical exchange of deuterons in a partly deuterated ammonium hydrogen selenate crystal is investigated by deuteron magnetic resonance (²H NMR) spectroscopy over a wide range of temperatures. The changes observed in the line shape of the NMR spectra at temperatures above 350 K are characteristic of chemical exchange processes. The exchange processes are thoroughly examined by two-dimensional ²H NMR spectroscopy. It is established that, over the entire temperature range, only deuterons of hydrogen bonds are involved in the exchange and the rates of exchange between deuterons of all types are nearly identical. No deuteron exchange between the ND₄ groups and hydrogen bonds is found. A new model of proton transport in ammonium hydrogen selenate is proposed on the basis of the experimental data. This model makes it possible, within a unified context, to explain all the available experimental data, including macroscopic measurements of the electrical conductivity.     

An isotope effect in electrolytic hydrogen absorption of some transition metals studied by ERDA and SIMS techniques

The depth profiles of protium and deuterium which were charged electrolytically, were measured by elastic recoil detection analysis (ERDA) and secondary ion mass spectrometry (SIMS) techniques in order to study the isotope effect in hydrogen absorption of Ti, Zr, Nb, Ni and Pd. The absolute loading ratios of H(D)/metal were calculated from the ERDA spectra and the depth profiles of SIMS were compared with the results of the ERDA. The isotope absorption ratios are estimated to be (D/H)_Ti=0.43, (D/H)_Zr=0.53, (D/H)_Nb=0.17 and (D/H)_Pd=0.10. The content in Ni is below the detection limit. The mass balance equations based on the transport–absorption model, were applied to analysis of the experimental results. This model reveals that the isotope absorption ratios for the Nb and Pd cases are governed mainly by the flux of hydrogen ions flowing to the surface of the metal electrode. However, the competition between the absorption–conversion process and the recombination process mainly determine the isotope ratio for the Ti and Zr cases.     

H/D isotope effect for solubility of hydrogen in doped perovskites

A novel method for studying the H/D isotope separation effect in the “nonstoichiometric oxide-gas” system is suggested. The theoretical scheme of this method is represented for doped perovskites of the ABO₃ family, but this approach is also applicable to other compounds where the solubility of hydrogen is determined by the content of oxygen vacancies. The suggested approach is used to determine the H/D isotope effect in hydrogen solubility from the experimental data for proton-conducting oxides. The measurements have been taken using the nuclear microanalysis of fine-grain BaZr_0.9Y_0.1O_{3 − y} powders. The method is based on the study of the products of the ²H(d, p)³H nuclear reaction. The observed pronounced isotope effect is in quantitative agreement with our theoretical predictions.     

One- and two-dimensional 15N exchange CP/MAS NMR studies of the structure and electronic properties of the intermolecular N-H...N hydrogen bond in imidazole crystal

The hydrogen bond of the type N-H...N in imidazole crystal has been studied by one and two-dimensional 15N exchange CP/MAS NMR measurements as well as the powder NMR spectrum. The chemical shift anisotropies for -N= and -N< were determined from the powder 1D spectrum. In 2D exchange CP/MAS NMR spectrum, the cross peaks between the 15N main resonance peaks for -N= and -N< were observed, implying that magnetization exchange between -N= and -N< takes place. The 1D exchange CP/MAS NMR measurements determined the exchange rate of magnetization at 289 K to be 1.3 and 1.5 s(-1) for -N= and -N<, respectively. The proton-driven spin-diffusion model interprets the experimental values, and the exchange rate depends strongly on the RF power of the proton decoupling field, suggesting that the magnetization transfer between -N= and -N< takes place by the 1H-driven spin-diffusion mechanism.     

Nuclear Overhauser Enhancement Effect in Distinguishing Rapid Aromatic Hydrogen Exchange in Primaquine and Related Analogues

NOE phenomenon has been observed and employed to distinguish rapid aromatic hydrogen exchange in primaquine and related analogues. The hydrogens at carbons 5 and 7 in the quinoline nucleus undergo acid-catalyzed H/D exchange with faster exchange at C-5 relative to C-7.     

Supramolecular encapsulation of 1,3‐bis(1‐adamantyl)imidazolium chloride by β‐cyclodextrins: towards inhibition of C(2)‐H/D exchange

The study of the hydrogen/deuterium exchange reactions of the C(2)‐proton for different carbene precursors has been carried out in the absence and presence of β‐cyclodextrin in D₂O at 25°C. Formation of the inclusion complexes of imidazolium salts with the native β‐cyclodextrin and the β‐dimethylcyclodextrin is demonstrated by 1D and 2D ¹H NMR, ESI/HRMS and a molecular modelling study. Formation of the inclusion complexes of imidazolium salts with the native β‐cyclodextrin and the β‐dimethylcyclodextrin is a simple and efficient method to modify the acidity of the imidazolium H(2) and to modify its environment. Encapsulation of 1,3‐disubstituted imidazolium chloride by β‐cyclodextrins results in the inhibition of the H(2)/D exchange in the complex. Copyright © 2008 John Wiley & Sons, Ltd.     

Liquid Phase Kinetic and Thermodynamic Studies on Promoted Nickel Catalysts used for H/D Exchange

Successful choice of the suitable catalyst composition for hydrogen/deuterium exchange reaction between hydrogen and water requires understanding of chemical kinetics as well as surface properties and activity in both liquid- and vapour phases. The present study deals with the thermodynamic and kinetic behaviour of a simple liquid phase reaction on the surface of nickel catalyst promoted with zirconium oxide used for the H/D exchange. This study helps understand the condensation of water on the catalyst surface during operation which leads to its poisoning. In this specific case water molecules are responsible for selective poisoning of this type of catalysts. The reaction rate constant, the increase in Gibb,s free energy, the enthalpy, the entropy of activation and the energy of activation were calculated.     

Interaction Between Cytochrome c and the Hapten 2,4-Dinitro-fluorobenzene by Electrospray Ionization Mass Spectrometry

采用电喷雾质谱、H/D交换和紫外光谱测定了半抗原2,4-二硝基氟苯和模型蛋白细胞色素c的相互作用. 电喷雾质谱结果表明,随着2,4-二硝基氟苯体积比百分含量的增加,细胞色素c的构象可以由天然的折叠构象转变为部分非折叠构象,最后转变为完全非折叠构象.细胞色素c在平衡态的H/D交换结合电喷雾质谱实验结果进一步确认了上述构象变化. 紫外光谱结果表明半抗原的加入对辅基血红素上的亚铁离子和细胞色素c上His18和Met80的强场配位作用没有明显的影响.     

圆筒内氢等离子体非定常化学反应羽流场DSMC分析

利用直接模拟Monte Carlo方法研究圆筒侧壁注入氢等离子体羽流场在8×10^-6s内的非定常流动特性.根据Bird的化学反应模型考虑离解-复合反应模型和电荷转移反应模型.在流场中注入H₂、H、金属原子X、H₂⁺和H⁺五种组分,研究离解-复合反应对流场中粒子分布和密度的影响,结果表明离解-复合反应使H₂数密度降低,H数密度增加,说明在流场中H₂的离解反应速率大于H的复合反应速率.加入电荷转移反应后H₂⁺数密度降低,H⁺数密度增加,对其他组分数密度没有显著影响.     

A local mixing model for deuterium replacement in solids

A new model for hydrogen isotope exchange by ion implantation has been developed. The basic difference between our approach and previous work is that we include the depth distribution of the implanted species. The outstanding feature of this local mixing model is that the only adjustable parameter is the saturation hydrogen concentration which is specific to the target material and dependent only on temperature. The model is shown to give excellent agreement both with new data on H/D exchange in the low Z, coating materials VB₂, Tie, TiB₂, and B reported here and with previously reported data on stainless steel. The saturation hydrogen concentrations used to fit these data were 0.15, 0.25, 0.15, 0.45, and 1.00 times atomic density respectively. This model should be useful in predicting the recycling behavior of hydrogen isotopes in tokamak limiter and wall materials.     

正负离子碰撞过程中电荷转移的理论研究

文中用渐近方法，采用未微扰的原子波函数，导出了正负离子碰撞过程中，当离子间的距离很大时，入射离子道与出射共价道之间的交换相互作用的解析表达式。利用该相互作用的解析表达式，并考虑在入射通道里Ｈ－离子核外有两个同科电子的情况，由多通道Ｌａｎｄａｕ－Ｚｅｎｅｒ模型分别计算了低能Ｈ＋＋Ｈ－和Ｄ＋＋Ｈ－碰撞过程中的电荷转移总截面。计算结果与已有的实验数据进行了比较。     

Hydrogen atoms in impurity-helium solids

Electron spin resonance (ESR) is employed to study atomic impurities (H and D) stabilized in impurity-helium (Im-He) solids at 1.35-1.5 K. The kinetics of the low temperature tunneling exchange reactions (D+H2-->H+HD, D+HD-->H+D2) are investigated in Im-He samples containing several different mixtures of hydrogen and deuterium impurities. The ESR line structures help determine the local environment of atoms trapped in Im-He solids. High concentrations of atomic hydrogen stored in Im-He solids may ultimately find applications in energy storage, matrix-isolation spectroscopy, and studies of different quantum statistical effects.     

计算氢同位素水分子汽化焓的比较法

本文首次提出计算氢同位素水分子汽化焓的比较法,得到0～374℃时H2O,D2O,DTO和T2O的汽化焓,并提出用D2从含氚重水中分离出DT气的适宜温度.     

Hydrogen bonding in different pyrimidine–methanol clusters probed by polarized Raman spectroscopy and DFT calculations

We report on the hydrogen bonding between pyrimidine (Pd) and methanol (M) as H‐donor in this study. Hydrogen bonds between pyrimidine and methanol molecules as well as those between different methanol molecules significantly influence the spectral features at high dilution. The ring‐breathing mode ν₁ of the reference system Pd was chosen as a marker band to probe the degree of hydrogen bonding. Polarized Raman spectra in the region 970–1020 cm⁻¹ for binary mixtures of (pyrimidine + methanol) at 28 different mole fractions were recorded. A Raman line shape analysis of the isotropic Raman line profiles at all concentrations revealed three distinct spectral components at mole fractions of Pd below 0.75. The three components are attributed to three distinct groups of species: ‘free Pd’ (pd), ‘Pd with low methanol content’ (pd1) and ‘Pd with high‐methanol content’ (pd2). The two latter species differ considerably in the pattern and the strengths of the hydrogen bonds. The results of density functional theory calculations on structures and vibrational spectra of neat Pd and eight Pd/M complexes with varying methanol content support our interpretations of the experimental results. A nice spectra–structure correlation for the different cluster subgroups was obtained, similar to earlier results obtained for Pd and water. Apart from N···H and O···H hydrogen bonds between pyrimidine and methanol, O···H hydrogen bonds formed among the methanol molecules in the cluster at high methanol content also play a crucial role in the interpretation of the experimental results. Copyright © 2010 John Wiley & Sons, Ltd.     

On the H-exchange of ammonia and silica hydroxyls in the presence of Rh nanoparticles

Attenuated total reflection infrared spectroscopy (ATR-FT-IR) is employed to study the H/D-exchange of planar hydroxylated silica during ND₃ and D₂ dosing, and catalyzed by Rh nanoparticles. For ND₃ dosing, it is observed that the H/D-exchange is about 10 times more efficient in the presence of Rh nanoparticles on the hydroxylated silica than for bare hydroxylated silica. When the Rh adsorption sites are blocked by CO, the H/D-exchange is similar to the case without Rh nanoparticles. No H/D-exchange is observed for exposure to D₂ regardless of the presence of Rh nanoparticles. Hydrogen spillover, involving the decomposition of D₂ on the Rh and subsequent transfer of atomic D to the oxide support, therefore does not explain the observed effects. Alternatively, we conjecture that for ND₃, the exchange is through a mechanism in which ND₃ adsorption on the edge of the Rh particles takes place, followed by direct H/D exchange with the hydroxyls of the support. This exchange is possibly aided by the formation of ammonium complexes with the help of hydrogen from the hydroxyls.