Production of nitrogen-free, hyperpolarized 129Xe gas

129 Xe with a nuclear polarization far above the thermal equilibrium value (hyperpolarized) is used in NMR studies to increase sensitivity. Gaseous, adsorbed, or dissolved xenon is utilized in physical, chemical, and medical applications. With the aim in mind to study single-crystal surfaces by NMR of adsorbed hyperpolarized ¹²⁹Xe, three problems have to be solved. The reliable production of ¹²⁹Xe with highest nuclear polarization possible, the separation of the xenon gas from the necessary quench gas nitrogen without polarization loss, and the dosing/delivery of small amounts of polarized xenon gas to a sample surface. Here we describe an optical pumping setup that regularly produces xenon gas with a ¹²⁹Xe nuclear polarization of 0.7(±0.07). We show that a freeze–pump–thaw separation of xenon and nitrogen is feasible without a significant loss in xenon polarization. The nitrogen partial pressure can be suppressed by a factor of 400 in a single separation cycle. Dosing is achieved by using the low vapor pressure of a frozen hyperpolarized xenon sample. Received: 12 June 1998     

Characteristics of adsorption phase with water/organic mixtures at a surface of activated carbons possessing intraparticle and textural porosities

The behaviour of water and water/organic mixtures adsorbed onto activated microporous carbons or a carbon adsorbent with narrow intraparticle micropores and broad mesopores and macropores between nanoparticles was studied using low-temperature adsorption method and ¹H NMR spectroscopy with layer-by-layer freezing-out of liquids at 190-273 K. These investigations revealed concentration-dependent effects of benzene, DMSO, acetone, chloroform, methane and acetonitrile on the characteristics of adsorbed water and the influence of this water on the interfacial behaviour of adsorbed organics. The influence of organics causes the structural and energetic differentiations of adsorbed water. The latter can be displaced by organics from micropores into broader pores and/or form mixture with polar solvents in meso and macropores. Freezing of adsorbed water can affect the adsorbent structure because ice crystallites have a larger size than that of liquid water droplets that lead to changes in the behaviour of adsorbed water/organic mixtures observed by the ¹H NMR and adsorption methods.     

基于气液混合层的吸附气体稳定性机理

实验表明溶解在水中的气体会在疏水表面吸附和集聚,学界普遍认为其有"纳米气泡"和"微气饼"两种存在形式.对于这两种形式,经典理论无法解释其稳定存在.本文采用分子动力学方法对气体吸附和积聚过程进行模拟,结果显示吸附气体表层覆盖着气液混合层,对该混合层的形状和特性进行分析和研究,发现该气液混合层具有较高的粘度并且对气体的扩散...     

CH4水合物在SDS和CTAB溶液中的生成特性研究

为探究不同促进剂在甲烷水合物生成过程的微观作用机理,选取动力学促进剂十二烷基硫酸钠(SDS)和热力学促进剂十六烷基三甲基溴化铵(CTAB)作为添加剂,采用分子动力学方法研究其对甲烷水合物生成速率的影响.通过分析势能变化、均方位移、径向分布函数、分子簇生长速率,发现质量分数为0.9%SDS、1.2%SDS、1.2%CTAB、1.6%CTAB的溶液均可促进水合物生成.质量分数为1.2%的SDS溶液水合物生长速率最快,且SDS促进效果优于CTAB.通过分析甲烷分子密度分布云图,发现呈阴性的SDS分子头部基团吸附了大量甲烷分子,水分子受挤压向中间聚集;CTAB含氮的头部基团朝向均相溶液,包含在不稳定的水合物笼中,形成半笼型水合物.相比之下,CTAB溶液中水合物含气率更高.     

Proton NMR study of α-MnH0.06

Proton nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rates for the solid solution α-MnH_0.06 have been measured over the temperature range 11-297 K and the resonance frequency range 20-90 MHz. A considerable shift and broadening of the proton NMR line and a sharp peak of the spin-lattice relaxation rate are observed near 130 K. These effects are attributed to the onset of antiferromagnetic ordering below the Néel temperature T_N≈130 K. The proton NMR line does not disappear in the antiferromagnetic phase; this suggests a small magnitude of the local magnetic fields at H-sites in α-MnH_0.06. The spin-lattice relaxation rate in the paramagnetic phase is dominated by the effects of spin fluctuations.     

Melting mechanism of monolayers adsorbed in cylindrical pores: An influence of the pore wall roughness

We have analyzed the mechanism of melting of layers adsorbed in cylindrical pores of porous materials. The goal was to understand the melting mechanism of simple fluids adsorbed in pores with heterogeneous wall surface. The studied system was a monolayer of methane molecules adsorbed in MCM-41 pore of diameter d = 4 nm. Both experimental (neutron scattering) and simulation (Monte Carlo) results proved extremely strong influence of the wall roughness on the melting mechanism. The most striking difference between melting on smooth and rough surfaces was in the temperatures of the transition. The transformation between solid-like and liquid-like monolayer phases adsorbed on a rough surface was observed in a very large temperature range and the solid like properties were observed even above the bulk methane melting temperature.     

石墨狭缝中甲烷吸附的分子动力学模拟

用分子动力学模拟研究石墨狭缝中甲烷的吸附,考察狭缝宽度和温度对甲烷吸附的影响.模拟发现甲烷在石墨狭缝中出现分层现象,吸附层中甲烷具有类液特征,第一吸附层内甲烷中总有两个氢原子的连线与另外两个氢原子的连线分别位于平行于狭缝壁的两个平面内,游离层中甲烷呈现气体的特征;碳原子间的平均作用势说明吸附层中甲烷分子间结合能力大于游离层,吸附态是甲烷在石墨狭缝中的主要赋存形式之一;伦敦力以及由吸附层净电荷产生的电场力是甲烷吸附和分层的主要原因;甲烷的吸附量随狭缝宽度增大或温度升高而减少,当狭缝宽度小于16.46Å时,甲烷仅以吸附形态存在.甲烷在第一吸附层中的扩散能力最弱、游离层中最强,甲烷扩散系数随狭缝宽度的增大或温度的升高而增大.     

Investigation of chemisorbed oxygen, surface segregation and effect of post-treatments on La0.8Sr0.2MnO3 powder and screen-printed layers for solid oxide fuel cell cathodes

In order to better understand the mechanism of the reaction of oxygen reduction at the surface of strontium doped lanthanum manganites (LSM) cathodes in solid electrolyte fuel cells (SOFC), the surface properties of La_0.8Sr_0.2MnO₃ powders and screen-printed layers have been characterised by various techniques.Strontium enrichment at the surface has been evidenced by X-ray photoelectron spectroscopy according to the conditions of annealing (temperature, oxygen pressure) and polarisation treatments of the samples.The interaction between oxygen and La_0.8Sr_0.2MnO₃ for SOFC cathodes has been studied by thermo-programmed desorption, in situ infrared spectrometry and calorimetry. The results indicate that various adsorbed oxygen species may exist on the surface of LSM depending on temperature.The presence of various adsorbed oxygen species and the surface Sr segregation are important factors to consider in the mechanism of oxygen reduction at LSM SOFC cathodes since they could be responsible for many discrepancies between the interpretations that can be found in the literature data.     

Quantum computation based on magic-angle-spinning solid state nuclear magnetic resonance spectroscopy

Magic-angle spinning (MAS) solid state nuclear magnetic resonance (NMR) spectroscopy is shown to be a promising technique for implementing quantum computing. The theory underlying the principles of quantum computing with nuclear spin systems undergoing MAS is formulated in the framework of formalized quantum Floquet theory. The procedures for realizing state labeling, state transformation and coherence selection in Floquet space are given. It suggests that by this method, the largest number of qubits can easily surpass that achievable with other techniques. Unlike other modalities proposed for quantum computing, this method enables one to adjust the dimension of the working state space, meaning the number of qubits can be readily varied. The universality of quantum computing in Floquet space with solid state NMR is discussed and a demonstrative experimental implementation of Grover's search is given. Received 19 April 2001     

Proton magnetic resonance study of the low-temperature phase transition in a LiNH4SO4 single crystal

The proton NMR line width and spin-lattice relaxation times for LiNH₄SO₄ single crystal were studied at low temperature range of 6 and 280 K. The changes in the proton relaxation behavior near the phase transition temperature indicates a change in the state of internal motion at the transition. The molecular motions obtained by the spin-lattice relaxation processes were found to be determined by molecular reorientation of the NH₄ ions in phases III, IV, and V. We also confirmed that the phase transitions occur at 26 and 133 K.     

Displacive and order-disorder behavior of KDP-type ferroelectrics on the local scale

The modified strong dipole-proton coupling (MSDPC) model, which predicted several static and dynamic dielectric properties of KH₂PO₄ or KDP-type ferroelectrics, was used to investigate the properties of these crystals on the local scale. Results calculated by molecular dynamics (MD) simulation show that both order-disorder and displacive characteristics of one PO₄ dipole are present in KDP and KD₂PO₄ (DKDP). These results correlate with experimental data from NMR and neutron scattering studies of local properties.     

Studies of positron moderation in surface charged rare gas solids

With the use of surface charging the efficiency of a rare gas solid (RGS) positron (e⁺) moderator has been determined as a function of applied electric field. This technique relies on electron (e⁻) capture by adsorbed molecular species such as oxygen. These studies have shown that the emitted e⁺ yield from an RGS moderator can be enhanced by at least a factor of three by negative surface charging or almost totally reduced by positive surface charging. Even under ultra high vacuum conditions significant surface charging of RGS films can occur and such effects should be considered if moderating materials of this type are to be used.     

Neutron diffraction and inelastic scattering from adsorbed molecules

Neutron scattering measurements on the structure and dynamics of adsorbed phases at the gas solid interface have proliferated in the last five years and this paper reports some recently obtained results for the systems methane-graphite and ammonia-graphite, which show BET type I and type III isotherms respectively. These systems clearly illustrate the differences in both structure and dynamics to be expected in other examples where either wetting of the surface or non-wetting behaviour occurs upon adsorption. Evidence for phase transitions in both types of system coming from diffraction is reported, and this is substantiated by measurements using inelastic scattering to follow the molecular dynamics. The neutron inelastic scattering from molecules adsorbed on platinum black and in zeolites reveals some of the virtues of neutron inelastic scattering for the study of chemisorbed species. Finally, some preliminary experiments on neutron small angle scattering at the solid liquid interface in polystyrene latex-water sols are reported.     

Molecular-beam mass spectrometry study of oxy-combustion in a novel coal-plate experiment

Oxy-fuel coal combustion could play a significant role in the foreseeable future for its application in carbon capture and storage (CSS) technologies. Therefore, detailed knowledge about the ongoing chemical kinetics in the combustion process is necessary. Here, we present an explorative approach to study volatile species gas phase kinetics in a novel coal-plate experiment probed with molecular-beam mass spectrometry. This coupling allows for time-resolved quantitative measurements of the gas-phase directly above the surface of solid fuels, which aid gaining more insight into the gas phase chemistry during coal combustion by detailed speciation information. Two coal samples, a rhenish lignite and a coal manufactured from hydrothermal carbonization, were chosen for this investigation due to their similar classification but different molecular structures. For both samples, our measurements show a two-stage devolatilization phase separated by a char-oxidation phase which can be attributed to the interaction of oxygen consumption in the gas phase and on the surface and the release of volatiles from deeper layers of the plate. Furthermore, detailed speciation data of light, oxygenated, and tar species allowed to identify fuel structure-specific decomposition patterns of the two different coal materials, thus providing comprehensive data that can be used for future model validation purposes.     

Molecular-dynamics simulation of methane adsorbed on MgO: Evidence for a Kosterlitz-Thouless transition

A realistic model of a monolayer molecular crystal of methane adsorbed on the (100) surface of MgO has been studied by means of molecular dynamics. The model treates the atomicity of the MgO substrate explicitly. Large corrugations in energy are found for both the translational and rotational motion of methane across the substrate. The preferred configurations of adsorption is over an Mg²⁺ ion in a tripod-down orientation. The orientationally ordered low-energy states of the monolayer have been found. Finite-size-scaling calculations on systems of different sizes indicate, however, that the ordered state exhibits only quasi-long-range order. The disclinations in the ordered phase exist in low concentrations and in bound pairs. Evidence is presented for a Kosterlitz-Thouless-type unbinding transition occurring at T _c ≈ 27 K. No evidence is found for a first-order transition. The specific heat exhibits an anomaly at T ≈ 32 K. The disclination density in the region of the transition is reported; below T _c, this density can be fitted to an Arrhenius-type law, yielding an estimate of the core enegy for a bound vortex-antivortex pair.     

Solid state and solution 43Ca NMR of calcium peroxides involved in the disproportionation of hydrogen peroxide by calcium hydroxide

In order to get some insight into the mechanism of the disproportionation of hydrogen peroxide catalyzed by calcium hydroxide, 43Ca NMR spectra of enriched samples of calcium peroxides and of their precursors have been studied in both solution and solid state. This study demonstrates that no well-defined peroxidized calcium species are formed in solution, showing that the catalytic role of calcium is likely restricted to the solid state. Most of the calcium compounds that could be involved in the catalytic process have been investigated with solid state NMR. The shift and quadrupolar parameters of Ca(OH)2, CaO2.8H2O and CaO2.2H2O2 are reported for the first time. These parameters are different enough to allow the quantitative analysis of a complex mixture of these compounds by NMR.     

Observation of micropores in hard-carbon using Xe NMR porosimetry

The existence of micropores and the change of surface structure in pitch-based hard-carbon in xenon atmosphere were demonstrated using ¹²⁹Xe NMR. For high-pressure (4.0 MPa) ¹²⁹Xe NMR measurements, the hard-carbon samples in Xe gas showed three peaks at 27, 34 and 210 ppm. The last was attributed to the xenon in micropores (<1 nm) in hard-carbon particles. The NMR spectrum of a sample evacuated at 773 K and exposed to 0.1 MPa Xe gas at 773 K for 24 h showed two peaks at 29 and 128 ppm, which were attributed, respectively, to the xenon atoms adsorbed in the large pores (probably mesopores) and micropores of hard-carbon. With increasing annealing time in Xe gas at 773 K, both peaks shifted and merged into one peak at 50 ppm. The diffusion of adsorbed xenon atoms is very slow, probably because the transfer of molecules or atoms among micropores in hard-carbon does not occur readily. Many micropores are isolated from the outer surface. For that reason, xenon atoms are thought to be adsorbed only by micropores near the surface, which are easily accessible from the surrounding space.     

Characterization of LaMnAl11O19 by FT-IR spectroscopy of adsorbed NO and NO/O2

The nature of the NO_x species produced during the adsorption of NO at room temperature and during its coadsorption with oxygen on LaMnAl₁₁O₁₉ sample with magnetoplumbite structure obtained by a sol-gel process has been investigated by means of in situ FT-IR spectroscopy. The adsorption of NO leads to formation of anionic nitrosyls and/or cis-hyponitrite ions and reveals the presence of coordinatively unsaturated Mn³⁺ ions. Upon NO/O₂ adsorption at room temperature various nitro-nitrato structures are observed. The nitro-nitrato species produced with the participation of electrophilic oxygen species decompose at 350 °C directly to N₂ and O₂. No NO decomposition is observed in absence of molecular oxygen. The adsorbed nitro-nitrato species are inert towards the interaction with methane and block the active sites (Mn³⁺ ions) for its oxidation. Noticeable oxidation of the methane on the NOx⁻-precovered sample is observed at temperatures higher than 350 °C due to the liberation of the active sites as a result of decomposition of the surface nitro-nitrato species. Mechanism explaining the promoting effect of the molecular oxygen in the NO decomposition is proposed.     

Modelling of dynamical processes in a molecular crystal by NMR

In this contribution we report on the plastic crystal 1-chloroadamantane dynamics via conventional frequency dependent (¹H and ¹³C) and field cycling NMR measurements. A suitable microscopic dynamical model, worked out from from X-ray analysis is developed and the molecular motions are interpreted in terms of: self diffusion and dipolar molecular axis combined with uniaxial rotation. In the rotator phase the molecules execute a bimodal reorientation process whereas the uniaxial rotation solely persists in the low temperature phase. In both phases, the residence times exhibit an Arrhenius temperature dependence. The results confirm the existence of a dynamic crossover transition predicted by molecular dynamics simulation.     

甲烷气体在泡沫陶瓷中预混燃烧的数值模拟和实验研究

本文对甲烷气体在泡沫陶瓷内燃烧进行了数值模拟和实验研究.根据预混燃烧理论,建立了基于气固两相局部非热平衡模型,采用 26 种组分,77 步详细化学反应机理来模拟反应过程.边界上的辐射换热采用双通量法求解,为减少计算时间,计算区域内部利用扩散近似法求解.为减少边界条件对模拟结果精度的影响,提出了采用能量平衡方法,建立边界上的对流,导热和辐射的整个换热过程,模拟表明这种边界条件具有二阶离散精度.