High specific surface area TEOS-based aerogels with large pore volume prepared at an ambient pressure

The experimental results on the synthesis of tetraethoxysilane (TEOS)-based silica aerogel with high specific surface area and large pore volume, via ambient pressure drying (APD) route, are reported. The silica aerogels were prepared by the acid-base sol-gel polymerization of TEOS precursor followed by the drying of the alcogels at an ambient pressure. The solvent present in the alcogel (i.e. ethanol) was replaced by a non-polar solvent such as hexane prior to the surface modification step. In order to minimize the drying shrinkage, the surface of the gels was modified using trimethylchlorosilane (TMCS) before the APD. The FTIR spectra of the surface modified aerogels showed Si-CH₃ peaks at 2965 and 850 cm⁻¹. The effect of the base catalyst (NH₄OH) addition to the sol, at different time intervals (T), on the physical and textural properties of the resulting aerogels has been investigated. It has been observed that the surface area and the cumulative pore volume of the aerogels enhanced considerably from 819 to 1108 m² g⁻¹ and 2.65 to 4.7 cm³ g⁻¹, respectively with an increase in the T value from 6 to 48 h. Silica aerogels with very low bulk density (0.06 g cm⁻³), extremely high specific surface area (1108 m² g⁻¹) and large cumulative pore volume (4.7 cm³ g⁻¹) could be synthesized by drying the alcogels at the ambient pressure. The aerogels were mesoporous solids with the average pore size ranging from 12 to 17 nm. The results have been discussed by taking into consideration the hydrolysis and condensation reactions during the sol-gel polymerization of the TEOS precursor.     

Pulsed-Field-Gradient Measurements of Time-Dependent Gas Diffusion

Pulsed-field-gradient NMR techniques are demonstrated for measurements of time-dependent gas diffusion. The standard PGSE technique and variants, applied to a free gas mixture of thermally polarized xenon and O₂, are found to provide a reproducible measure of the xenon diffusion coefficient (5.71 × 10⁻⁶m²s⁻¹for 1 atm of pure xenon), in excellent agreement with previous, non-NMR measurements. The utility of pulsed-field-gradient NMR techniques is demonstrated by the first measurement of time-dependent (i.e., restricted) gas diffusion inside a porous medium (a random pack of glass beads), with results that agree well with theory. Two modified NMR pulse sequences derived from the PGSE technique (named the Pulsed Gradient Echo, or PGE, and the Pulsed Gradient Multiple Spin Echo, or PGMSE) are also applied to measurements of time dependent diffusion of laser polarized xenon gas, with results in good agreement with previous measurements on thermally polarized gas. The PGMSE technique is found to be superior to the PGE method, and to standard PGSE techniques and variants, for efficiently measuring laser polarized noble gas diffusion over a wide range of diffusion times.     

Measurement of diffusion coefficients in polystyrene using xenon-129 NMR

A sample of polystyrene beads, 18 μm in diameter, has been sealed in an NMR tube under 10 atm of xenon gas. Two dimensional,¹²⁹Xe NMR spectra show cross peaks between the resonances corresponding to xenon in the free gas and the sorbed state, indicating that appreciable exchange occurs during the mixing time of the NMR experiment. Selective saturation of the free gas resonance attenuates the integrated intensity of the sorbed xenon resonance as a function of saturation time, thus allowing the accurate measurement of the exchange rates between the gas and the sorbed states. A model has been developed using a slightly modified form of Crank’s treatment of diffusion in a sphere which allows for the accurate determination of the diffusion coefficient for xenon in the sorbed state. The diffusion coefficient for xenon in polystyrene at 25°C is determined to be 2.9·10^?9 cm²/s.     

Noninvasive Measurements of Gas Exchange in a Three-Dimensional Fluidized Bed by Hyperpolarized 129Xe NMR

We present a novel nuclear magnetic resonance (NMR) technique that provides a noninvasive, direct measurement of gas exchange in a three-dimensional gas-fluidized bed of solid particles. The NMR spectrum of hyperpolarized ¹²⁹Xe gas in an Al₂O₃ particle bed displays three resolved peaks corresponding to xenon in bubbles, the interstitial spaces (emulsion), and adsorbed on particles. Modified NMR exchange and saturation recovery sequences, together with data analysis based on an exchange-coupled set of Bloch equations, yield gas exchange rate constants between the emulsion and adsorbed phases, and between the bubble and emulsion phases. The results are in approximate agreement with previously unverified predictions from well-known models of fluidized bed behavior. Incorporation of NMR imaging methodologies would straightforwardly allow similar measurements on a spatially resolved basis. Authors' address: Ross W. Mair, Harvard Smithsonian Center for Astrophysics, MS 59, 60 Garden Street, Cambridge, MA 02138, USA     

Spatially resolved adsorption isotherms of thermally polarized perfluorinated gases in yttria-stabilized tetragonal-zirconia polycrystal ceramic materials with NMR imaging

This paper presents the results obtained by nuclear magnetic resonance (NMR) imaging of perfluorinated gases in mesoporuous solids. NMR images of nuclear spin density as a function of gas pressure permits spatially resolved measurements that are analogous to conventional bulk Brunauer-Emmett-Teller adsorption isotherm measurements. The use of NMR imaging allows the nondestructive evaluation of macroscopic spatial variations in the underlying mesoporous structure, for materials such as partially sintered Y-TZP (yttria-stabilized tetragonal-zirconia polycrystal) ceramics. All NMR measurements were performed with octafluorocyclobutane (C₄F₈) gas, using only the thermal Boltzman nuclear magnetization.     

Diffusion studies in confined nematic liquid crystals by MAS PFG NMR

Pulsed field gradient (PFG) NMR and magic-angle spinning (MAS) NMR have been combined in order to measure the diffusion coefficients of liquid crystals in confined geometry. Combination of MAS NMR with PFG NMR has a higher spectroscopic resolution in comparison with conventional PFG NMR and improves the application of NMR diffusometry to liquid crystals. It is found that the confinement of the liquid crystal 5CB in porous glasses with mean pore diameters of 30 and 200 nm does not notably change its diffusion behavior in comparison with the bulk state.     

Evidence of microphase separation in controlled pore glasses

The phase separation of a mixture of water and isobutyric acid (iBA) confined in the pore space of Controlled Pore Glass (CPG) 10-75 has been studied by ¹H NMR relaxometry and ¹H-pulsed field gradient (PFG) diffusion measurements. For an acid-rich mixture (mass fraction 54 wt% iBA), evidence of a phase separation process in the pores was obtained, which occurs in a temperature window between 32 and 39 °C, as indicated in the PFG data by an anomalous temperature dependence of the diffusion coefficient and in the relaxation data by a bi-exponential magnetization decay. The phase separation temperature of the mixture in the pore is slightly lower than in the bulk mixture of the same composition (41 °C) and extends over a finite temperature range. A qualitative model of the phase separation process in the pores is developed, which assumes a temperature-dependent domain-like structure of the liquid below the phase transition temperature and a breakdown of these domains upon reaching the transition temperature.     

Spatially resolved emulsion droplet sizing using inverse Abel transforms

Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) is well established as a tool for determining emulsion droplet-size distributions via measurement of restricted self-diffusion. Most measurements made to date have not been spatially resolved, but have measured an average size distribution for a certain volume of emulsion. This paper demonstrates a rapid method of performing spatially resolved, restricted diffusion measurements, which enables emulsion droplet sizing to be spatially resolved as a function of radius in cylindrical geometries or pipes. This is achieved by the use of an Abel transform. The technique is demonstrated in various annular systems containing two emulsions, with different droplet-size distributions, and/or a pure fluid. It is also shown that by modifying the pulse sequence by the inclusion of flow-compensating magnetic field gradients, the technique can measure spatially resolved droplet-size distributions in flowing emulsions, with potential applications in spatially resolved on-line droplet-size analysis.     

Extremely fast ambipolar diffusion in n-i-p-i doping superlattices investigated by an all-optical pump-and-probe technique

We report on investigations of the ambipolar diffusion process in n-i-p diodes and n-i-p-i doping superlattices performed by a new all-optical pump-and-probe technique. This new technique allows not only the determination of the ambipolar diffusion coefficient but also the spatially resolved investigation of the stationary distribution of the optically-induced excess carriers. The n-i-p-i doping superlattice exhibited an extremely large ambipolar diffusion coefficient in the range of 10⁴cm²s⁻¹. The ambipolar diffusion coefficient of the n-i-p and n-i-p-i structure was demonstrated not to be a constant but a function of the charge carrier density. This strongly affects the spatial distribution of the excess carriers especially in the large signal regime (density of photo-generated carriers much larger than dark carrier concentration). The spatial distribution of the carriers in the small as well as in the large signal case can be understood theoretically if the real dependence of the ambipolar diffusion coefficient on the carrier density is taken into account.     

Pore diameter mapping using double pulsed-field gradient MRI and its validation using a novel glass capillary array phantom

Double pulsed-field gradient (d-PFG) MRI can provide quantitative maps of microstructural quantities and features within porous media and tissues. We propose and describe a novel MRI phantom, consisting of wafers of highly ordered glass capillary arrays (GCA), and its use to validate and calibrate a d-PFG MRI method to measure and map the local pore diameter. Specifically, we employ d-PFG Spin-Echo Filtered MRI in conjunction with a recently introduced theoretical framework, to estimate a mean pore diameter in each voxel within the imaging volume. This simulation scheme accounts for all diffusion and imaging gradients within the diffusion weighted MRI (DWI) sequence, and admits the violation of the short gradient pulse approximation. These diameter maps agree well with pore sizes measured using both optical microscopy and single PFG diffusion diffraction NMR spectroscopy using the same phantom. Pixel-by-pixel analysis shows that the local pore diameter can be mapped precisely and accurately within a specimen using d-PFG MRI.     

Direct synthesis of mesoporous carbon from the carbonization of hydroxypropyl-β-cyclodextrin/silica composite and its catalytic performance

A simple and efficient route is reported for the synthesis of mesoporous carbon materials by directly carbonizing hydroxypropyl-β-cyclodextrin-silica composites. The resulting carbon materials, with uniform wormlike mesoporous structure and certain degree graphitic phase characteristics in porous wall, possess narrow pore size distribution, high surface area (>1000 m² g⁻¹) and pore volume (>1.2 cm³ g⁻¹). It is worth mentioning that the carbon materials have high catalytic activity for the reduction of p-nitrotoluene using hydrazine hydrate as the reducing agent; moreover, the catalytic activity is not reduced notably after being reused for six times.     

NMR study of the dissolution of laser-polarized xenon

NMR of laser-polarized xenon is used to probe the dissolution behaviour of the noble gas in different liquids. The dissolution and self-relaxation rates are extracted via a macroscopic model, and comparison of the decay rate of the xenon magnetization in deuterated and non-deuterated solvent pairs allows the determination of the pure dipole-dipole contribution to relaxation. A transient convective effect, tentatively assigned to the xenon concentration gradient, is observed and characterized by diffusion encoding MRI experiments. The flow of xenon penetrates inside the solvent near the walls of the NMR tube, the longitudinal images showing a “” shape, the transverse ones a “O” shape. This convection effect has implications for delivery conditions of laser-polarized xenon in continuous flow experiments and magnetic resonance imaging. Received 29 April 2002 / Received in final form 26 July 2002 Published online 22 October 2002 RID="a" ID="a"e-mail: hdesvaux@cea.fr RID="b" ID="b"URA CNRS/CEA 331     

固体核磁共振技术在甲醇制烯烃反应中的应用

甲醇制烯烃过程是由非石油路线生成低碳烯烃的重要途径之一.分子筛因具备独特的孔结构和可调变的酸性质,而成为甲醇制烯烃过程的核心催化剂.固体核磁共振(NMR)是鉴定物质结构、阐释催化反应机理的强有力的工具,在甲醇制烯烃的研究中被广泛应用.本文主要总结了近年来利用原位固体NMR、多维多核NMR、脉冲梯度场NMR等固体NMR技术研究甲醇制烯烃反应机理取得的重要进展.原位固体NMR可以在真实反应条件下监测催化反应中反应物、中间体和产物的动态演变过程;多维多核NMR可以在不破坏催化剂结构情况下确定反应中间体结构信息,特别是¹²⁹Xe NMR可以很灵敏探测反应中催化剂的孔道结构变化;脉冲梯度场NMR可用于测定孔道内分子的扩散系数,阐明分子筛的扩散机制.     

Neutron electric dipole moment measurement with a buffer gas comagnetometer

A neutron EDM measurement with a comagnetometer is discussed. For magnetometry, polarized xenon atoms are injected into a cylindrical cell where a cylindrically symmetric magnetic field and an electric field are applied for the EDM measurement. The geometric phase effect (GPE), which originates from particle motion in a magnetic field gradient, is analyzed in terms of the Dyson series. The motion of the xenon atom is largely suppressed because of a small mean free path. The field gradient is controlled by means of NMR measurements, where the false effect of Earth?s rotation is removed. As a result, the GPE is reduced below 10⁻²⁸e cm${10}^{-28}e\text{cm}$.     

High resolution Fourier transform infrared spectra and analysis of the ν14, ν15 and ν16 bands of azetidine

Rotationally resolved vibrational spectra of the three lowest frequency bands of the four-membered heterocycle azetidine (c-C₃H₆NH) have been collected with a resolution of 0.00096 cm⁻¹ using the far infrared beamline at the Canadian Light Source synchrotron. The modes observed correspond principally to motions best described as: β-CH₂ rock (ν₁₄) at 736.701310(7) cm⁻¹, ring deformation (ν₁₅) at 648.116041(8) cm⁻¹, and the ring puckering mode (ν₁₆) at 207.727053(9) cm⁻¹. A global fit of 14 276 rovibrational transitions from the three bands provided an accurate set of ground state spectroscopic constants as well as excited state parameters for each of the three vibrational modes. The ground state structure was determined to be that of the puckered conformer having the NH bond in an equatorial arrangement.     

The hierarchical porous structure of carbon aerogels as matrix in cathode materials for Li-S batteries

For Li-S batteries, commercial application was hindered by the insulating nature of S and the solubility of polysulfide. Porous carbon materials had proven themselves to be an ideal immobilizer host for S impregnation. Herein, carbon aerogels (CAs) with tunable pore microstructure were synthesized from resorcinol-formaldehyde reaction with increasing catalyst concentration and pyrolysis under high temperature. The results demonstrated that the catalyst concentration played a key role in tuning the porous microstructure of the CAs. In addition, potassium hydroxide (KOH) was introduced to activate the obtained CAs. The activated carbon aerogels (A-CAs) with hierarchical porous structure exhibited the highest specific surface area (1837.4 m² g^?1) and the largest total pore volume (2.276 cm³ g^?1), which combined the advantages of both mesoporous and microporous. The effects of porous microstructure, specific surface area, and pore volume of the CAs and A-CAs on S incorporation were studied. The S/A-CAs exhibited significantly improved reversible capacity (1260 mAh g^?1 at a rate of 0.1 C), enhanced high-rate property, and excellent cycling performance (229 mAh g^?1 after 500 cycles at 1 C) as a cathode for Li-S batteries.     

A reevaluation of the assignment of the vibrational fundamentals and the rotational analysis of bands in the high-resolution infrared spectra of trans- and cis-1,3,5-hexatriene

Assignments of the vibrational fundamentals of cis- and trans-1,3,5-hexatriene are reevaluated with new infrared and Raman spectra and with quantum chemical predictions of intensities and anharmonic frequencies. The rotational structure is analyzed in the high-resolution (0.0013-0.0018 cm⁻¹) infrared spectra of three C-type bands of the trans isomer and two C-type bands of the cis isomer. The bands for the trans isomer are at 1010.96 cm⁻¹ (ν₁₄), 900.908 cm⁻¹ (ν₁₆), and 683.46 cm⁻¹ (ν₁₇). Ground state (GS) rotational constants have been fitted to the combined ground state combination differences (GSCDs) for the three bands of the trans isomer. The bands for the cis isomer are at 907.70 cm⁻¹ (ν₃₃) and 587.89 cm⁻¹ (ν₃₅). GS rotational constants have been fitted to the combined GSCDs for the two bands of the cis isomer and compared with those obtained from microwave spectroscopy. Small inertial defects in the GSs confirm that both molecules are planar. Upper state rotational constants were fitted for all five bands.     

Direct observation of atomic diffusion in warm rubidium ensembles

We present a robust method for measuring diffusion coefficients of warm atoms in buffer gases. Using optical pumping, we manipulate the atomic spin in a thin cylinder inside the cell. Then, we observe the spatial spread of optically pumped atoms in time using a camera, which allows us to determine the diffusion coefficient. As an example, we demonstrate measurements of diffusion coefficients of rubidium in neon, krypton and xenon acting as buffer gases. We have determined the normalized (273 K, 760 Torr) diffusion coefficients to be 0.18 ± 0.03 cm²/s for neon, 0.07 ± 0.01 cm²/s for krypton and 0.052 ± 0.006 cm²/s for xenon.     

High resolution infrared measurements on the ν3 vibration-rotation band of SiH4

The ν₃ vibration-rotation band of silane (²⁸SiH₄) has been measured at high resolution (0.030–0.045 cm⁻¹). The tetrahedral splitting has been partially resolved. The analysis of the band has yielded an improved set of molecular constants.     

Nucleation, growth and properties of Co nanostructures electrodeposited on n-Si(1 1 1)

In the present work, cobalt thin films deposited directly on n-Si(1 1 1) surfaces by electrodeposition in Watts bath have been investigated. The electrochemical deposition and properties of deposits were studied using cyclic voltammetry (CV), chronoamperometry (CA), ex situ atomic force microscopy (AFM), X-ray diffraction (XRD) and alternating gradient field magnetometer (AGFM) techniques. The nucleation and growth kinetics at the initial stages of Co studied by current transients indicate a 3D island growth (Volmer-Weber); it is characterized by an instantaneous nucleation mechanism followed by diffusion limited growth. According to this model, the estimated nucleus density and diffusion coefficient are on the order of magnitude of 10⁶ cm⁻² and 10⁻⁵ cm² s⁻¹, respectively. AFM characterization of the deposits shows a granular structure of the electrodeposited layers. XRD measurements indicate a small grain size with the presence of a mixture of hcp and fcc Co structures. The hysteresis loops with a magnetic field in the parallel and perpendicular direction and showed that the easy magnetization axis of Co thin film is in the film plane.