Surface diffusion and entrapment of simple molecules on porous silica

Interactions of simple molecules with the surface of porous silica have been investigated using time-of-flight secondary ion mass spectrometry and temperature programmed desorption. A monolayer of water diffuses into pores at temperatures higher than 110 K. Multilayers of water are also incorporated in pores via sequential surface diffusion. In contrast, a methanol monolayer tends to stay on the surface up to 150 K, and carbon dioxide diffuses into pores rather gradually. Results can be explained as the contribution of hydrogen bonds between the adsorbate–substrate and adsorbate–adsorbate interactions. The predominance of the former (latter) might be responsible for single-molecule migration of methanol and carbon-dioxide (collective diffusion of water molecules) on the surface. These molecules are entrapped at higher coordination sites in pores, as revealed from thermal desorption peaks appearing at higher temperatures than those from non-porous silica. However, no significant difference is observed in desorption kinetics of CF₂Cl₂, Kr, CH₄, and N₂ molecules between the porous and non-porous silica substrates.     

Resonant radiationless excitation transfer to I2 molecules sorbed in pores of porous silicon

Resonant radiationless electronic excitation transfer to I₂ molecules sorbed in pores of porous silicon was observed. The mass-spectrometry technique was used to show that iodine excitation through the resonant transfer results in the desorption of sorbed I₂ molecules with relatively high kinetic energies (1?3 eV).     

Electronic Excitation Energy Transfer between Different Types of Dye Molecules in a Porous Glass Matrix

The processes of electronic excitation energy transfer (EEET) between different types of dye molecules inserted into the matrix of a porous glass have been investigated. An extreme character of the dependence of the EEET efficiency on the size of pores has been revealed. The dependence of the fractal dimensionality of the distribution of dye molecules on the sizes of the pores has been determined. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 4, pp. 446–449, July–August, 2005.     

Enhancement of fluorescence of porous silicon upon saturation by liquid crystal

The fluorescence of samples of porous silicon of various morphologies that are filled with a liquid crystal (LC), n-pentyl-n′-cyanobiphenyl (5CB), is studied. The fluorescence spectra of the sample, along with the long-wavelength band of porous silicon with a maximum in the range 627–667 nm, exhibit a short-wavelength band of 5CB with a maximum in the range 385–410 nm. The radiative relaxation times of porous silicon and 5CB lie in the micro- and nanosecond ranges, respectively. It is found that the filling of pores with 5CB enhances the fluorescence of porous silicon by two to three times. This enhancement is caused by non-radiative energy transfer from 5CB to the porous matrix as a result of efficient interactions between LC molecules and pore walls. Using IR spectroscopy, it is shown that the formation of hydrogen bonds between cyano groups of 5CB molecules and silanol groups of pore surface is the predominant type of these interactions. A transfer mechanism is suggested according to which excited associates of 5CB molecules transfer their energy via surface channels to excitons of porous silicon, enhancing its fluorescence.     

Fluorescence of the nematic liquid crystal 5CB in nanoporous glasses

The fluorescence spectra of the nematic liquid crystal n-pentyl-n′-cyanobiphenyl (5CB) in porous glasses with pores from 1 to 44 nm in diameter are investigated. A decrease in the pore diameter leads to suppression of some long-wavelength spectral components corresponding to H-type predimer and dimer pairs (the molecular sieve effect). The spectrum of 5CB in small pores (smaller than 4 nm in diameter) can be explained by the superposition of the monomer fluorescence and the fluorescence of J-type dimer pairs of 5CB molecules, as well as associates of 5CB molecules and surface groups on pore walls. Exposure of samples to UV light enhances the molecular interaction in associates, possibly, due to the formation of strong chemical bonds.     

Pore-Size Distributions and Tortuosity in Heterogeneous Porous Media

The diffusion coefficient, measured at long observation times by pulsed-held-gradient NMR, can in principle be used to estimate the tortuosity of a porous medium. This method is useful for glass-sphere packs, but we find that it does not generally work for porous sedimentary rock. Natural sedimentary rocks are characterized by complex microgeometries and broad distributions of pore sizes, which cannot be adequately sampled by diffusing molecules in experimentally accessible observation times. The time-dependent diffusion coefficient D(t) can be distinctly irregular for rocks with very large pores. In heterogeneous porous media, determination of pore-size distribution by relaxation-time measurements and tortuosity by PFG diffusion measurements are mutually exclusive.     

Diffusion kinetics of water molecules in a nanoporous adsorbent

The diffusion of water vapor into porous polymer adsorbent MN-200 has been investigated by diode laser spectroscopy with a time resolution of 0.1 s. The cascade character of diffusion, caused presumably by the fractality of the porous matrix space, is established by decomposition analysis. The collisionless (Knudsen) mode of water motion in pores, in which water molecules can be sorted according to their spin states, is selected.     

Phase transitions in a metal–organic coordination polymer: [Zn2(C8H4O4)2(C6H12N2)] with guest molecules. Thermal effects and molecular mobility

Thermal effects of a series of [Zn₂(C₈H₄O₄)₂(C₆H₁₂N₂)] porous compound with the guest molecules located in the pores were studied using differential scanning calorimetry combined with solid-state ¹H nuclear magnetic resonance spectroscopy. The intercalation of the molecules was shown to produce various thermal anomalies and phase transitions, which were characterized and analyzed.     

Self-diffusion of water and benzene molecules adsorbed in synthetic opal samples

The self-diffusion of adsorbed molecules of water and benzene in porous synthetic opals has been studied by pulsed field gradient nuclear magnetic resonance. The study indicates two “phases” of water molecules differing by the self-diffusion coefficients, indicating two types of porosities existing in the synthetic opals. The smallest self-diffusion coefficient characterizes water in ultramicropores found on the surface of nanospheres. The form of the diffusion decay depends on temperature in the region of high temperatures as a result of exchange between pores of different sizes. The ultramicropores are inaccessible for the largest benzene molecules. Water adsorption and self-diffusion data confirm that annealing of the opal samples at 1293 K caused the collapse of ultramicropores.     

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.     

Investigation of structural and optical properties of nanoporous GaN film

The structural and optical characteristics of porous GaN prepared by Pt-assisted electroless etching under different etching durations are reported. The porous GaN samples were investigated by scanning electron microscopy (SEM), high-resolution X-ray diffraction (HR-XRD), photoluminescence (PL) and Raman scattering. SEM images indicated that the density of the pores increased with the etching duration; however, the etching duration has no significant effect on the size and shape of the pores. XRD measurements showed that the (0 0 0 2) diffraction plane peak width of porous samples was slightly broader than the as-grown sample, and it increased with the etching duration. PL measurements revealed that the near band edge peak of all the porous samples were red-shifted; however, the porosity-induced PL intensity enhancement was only observed in the porous samples; apart from that, two additional strain-induced structural defect-related PL peaks observed in as-grown sample were absent in porous samples. Raman spectra showed that the shift of E₂ (high) to lower frequency was only found in samples with high density of pores. On the contrary, the absence of two forbidden TO modes in the as-grown sample was observed in some of porous samples.     

Phonon scattering from the boundaries of small crystals embedded in a dielectric porous-glass matrix

The thermal conductivity of porous glass with randomly distributed connecting pores ～70 Å in size (glass porosity ～25%), as well as of a porous glass + NaCl composite, was measured in the temperature range 5–300 K. NaCl filled one fourth of the pores in the composite. The experimental results on the composite thermal conductivity can be accounted for only by assuming that phonons scatter from the boundaries of NaCl nanocrystals embedded in channels of the porous glass.     

Transport in solid oxide porous electrodes: Effect of gas diffusion

We extend our previous treatment of a mixed ionic electronic conductor membrane, consisting of a porous cathode and anode separated by a thin non-porous layer, to the case where mass transport of molecules in the porous electrodes can be the rate-limiting step. The linearized transport equations for the ion-hole pairs in the solid and of the gas molecules in the pores are characterized by the length scales L_P = √L_d(1 − φ)/Sτ_s and L_g = 2L_p√[τ_sφ/τ(1 − φ)][D_gc_g/D_IEc_i] respectively, where L_d = D_IE/K is the length scale that determines the transition from diffusion limited to surface exchange limited transport in the non-porous electrodes, K is the surface exchange coefficient, D_IE and D_g are the diffusion coefficients of the ion-hole pairs and of the molecules, c_i and c_g are the concentrations of the ions and molecules, S is the pore surface area per unit volume, φ the porosity and τ_s and τ the tortuosities of the solid and pore phases respectively. When L_g L_p, which is the case treated previously, the rate-limiting step in the transport is ionic diffusion and surface exchange. Enhancements in oxygen ion current of two orders in magnitude, over non-porous electrodes, are in principle achievable with porous perovskite MIEC having surface area s = 10⁶ cm⁻¹. When L_g L_p the rate-limiting step is mass transport in the pores and the enhancement in ion current is substantially reduced.     

The molecular dynamics of nematic liquid crystal confined in porous membranes treated by different surfactants

The molecular dynamics of the well-known nematic liquid crystal 4-n-pentyl-4′-cyanobiphenyl geometrically restricted in Anopore and Synpor porous membranes with various pore structure and treated by different surfactants (namely decanoic acid and lecithin) is compared. In the Anopore membrane the chosen surfactants induce the homeotropic orientation of the molecules on the walls of the cylindrical pores and observed corresponding relaxation processes (librational modes) are practically the same. The dielectric measurements of lecithin treated Synpor membranes reveals the reorientation of the molecules from planar to homeotropic on the complex multilayer structure present in their volume. The dielectric strengths of the observed two molecular processes (δ-process and librational mode) are inversed in the ratio compared to the untreated membranes. The observed differences in molecular dynamics results from the orientation of the liquid crystal molecules in untreated and treated membranes and the structure of the membranes themselves.     

Optical fiber humidity sensor based on evanescent-wave scattering

The phenomenon of evanescent-wave scattering (EWS) is used to design an optical-fiber humidity sensor. Porous solgel silica (PSGS) coated on the surface of a silica optical-fiber core scatters evanescent waves that penetrate the coating layer. Water molecules in the gas phase surrounding the optical fiber can be absorbed into the inner surface of the pores of the porous silica. The absorbed water molecules form a thin layer of liquid water on the inner surface of the porous silica and enhance the EWS. The amount of water absorbed into the PSGS coating is in dynamic equilibrium with the water-vapor pressure in the gas phase. Therefore the humidity in the air can be quantitatively determined with fiber-optic EWS caused by the PSGS coating. The humidity sensor reported here is fast in response, reversible, and has a wide dynamic range. The possible interference caused by EWS to an optical-fiber gas sensor with a reagent-doped PSGS coating as a transducer is also discussed.     

NMR diffusometry and the short gradient pulse limit approximation

In NMR diffusometry, one often uses the short gradient pulse (SGP) limit approximation in the interpretation of data from systems with restricted diffusion. The SGP limit approximation means that the gradient pulse length, delta, is so short that the spins do not diffuse during the pulse duration, but this condition is rarely met. If the length scale of the pores corresponds to the molecular mean square displacement during the gradient pulse, the measured echo intensities become a function of the gradient pulse length. Here, we have studied highly concentrated emulsions to show how the length of the gradient pulse influences NMR diffusion experiments. We have focused on molecules confined to one pore and molecules that can migrate through the porous system. For the former the echo decays give smaller pores than the actual case and for the latter we show large changes in echo decay depending on the gradient pulse length, everything else being equal.     

Morphology, luminescence, and electrical resistance response to H2 and CO gas exposure of porous InP membranes prepared by electrochemistry in a neutral electrolyte

Porous InP membranes have been prepared by anodization of InP wafers with electron concentration of 1 × 10¹⁷ cm⁻³ and 1 × 10¹⁸ cm⁻³ in a neutral NaCl electrolyte. The internal surfaces of pores in some membranes were modified by electrochemical deposition of gold in a pulsed voltage regime. Photoluminescence and photosensitivity measurements indicate efficient light trapping and porous surface passivation. The photoluminescence and electrical resistivity of the membranes are sensitive to the adsorption of H₂ and CO gas molecules. These properties are also influenced by the deposition of Au nanoparticles inside the pores.     

Atomic mobility in a ternary liquid Ga–In–Sn alloy of the eutectic composition

The nuclear spin–lattice relaxation and Knight shift of ⁷¹Ga, ⁶⁹Ga, and ¹¹⁵In nuclei in a ternary liquid gallium–indium–tin alloy of the eutectic composition, which was introduced into pores of an opal matrix and porous glasses with pore sizes of 18 and 7 nm, have been investigated and compared with those for the bulk melt. It has been found that longitudinal relaxation is accelerated and the Knight shift is decreased, depending on the size of pores. The correlation time of the atomic motion has been calculated for the nanostructured melt in porous matrices. It has been shown that the atomic mobility in the melt decreases with decreasing size of pores in the glasses.

     

多孔表面推迟高超声速边界层转捩的机理

利用线性稳定性理论分析（LST）结合直接数值模拟（DNS）研究高超声速多孔表面边界层流动的失稳特征,分析多孔表面推迟高超声速边界层转捩的机理.在Ma=6,Re=2.0×10⁴（参考长度为入口处边界层位移厚度）条件下获得平板边界层及不同孔隙排列情形下平板边界层的典型流动特征,并采用LST方法分析光滑平板及多孔平板扰动的增长率及累计放大率.研究表明三维顺排及错排多孔表面都可以抑制第二模扰动的发展,推迟高超声速边界层转捩,但顺排多孔表面推迟高超声速边界层转捩能力更强.