Correlating surface permeability with intracrystalline diffusivity in nanoporous solids

The rates of uptake and release of guest molecules in nanoporous solids are often strongly influenced or even controlled by transport resistances at the external surface ("surface barriers") rather than by intraparticle diffusion, which was assumed to be rate controlling in many of the earlier kinetic studies. By correlating the surface resistance with the intracrystalline diffusivity, we develop here a microkinetic model which closely reproduces the experimentally observed results for short-chain alkanes in Zn(tbip), a member of the novel metal-organic framework family of nanoporous materials. It seems likely that this mechanism, which is shown to provide a rational explanation of the commonly observed discrepancies between "macro" and "micro" measurements of intracrystalline diffusion, may be fairly general.     

Effects of surface roughness on self- and transport diffusion in porous media in the Knudsen regime

The effect of surface roughness on Knudsen diffusion in nanoporous media is investigated by means of dynamic Monte Carlo simulations in three-dimensional rough fractal pores. These simulations yield new insight and explain a number of apparent inconsistencies by revealing a striking difference between the roughness dependence of transport diffusion and gradientless (self- or tracer) diffusion. Both analytical and simulation results show a significant roughness dependence of self-diffusion in the Knudsen regime. Transport diffusion, on the other hand, is roughness independent, as the fluxes do not depend on the detailed residence time and molecular trajectories.     

On the problem of field-gradient NMR measurements of intracrystalline diffusion in small crystallites--water in NaA zeolites as an example

Necessary conditions for measuring intracrystalline diffusion in small crystal size systems via field-gradient NMR are discussed. As an illustrative case self-diffusion coefficients of water adsorbed in NaA zeolites (average crystal diameter about 1 μm) have been measured by ¹H-NMR stimulated echoes in static magnetic field gradients of up to 180 T/m in the temperature range of 254–344 K. Obtaining intracrystalline diffusion coefficients necessitates a sufficiently high spatial resolution only provided by such large field gradients.     

Structure-mobility relations of molecular diffusion in nanoporous materials

Depending on the measuring conditions, pulsed field gradient (PFG) NMR measurements of molecular diffusion in beds of nanoporous particles may provide information about the propagation rate of guest molecules in both the intra- and interparticle spaces, as well as through the interface between them. Recent progress in both PFG NMR instrumentation and computational techniques have initiated studies of novel aspects in each of these areas, which are reviewed in this communication. They concern the possibility of multicomponent diffusion measurements with ultra-high pulsed field gradients, the peculiarities of molecular diffusion in channel networks, the determination of the surface-to-volume ratio of nanoporous particles and the dependence of the tortuosity factor of long-range diffusion on the diffusion mode in the intercrystalline space.     

The propagator representation of molecular transport in microporous crystallites

NMR diffusion data may easily be represented by the propagator, that is, by the probability that after a time interval Δ a molecule, initially at position z = 0, will be found at position z. Such a propagator representation is used for visualizing the mean features of molecular diffusion in biporous systems as, e.g., a powder sample of zeolite crystallites. As an example, propagator representations for ethane in NaX and NaCaA zeolites in dependence on the temperature and on the crystallite radii are given. The observed diffusion characteristics are in satisfactory agreement with theoretical estimates of the influence of inter- and intracrystalline transport on the overall diffusion behavior.     

Long-range diffusion in beds of nanoporous particles: pitfalls and potentials

Owing to the recent progress in the area of hardware and software of the pulsed field gradient NMR technique, molecular transport in real-life zeolite systems, such as zeolite beds and particles of formulated fluid catalytic cracking (FCC) catalysts, can be investigated in detail. These studies have revealed a number of important features of molecular transport in zeolites, which are reviewed in the present paper. In particular, the anomalous character of intracrystalline diffusion in MFI-type zeolites, dependence of the tortuosity factor in zeolite beds on diffusion regime and the role of various modes of diffusion in transport limitations arising for catalytic reactions in FCC catalysts will be discussed.     

Influence of the temperature and duration of the annealing on the lattice structure and growth of the Mg-Al spinel layer

In this paper, MgO film is successfully grown on polycrystalline and monocrystalline alumina substrates using sol-gel method, and polycrystalline and monocrystalline Mg-Al spinels are fabricated by solid state reaction, respectively. The influence of annealing temperature and time on the lattice structure and growth of the formed Mg-Al spinel layer has been investigated. It is indicated that the annealing temperature and time on the as-synthesized polycrystalline Mg-Al spinel has more significant influence than that of single crystal Mg-Al spinel. The thickness of the Mg-Al spinel layer increases with the annealing temperature, both for polycrystalline and for monocrystalline alumina substrates. And the significantly intercrystalline diffusion of Mg²⁺ ions and Al³⁺ ions results in a quicker growth velocity of the Mg-Al spinel layer than that of intracrystalline diffusion.     

PAC Probes as Diffusion Tracers in Solids

Perturbed angular correlation (PAC) probe atoms have been used as tracers to study diffusion in solids. The method works for diffusion on a sublattice for which the point symmetry is noncubic and the electric field gradient (EFG) at the probe nucleus reorients in each jump. Such motion leads to relaxation of the nuclear quadrupole interaction. Precise values of the tracer jump frequency have been obtained from fits of measured PAC perturbation functions. Results obtained to date are reviewed for Cd tracer atoms in rare-earth indides such as LaIn3 that have the L1₂ crystal structure, for which each jump on the In-sublattice reorients the EFG by 90°. New results are presented for LaSn3 and prospects for future studies are outlined.     

High‐Pressure Evaporation‐Based Nanoporous Black Sn for Enhanced Performance of Lithium‐Ion Battery Anodes

Increasing the surface area to improve chemical activity is an unending task from conventional catalysis to recently emerging electrochemical energy conversion and storage. Here, a simple, vacuum‐deposition‐based method to form nanoporous structures of metals is reported. By utilizing thermal evaporation at a high pressure, fractal‐like nanoporous structures of Sn with porosity exceeding 98% are synthesized. The obtained nanostructure consists of nanoparticle aggregates, and the morphology can be controlled by adjusting the working pressure. The formation of the nanoporous structure is explained by homogeneous nucleation and diffusion‐limited aggregation, where nanoparticles produced by the repeated collisions of evaporated atoms adhere to the substrate without diffusion, forming porous aggregates. Due to the easy oxidation of Sn, the constituent nanoparticles are covered with amorphous SnO_x and crystalline SnO phases. When the nanoporous Sn/SnO_x aggregates are applied to a lithium‐ion battery anode through direct deposition on a Cu foil current collector without binders or conducting additives, the nanoporous Sn/SnO_x anode shows greatly enhanced cyclability and exceptional rate performance compared to those of a dense Sn thin film anode. The approach investigated in this work is expected to provide a new platform to other fields that require highly porous structures.     

Diffusivity control in nanoporous membrane through organic-inorganic hybridization

Nanoporous inorganic materials have attracted great interest due to their potential application as nanofilters, drug delivery carriers and adsorbents. In order to control the molecular passage through nanopores, we have modified the pore channel of inorganic materials with organic moieties and investigated the diffusion pattern of small molecules. The surface was modified by octyltriethoxysilane (OTS) by refluxing in toluene for 12 h. The water contact angle of OTS modified zirconia membrane was observed ∼110° showing hydrophobic surface. Contact angles to various solvents were also examined to verify the self-assembled monolayer of octyl chains on the inorganic membrane. The molecular passage patterns of both pristine and modified nanoporous membrane were evaluated by means of the diffusivity of small dye molecule, azobenzene. The diffusion coefficients of azobenzene on both membranes were measured in various solvents on the basis of Fick’s diffusion law. The diffusivities in various solvents for pristine and its modified zirconia membrane were determined. The diffusivity was observed to be influenced by surface energy of both membrane and solvent as well as the polarity of solvents.     

Combining macroscopic and microscopic diffusion studies in zeolites using NMR techniques

In this study the zero length column (ZLC) technique is extended to the case where the decay of the adsorbed phase concentration is observed directly by nuclear magnetic resonance (NMR). An adsorption-desorption apparatus compatible with a 400-MHz NMR spectrometer was developed. It operates with nitrogen or helium as the inert purge gas. The column of the adsorbent material is placed in the sensitive region of the superconducting magnet and the rf coil of the NMR spectrometer. The time scales of the adsorption and desorption processes depend on concentration, temperature and crystal shape and are found to be in the range of 1-10 min. From the desorption branch, the non-equilibrium ZLC-NMR measurements yield intracrystalline diffusion coefficients in the range of 10(-13) to 10(-11) m2/s for different alkanes in silicalite-1. These values are always found to be smaller than the values measured by pulsed field gradient NMR under equilibrium condition indicating that there must be additional transport resistance at the external surface of these silicalite-1 zeolite crystals.     

The trap-limited diffusivity of electrons in nanoporous semiconductor networks permeated with a conductive phase

The transport of photogenerated electrons in nanocrystalline semiconductor networks permeated with a conducting phase is studied, with a particular emphasis on dye-sensitized nanoporous TiO₂ solar cells. We extend the classical approach to the trap-limited mobility according to specific features of the nanoporous configuration: electron transport by diffusion, the capacitive behavior of the nanoporous film and the possible bandshifts due to the charging of surface states. We show that the trap-limited diffusivity, as measured by small-signal techniques, is proportional to the ratio of the conduction-band capacitance and the trap capacitance. These capacitances are defined in terms of a pseudopotential related to the chemical energy of the free electrons, in order to account for possible band unpinning. Several specific distributions of bandgap states are investigated. The dependence of the trap capacitance on the number of free electrons takes the general form C_trap=An^1-a, where 0a1 depends on the distribution of the traps. The trap-limited diffusivity depends on the number of free electrons as D_n=Bn^a, and D_n also shows a power-law dependence with the light intensity. We describe the correlation of the electron conductivity with the photovoltage in the solar cell and the photon irradiation intensity. PACS 81.07.Bc; 73.30.+y     

氢及其同位素在聚苯乙烯与Cu界面的扩散

为了探索气体在固体表面高分子链中的扩散,使用分子动力学（MD）的方法,对H2,D2,T2在聚苯乙烯与金属铜（PS-Cu）界面的扩散进行了计算模拟,通过所得到气体的均方位移计算了气体在不同金属表面与聚苯乙烯界面中的扩散系数。结果显示：气体在界面的扩散系数比在聚苯乙烯本体中的扩散系数小,气体在PS-Cu(110)界面的扩散系数最大,在PS-Cu(111)界面的扩散系数最小。计算和分析了PS与金属表面的相互作用,发现其相互作用能越大,气体在此界面的扩散系数越小。同时,金属表面的晶面密度对气体在界面中的扩散也有一定的影响。     

基于石墨烯的太赫兹漫反射表面快速设计方法

漫反射电磁表面能够提高目标被探测的难度,实现电磁消隐的功能.太赫兹漫反射电磁表面有望在下一代雷达与通信场景中作为一种智能隐身蒙皮使用,具有广阔的应用前景.本文利用石墨烯在太赫兹频段优异的电磁可调特性,并基于谐振模式的开关机理设计了一种反射场具有反相位的石墨烯/金属协同单元结构.且相位的切换由偏置电压动态控制.另一方面,不同于金属材料,石墨烯具有不可忽略的损耗特性,导致了所设计的结构在谐振/非谐振两种反相位状态对应的反射幅度不一致,根据场的干涉与叠加原理,其不利于远场相干相消,难以获得理想的漫反射效果.本文提出了一种将反相位单元结构进行二次组合形成"分子"结构的方法,并将其作为反射表面的基本元素,进而运用粒子群算法,优化"分子"结构的排布方式.计算结果表明,使用这种方法设计的动态漫反射表面,具有收敛速度快、远场峰值小的优势.     

氢及其同位素在聚苯乙烯与Cu界面的扩散

为了探索气体在固体表面高分子链中的扩散,使用分子动力学（MD）的方法,对H2,D2,T2在聚苯乙烯与金属铜（PS-Cu）界面的扩散进行了计算模拟,通过所得到气体的均方位移计算了气体在不同金属表面与聚苯乙烯界面中的扩散系数。结果显示:气体在界面的扩散系数比在聚苯乙烯本体中的扩散系数小,气体在PS-Cu(110)界面的扩散系数最大,在PS-Cu(111)界面的扩散系数最小。计算和分析了PS与金属表面的相互作用,发现其相互作用能越大,气体在此界面的扩散系数越小。同时,金属表面的晶面密度对气体在界面中的扩散也有一定的影响。     

Adsorption of proteins on nanoporous Ti surfaces

The cascade of events that regulate cell-substrate interactions is not yet fully understood. However, it is now generally recognized that proteins adsorbed on a substrate prior to its colonization have a major influence on initiating and directing cellular activities. Protein adsorption and the characteristics of the adsorbed layer are determined in part by the physical/chemical properties of the underlying surface. Chemical oxidation can be used to generate nanoscale textures on various metals used as implants in medicine. In this study, we exploit a mixture of H₂SO₄/H₂O₂ to etch sputtered titanium, and we evaluate the adsorption of a broad range of proteins on the resulting nanoporous surface. Untreated and nanoporous surfaces were characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM) and Fourier-transform infrared spectroscopy (FTIR). Protein adsorption was assessed by using a quartz crystal microbalance in conjunction with dissipation monitoring (QCM-D). Our results demonstrate that the network of nanometric pits resulting from controlled chemical oxidation confers to titanium the capacity to differentially regulate protein adsorption. The observed selectivity in adsorption may have a significant impact on initial molecular events that ultimately dictate cell fate and activity.     

Controlled ligament coarsening in nanoporous gold by annealing in vacuum versus nitrogen

The structural evolution of nanoporous gold during thermal treatment was studied by annealing samples in vacuum and in flowing nitrogen. As expected, ligament thickness generally increased in both environments. However, ligaments annealed at high temperature in vacuum remained relatively narrow, undergoing much less coarsening than nitrogen-annealed samples, albeit with some ligament agglomeration. When annealed in flowing nitrogen, gold ligaments coarsened significantly at temperatures above 300?°C. This discrepancy is attributed to different surface diffusion rates of gold in the two annealing environments. The current results suggest that diffusion on the surfaces of nanoporous gold ligaments proceeds more quickly in nitrogen than in vacuum.     

Integral one-point statistical characteristics of vector fields in stochastic magnetohydrodynamic flows

We study integral statistical characteristics of a vector passive tracer (homogeneous at the initial time) in a velocity field that is assumed to be a Gaussian random field homogeneous in space and delta-correlated in time. Such statistical characteristics describe the dynamical system as a whole in the entire space, separating out the field generation processes, which allows us to not digress into details of the dynamics related to the advection of these quantities. The density field gradient (in the general case of a compressible fluid) and the magnetic field vector with its spatial derivatives (in an incompressible fluid) are such a tracer. We study the isotropization in time, helicity, and dissipation of these fields in the absence of molecular diffusion effects. We formulate a method of successive approximations for the variance of the density field and the mean magnetic field energy that allows the solutions valid in the entire time interval to be obtained in the first order in molecular diffusion coefficients.     

Simulation of porous silicon formation and silicon epitaxy on its surface

Processes of porous silicon formation and silicon epitaxy on its surface are studied using the Monte Carlo method. The model for porous silicon formation under anode etching allows for non-uniformity of charge distribution over the silicon-electrolyte interface. Processes of diffusion, generation and recombination of holes, as well as dimensional quantization, are also considered. Gilmer's model, extended to the case of a rough surface, is used to study epitaxy. The structures obtained by simulations at different levels of doping of the crystal substrate and for various parameters (temperature, HF concentration, and anode current density) are presented. Analysis of nanoporous structures showed that the porosity changes with depth, and fractal dimensionality exists below 10 nm. It has been shown that epitaxy, developing by formation of metastable nuclei at the edges of pores, by their subsequent growth along the perimenter and by formation of a thin continuous overhanging layer, may be described within the framework of this model. Three-dimensional images of near-surface layers formed at different stages of epitaxy have been obtained. The dependence of the epitaxy kinetics on the amount of deposited silicon for different structure porosities has been revealed. Institute of Physics of Semiconductors, Siberian Branch, Russian Academy of Science. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 49–56, March, 1999.     

Diffusing passive tracers in random incompressible flows: Statistical topography aspects

The paper studies statistical characteristics of the passive tracer concentrations and of its spatial gradient, in random incompressible velocity fields from the viewpoint of statistical topography. The statistics of interest include mean values, probability distributions, as well as various functionals characterizing topographic features of tracers. The functional approach is used. We consider the influence of the mean flow (the linear shear flow) and the molecular diffusion coefficient on the statistics of the tracer. Most of our analysis is carried out in the framework of the delta-correlated (in time) approximation and conditions for its applicability are established. But we also consider the diffusion approximation scheme for finite correlation radius. The latter is applied to a diffusing passive tracer that undergoes sedimentation in a random velocity field.