Molecular dynamics simulation of pressure-driven water flow in silicon-carbide nanotubes

Many properties of silicon carbide (SiC) nanotubes, such as their high mechanical strength and resistance to corrosive environments, are superior to those of their carboneous counterparts, namely, carbon nanotubes (CNTs) and, therefore, SiC nanotubes can be a viable alternative to CNTs in a variety of applications. We employ molecular dynamics simulations to examine flow of water in SiC nanotubes and to study the differences and similarities with the same phenomenon in the CNTs. The simulations indicate that SiC nanotubes always provide larger flow enhancements than those reported for the CNTs. Moreover, a given flow enhancement in SiC nanotubes requires an applied pressure gradient that is at least an order of magnitude smaller than the corresponding value in a CNT of the same size.     

On the nonequilibrium thermodynamics of gas flow in nanoporous membranes

Gas flow has been considered in a porous membrane with nanosized channels, for which the influence of surface forces and relevant effects must be taken into account. The problem of entropy production in such systems has been discussed. It has been shown that, when calculating the total entropy production in such a system, it is necessary to take into account the entropy production at the inlets and outlets of the channels of the porous body. The entropy production has been determined, and the phenomenological equations describing the heat and mass transfer through the porous body-gas interface have been found.     

Molecular dynamics simulation of a pressure-driven liquid transport process in a cylindrical nanopore using two self-adjusting plates

Fluid transport through a nanopore in a membrane was investigated by using a novel molecular dynamics approach proposed in this study. The advantages of this method, relative to dual-control-volume grand-canonical molecular dynamics method, are that it eliminates disruptions to the system dynamics that are normally created by inserting or deleting particles from control volumes, and that it functions well for dense systems due to the number of particles being fixed in the system. Using the proposed method, we examined liquid argon transport through a nanopore by performing nonequilibrium molecular dynamics (NEMD) simulations under different back pressures. Validation of the code was performed by comparing simulation results to published experimental data obtained under equilibrium conditions. NEMD results show that constant pressure difference across the membrane was readily achieved.     

Molecular simulation of loading-dependent diffusion in nanoporous materials using extended dynamically corrected transition state theory

A dynamically corrected transition state theory method is presented that is capable of computing quantitatively the self-diffusivity of adsorbed molecules in confined systems at nonzero loading. This extension to traditional transition state theory is free of additional assumptions and yields a diffusivity identical to that obtained by conventional molecular-dynamics simulations. While molecular-dynamics calculations are limited to relatively fast diffusing molecules, our approach extends the range of accessible time scales significantly beyond currently available methods. We show results for methane, ethane, and propane in LTL- and LTA-type zeolites over a wide range of temperatures and loadings, and demonstrate the extensibility of the method to mixtures.     

Dynamic interactive membranes with pressure-driven tunable porosity and self-healing ability

When pressure is applied to dynamic interactive membranes consisting of micelles composed of a triblock copolymer, their morphologies can be fine-tuned. Membranes with a range of porosities are accessible which can regulate and thereby control filtration performance and also display effective autonomous healing.     

Stockmayer流体在活性炭孔中的吸附的分子模拟

应用巨正则系综monteCarlo方法模拟Stockmayer流体[以一氯二氟甲烷(R22)为代表]在活性炭孔中的吸附。模拟中R22分子采用等效Stockmayer势能模型,狭缝碳孔墙采用10-4-3模型。通过模拟得到了最佳孔径,并在最佳孔径下,针对不同的主体压力及活性基团密度,得到了吸附等温线、孔中流体的局部密度分布图和较为直观的孔内流体分子的瞬时构象,分析了吸附等温线的特征及孔内流体的吸附结构,认为在0.0,1.0sites/nm^2的活性基团密度下的碳孔内分别发生物理及化学吸附,并确定了最佳操作压力,为工业设计合适的催化剂提供依据。     

Electrocatalytic oxidation of glucose on nanoporous gold membranes

With characteristic of structural integrity and high surface area, nanoporous gold (NPG) prepared by dealloying method is proposed to be a highly sensitive catalyst for glucose electrooxidation. It can be found that a-NPG which obtained by electrochemical corrosion method has the highest sensitivity for glucose electrooxidation among the three studied samples. Under alkaline conditions, the catalytic current density of a-NPG is over 1.5 times and 17 times higher than that of f-NPG (prepared by free corrosion) and poly-Au electrode, respectively. Using a-NPG sample for glucose detection, the obtained minimum sensible concentration are 413 nM in alkaline media and 1 μM in neutral solutions. The a-NPG electrode also shows stable recovery and reproducibility characteristics. These results indicate that NPG may work as an efficient electrode material for electrochemical sensors and a promising catalyst for alkaline glucose fuel cells.     

Effects of fluid slippage on pressure-driven electrokinetic energy conversion in conical nanochannels

The effects of fluid slippage on the pressure-driven electrokinetic energy conversion in conical nanochannels are systematically investigated in this paper. We present a multiphysical model that couples the Planck–Nernst–Poisson equations and the Navier–Stokes equation with a Navier slip condition to fulfill this purpose. We systematically look into the variation of various performance indicators of electrokinetic energy conversion, for example, streaming current, streaming potential, generation power, energy conversion efficiency, regulation parameter, and enchantment ratio, with the conicity of nanochannels and the slip length for two pressure differences of the same magnitude but opposite directions. Particularly, enhancement ratios related to streaming current, streaming potential, generation power, and energy conversion efficiency are defined to comprehensively measure the enhancement of the performance of electrokinetic energy conversion due to the slip length. The results demonstrate that a combination of large slip length and small conicity enhances the electrokinetic energy conversion performance significantly. Furthermore, the fluid slippage-induced enhancement of the electrokinetic energy conversion in the backward pressure difference mode is stronger than that in the forward pressure difference mode. Our results provide design and operation guidelines for pressure-driven electrokinetic energy conversion devices.     

Correlation of structural and permeation properties in sol-gel-made nanoporous membranes

The aim of the present work was to establish a fundamental link between the basic structural properties of ceramic nanoporous membranes made by the sol-gel process and their respective transport properties, for a systematic evaluation of their performance in gas and liquid applications. For this purpose, supported and unsupported gamma-Al2O3 and TiO2 membranes were prepared from different colloidal dispersions (sols) by a sol-gel dipping process followed by drying and calcination, resulting in structures of crystallites of different shape and stacking arrangement. Accordingly, the pore structure of each membrane was simulated employing process-based reconstruction techniques and the permeation properties were predicted by solving the appropriate transport equations in the generated structures. Excellent agreement was achieved between the computed and experimental permeability values in the Knudsen and viscous flow regimes, validating the considerations made regarding the basic structural characteristics and the procedure for generation of the membrane structures. Moreover, it was shown that the shape and stacking arrangement of the primary particles (crystallites) of the sol have a major impact on the formation of pathways in the membrane pore structures and control the transport and therefore also the separation properties of these materials.     

Chemically modified opals as thin permselective nanoporous membranes

Thin-film opals comprising three layers of 440 nm diameter SiO2 spheres were assembled on Pt electrodes and modified with amino groups on the silica surface. Diffusion of anionic, cationic, and neutral redox species through the opals was studied by cyclic voltammetry. The chemically modified opal membranes demonstrate high molecular throughput and, at low pH, selectively block transport of a cationic redox species relative to that of anionic and neutral redox species. This permselective behavior is attributed to the electrostatic interactions that are enhanced by the tortuous pathway within the opal and by the high surface area of the chemically modified spheres.     

Theory of pressure-driven transport of neutral solutes and ions in porous ceramic nanofiltration membranes

Hindered transport theory and homogeneous electro-transport theory are used to calculate the limiting, high volume flux, rejection of, respectively, neutral solutes and binary electrolytes by granular porous nanofiltration membranes. For ceramic membranes prepared from metal oxides it is proposed that the membrane structural and charge parameters entering into the theory, namely the effective pore size and membrane charge density, can be estimated from independent measurements: the pore radius from the measured hydraulic radius using a model of sintered granular membranes and the effective membrane charge density from the hydraulic radius and the electrophoretic mobility measurements on the ceramic powder used to prepare the membrane. The electro-transport theory adopted here is valid when the membrane surface charge density is low enough and the pore radius is small enough for there to be strong electrical double layer overlap in the pores. Within this approximation the filtration streaming potential is also derived for binary electrolytes.     

Ionic transport across tailored nanoporous anodic alumina membranes

Monodispersed silica particles with bimodal size distribution were successfully prepared through adding an ethanol (EtOH) solution containing tetraethylorthosilicate (TEOS) dropwise into an ammonia EtOH solution at a constant low rate. The effects of the reaction parameters such as ammonia/ethanol ratio, feeding rate of TEOS solution, reaction temperature, and time on the size and size distribution of the as-obtained particles were investigated. Based on these phenomena, a modified LaMer model of nucleation and growth mechanism was proposed to reasonably explain the formation of the as-obtained silica particles with bimodal size distribution. The as-prepared monodispersed silica particles with bimodal size distribution can be directly fabricated into binary colloidal crystals with small particles surrounding large particles by evaporation-induced cooperative self-assembly. This suggests that the method reported here provides a straightforward and effective route to the in situ fabrication of novel binary colloidal crystals and their replicated patterns in one reaction system.     

A fluorogenic assay using pressure-driven flow on a microchip.

A fluorogenic assay for human T-cell phosphatase (TCPTP) was conducted on an etched glass microchip using pressure driven flow. The TCPTP enzyme catalyzes the removal of a phosphate group from 6,8-difluoro-4-methylumbelliferyl/phosphate (DiFMUP) to produce the fluorogenic product 6,8-difluoro-4-methylumbelliferone (DiFMU). Enzyme assays with real-time on-chip dilution were performed in both low-viscosity (1 cP) buffer and an enzyme solution containing 50% glycerol (6 cP). Single side channels connect a series of reagent wells to a main channel where the fluorescent product of the enzyme reaction passes the detector region. Flow regulation of mixed viscosity fluids requires a pressure control on each arm of the chip contributing to the overall flow. An 8-channel pressure controller was built to regulate the air pressure above all wells feeding channels of the chip, thereby controlling the dilution ratios of buffer, substrate and enzyme. Well pressures maintained a constant concentration of enzyme in the detector channel while adjusting the flow contribution of substrate and buffer. The substrate concentration was stepped over two orders of magnitude while verifying fluid dilutions using marker dyes. The kinetic parameters, Km, Vmax, and Kcat, showed good agreement with the values determined using a standard well plate and fluorometer.     

Preparation of novel organic‐inorganic nanoporous membranes

In this study, the water permeability, the rejection property of sucrose and glucose, the fouling property of humic acid as the foulant for a novel porous fluorinated polyimide membrane made by combining the ion irradiation and plasma treatment have been reported. First, an asymmetric polyimide membrane with a defect‐free and thin skin layer was prepared, then ions on the skin layer were irradiated and the ion‐irradiated layer was treated by plasma to form nanopores in the layer. The asymmetric polyimide membranes with a defect‐free skin layer were irradiated with 50 keV He⁺ at 1 × 10¹⁵ ions/cm², and the irradiated polyimide surfaces were treated by Ar glow discharge. The porous polyimide membrane showed a high water flux and excellent rejection properties and fouling resistance when compared with NTR‐7250, which is commercially available. These findings indicated that the pore size formed on the porous polyimide membrane was effectively controlled by the plasma treatment time and the skin layer thickness. Copyright © 2005 John Wiley & Sons, Ltd.     

Electroviscous effects on pressure-driven flow of dilute electrolyte solutions in small microchannels

A fundamental understanding of the flow characteristics of electrolyte solutions in microchannels is critical to the design and control of microfluidic devices. Experimental studies have shown that the electroviscous effect is appreciable for a dilute solution in a small microchannel. However, the experimentally observed electroviscous effects cannot be predicted by the traditional theoretical model, which involves the use of the Boltzmann distribution for the ionic concentration field. It has been found that the Boltzmann distribution is not applicable to systems with dilute electrolyte solutions in small microchannels because it violates the ion number conservation condition. A new theoretical model is developed in this paper using the Nernst equation and the ion number conservation, instead of the Boltzmann distribution, to obtain the ionic concentration field. The ionic concentration field, electrical potential field, and flow field in small microchannels are studied using the model developed here. In order to verify this model, the model-predicted dP/dx (applied pressure gradient) Re (Reynolds number) relationship is compared with the experimentally determined dP/dx approximately Re relationship. Strong agreement between the model predictions and the experimental results supports this model.     

Molecular dynamics simulation study of the interaction of trehalose with lipid membranes

The interactions of the cryoprotective agent trehalose with a lipid membrane made of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine at 323 K were studied by means of molecular dynamics simulations. It was observed that trehalose binds to the phospholipid headgroups with its main axis parallel to the membrane normal. Trehalose establishes hydrogen bonds with the carbonyl and phosphate groups and replaces water molecules from the lipid headgroup. Notably, the number of hydrogen bonds (HBs) that the membrane made with its environment was conserved after trehalose binding. The HBs between lipid and trehalose have a longer lifetime than those established between lipid and water. The binding of the sugar does not produce changes either in the lipid area or in the lipid order parameter. The effect of trehalose on the dipole potential is in agreement with experimental results. The contribution of the different components to the membrane dipole potential was analyzed. It was observed that the binding of trehalose produces changes in the different components and the sugar itself contributes to the surface potential due to the polarization of its hydroxyl in the interface.     

Colloidal lithography-based fabrication of suspended nanoporous silicon nitride membranes

Nanoporous membranes provide a basis for constructing non-supported biomembranes, which enable biological processes such as ion and molecule transport through the biomembranes to be investigated under physiological conditions with ease of control. Preparation of such membranes usually requires expensive equipments and extensive experiences. In this paper, we provide a cheap and controllable scheme of high volume fabricating suspended nanoporous Si₃N₄ membranes on a Si wafer by combined colloidal lithography and standard Si fabrication technology including low cost ICP etching and anisotropic Si wet-etch. Si₃N₄ layers are grown on Si wafers. Polystyrene particles of 200-nm-diameter are then monodispersed on the Si₃N₄ layers based on electrostatic repulsions with an average density of 2%. This is followed by Cr masking, ICP etching and Si wet-etch processes to form suspended Si₃N₄ membranes with 200-nm-deep nanopores through the membranes. The well-aligned cylindrical nanopores have a low aspect radio of ca. 0.9, which would be beneficial to forming stable suspended lipid bilayers.