Electrochemical impedance spectroscopy of lead(II) ion-selective solid-state membranes

Silver sulphide/lead sulphide membranes were studied using electrochemical impedance spectroscopy. The influence of the electrolyte concentration and the membrane thickness were evaluated. The complex impedance plots have shown two capacitive loops: one at high frequency range, related with the charge transfer resistance at the interface membrane-Ag and a second one at low frequency range, associated with the diffusion process through the membrane. A simple model was used to take into account the experimental results: the changes of the potential with the time and the electrolyte concentration; the changes of the charge transfer resistance and the diffusion resistance with the electrolyte concentration. An empirical equation was used to calculate the diffusion coefficient of Ag⁺ inside the membrane.     

Three-dimensional random resistor-network model for solid oxide fuel cell composite electrodes

A three-dimensional reconstruction of solid oxide fuel cell (SOFC) composite electrodes was developed to evaluate the performance and further investigate the effect of microstructure on the performance of SOFC electrodes. Porosity of the electrode is controlled by adding pore former particles (spheres) to the electrode and ignoring them in analysis step. To enhance connectivity between particles and increase the length of triple-phase boundary (TPB), sintering process is mimicked by enlarging particles to certain degree after settling them inside the packing. Geometrical characteristics such as length of TBP and active contact area as well as porosity can easily be calculated using the current model. Electrochemical process is simulated using resistor-network model and complete Butler-Volmer equation is used to deal with charge transfer process on TBP. The model shows that TPBs are not uniformly distributed across the electrode and location of TPBs as well as amount of electrochemical reaction is not uniform. Effects of electrode thickness, particle size ratio, electron and ion conductor conductivities and rate of electrochemical reaction on overall electrochemical performance of electrode are investigated.     

Faradaic impedance to analyze charge recombination in photoelectrode of dye-sensitized solar cell

Charge transfer on the photoelectrode of dye sensitized solar cell (DSC) is composed of the various processes as follows: photoexcitation of electron in the dye; electron injection from the excited dye into the conduction band of oxide semiconductor; electron diffusion in the oxide semiconductor, reaction between oxidized dye and iodide ions (I⁻); and charge recombination. The charge recombination is one of the main factors that limit the efficiency of photoelectric conversion at photoelectrode. It is well known that 4-tert-butyl pyridine (TBP) is the useful additive in order to suppress the charge recombination. The authors fabricated the DSC with two photoelectrode materials such as titanium dioxide (TiO₂) and zinc oxide (ZnO), and analyzed the charge recombination by using electrochemical impedance spectroscopy. Theoretical equation of Faradaic impedance was derived from the reaction model of photoelectorde, and the charge transfer resistance of the photoelectrode was defined from the Faradaic impedance. In addition, the influence of the charge recombination on the impedance spectrum of the photoelectrode was discussed by the comparison between simulated and experimental results.     

Pore-scale study of reactive transfer process involving coke deposition via lattice Boltzmann method

Coke deposition during catalytic industrial processes can lead to the narrowing and blockage of pore structures inside particles so as to influence the catalyst performance. In this work, a direct pore-scale simulation is carried out by the lattice Boltzmann method to investigate the change of pore structures caused by coke formation. Coke deposition processes in the single pore and complex porous medium are evaluated. The interaction of pore structure and mass transfer under the condition of coke deposition is analyzed. The results reveal that the pore narrowing and blockage can hinder the viscous flow and Knudsen diffusion, resulting in the change of mass transfer mechanism, which is sensitive to gas rarefaction effect and coke deposition rate as well as surface roughness. For the complex porous medium, the uniformity of pore size distribution becomes weak under the gas rarefaction effect and coke deposition.     

Theory of the electrochemical impedance of macrohomogeneous porous electrodes

An equation for the impedance of a macrohomogeneous porous electrode is derived for the general case (finite electrode thickness and resistivities of the solid and liquid phases), and it is shown how to obtain from it the general solution for the transient state. The electrode model is represented by a transmission line equivalent circuit, and the theory is further generalized by including an arbitrary time delay (a hindrance) of the charge transfer process at the pore surface. A reformulation leads to the definition of an appropriate dielectric function. Two hindrance processes are considered, namely control of the charge transfer by finite diffusion and control by both diffusion and formation of a pseudocapacity (ie charge storage) on a molecular scale. The resulting impedance characteristics for selected parameter values are discussed and preliminary results of fitting experimental data with the new theory are presented.     

Charge and Mass Transfer Across the Metal/Solution Interface

Electrode reactions are characterized by charge transfer across the interface. The charge can be carried by electrons or by ions. It is shown here that when both mass and charge cross the interface, the charge must be carried by the ionic species, not by the electrons, as a result of the very large difference in the time scale for electron and ion transfer. A prime example of charge transfer by ions is metal deposition. It is proposed that ion transfer occurs by migration of the ions across the interface, under the influence of the high electrostatic field in the double layer. The rate constants observed for metal deposition are comparable to those for outer-sphere charge transfer. These unexpectedly high rate constants for metal deposition are explained by a model in which removal of the solvation shell and reduction of the effective charge on the metal ion occur in many small steps, and a make-before-break mechanism exists, which lowers the total Gibbs energy of the system as it moves along the reaction coordinate from the initial to the final state.     

Theoretical studies of displacement deposition of nickel into porous silicon with ultrahigh aspect ratio

A model is developed to address the uniformity of displacement deposition of nickel inside porous silicon with an ultrahigh aspect ratio as high as 200. The nickel distribution is treated as a current distribution issue as in electrodeposition. It is shown that the deposition distribution along the pore depth exhibits a strong dependence on a polarization parameter ξ. High values of ξ correspond to mass transport limitations and lead to non-uniform distributions, whereas small ξ values, representing interfacial reaction control, produce uniform distributions. Non-uniform deposition primarily occurs at an initial stage in which the reaction is dominated by mass transfer. As the deposition process continues, the deposition rate drops to a low value, and the deposition uniformity shifts from Ni²⁺ mass transport limitations to its interfacial reaction control, leading to uniform Ni²⁺ concentration and deposition rate distributions. It is predicted that the non-uniformity at the initial stage could be remedied by increasing the bulk concentration of the nickel ions and decreasing the plating bath pH. In addition, the uniformity of the deposition distribution can be significantly improved by introducing inhibiting additive coumarin to the plating solution.     

Mechanistic study of cobalt catalyzed growth of carbon nanofibers in a confined space by plasma-assisted chemical vapor deposition

Carbon nanofibers (CNFs) were grown in the porous anodic aluminum oxide (AAO) thin film grown on the Si wafer by electron cyclotron resonance chemical vapor deposition using cobalt as the catalyst. A larger Co particle electrodeposited in the AAO pore channel produced vertically aligned CNFs with a tube diameter in compliance with the pore size of the AAO template. On the other hand, a smaller Co particle resulted in CNF growth with a nonuniform distribution of the tube diameter and a sparse tube density. Amorphous carbon residue produced under the plasma-assisted CNF growth condition seemed to play an essential role leading to the observation. A growth mechanism is proposed to delineate the volume effect of the electrodeposited Co catalyst on the CNF growth confined in pore channels of the AAO template.     

CHARACTERIZATION OF TWO-DIRECTIONAL DISPERSED PHASE FLOW THROUGH TIME SERIES ANALYSIS

A catalyst deactivation model is formulated which includes the combined effects of pore plugging and active site poisoning. Intraparticle mass transfer is described by an equation which accounts for the configurational nature of diffusion, and poison deposition is assumed to be in accord with a parallel poisoning mechanism. A computational algorithm is presented for solving the highly nonlinear system equations numerically. The relative extent of deactivation by pore plugging and active site poisoning is determined by a dimensionless parameter, α, and several examples illustrate the effects that this parameter and other system parameters have upon the computed results. The model when combined with laboratory experiments should prove useful in optimizing catalyst pore size.     

CATALYST DEACTIVATION BY PORE PLUGGING AND ACTIVE SITE POISONING MECHANISMS II. PARALLEL POISONING IN BIDISPERSE STRUCTURED CATALYST

A catalyst deactivation model is formulated which includes the combined effects of pore plugging and active site poisoning in bidisperse structured catalyst particles. Intraparticle mass transfer is described by an equation which accounts for the configurational nature of diffusion in the micropores, and poison deposition is assumed to be in accord with a parallel poisoning mechanism. The model is used to explore the effects of macroporosity and micropore size on initial activity and activity maintenance, and model predictions appear to be consistent with observations from a recent coal liquefaction catalyst development program.     

Modelling and simulation of self-ordering in anodic porous alumina

Real-time evolution of pre-textured anodic porous alumina growth during anodization is numerically simulated in two-dimensional cases based on a kinetic model involving the Laplacian electric field potential distribution and a continuity equation for current density within the oxide body. Ion current densities governed by the Cabrera–Mott equation in high electric field theory are formed by ion migration within the oxide as well as across the metal/oxide (m/o) and oxide/electrolyte (o/e) interfaces, and the movements of the m/o and o/e interfaces due to oxidation and electric field assisted oxide decomposition, respectively, are governed by Faraday's law. Typical experimental results, such as linear voltage dependence of the barrier layer thickness and pore diameter, time evolution of the current density, scalloped shape of the barrier layer, and the extreme difference in the reaction rates between pore bottoms and pore walls, are successfully predicted. Our simulations revealed the existence of a domain of model parameters within which pre-textured porous structures which do not satisfy self-ordering configurations are driven into self-ordering configurations through a self-adjustment process. Our experimental results also verify the existence of the self-adjustment process during anodization.     

Optimization of electroless Ni-Zn-P deposition process: experimental study and mathematical modeling

A mathematical model based on mixed potential theory was developed which was used to optimize a non-anomalous Ni-Zn-P electroless deposition process developed by us at USC. The model was developed by assuming an adsorption step in addition to the electrochemical steps. The concentrations of the Zn and Ni complex were estimated by solving the material balances in addition to the electroneutrality condition and the equilibrium relations. The composition of the coating was estimated from the partial current densities of all charge transfer reactions, which occur at the electrode-electrolyte interface. The model results showed that the adsorption plays a significant role in the alloy deposition process. From the model results, it was seen that the addition of Zn ions to the bath inhibits the deposition rate by changing the surface coverage of the adsorbed electroactive species on the electrode surface. The model indicated that an increase of pH of the bath increases the alloy deposition rate.     

中空纤维膜渗透汽化过程中Dean涡强化传质的CFD模拟

建立了一个三维的弯管式中空纤维膜渗透汽化传质CFD模型,研究Dean涡对渗透汽化过程传质的影响,描述了膜内侧的浓度和速率变化情况,该模型与Leveque传质关联式具有良好的一致性。研究结果显示：弯管膜中Dean涡的存在能降低边界层传质阻力,总传质系数比直管膜提高了4倍;在不同的入口速率和浓度条件下,弯管膜内侧的壁面剪应力均大于直管膜。在膜阻力远小于边界层阻力的情况下,入口速率0.275 m·s^-1,水浓度10%（质量）时,弯管膜的渗透通量为12636 g·m^-2·h^-1,是直管膜的5倍。可见,弯管式中空纤维膜在渗透汽化过程中具有显著的强化传质效果。     

Regulation of film thickness, surface roughness and porosity in thin film growth using deposition rate

This work focuses on distributed control of film thickness, surface roughness and porosity in a porous thin film deposition process using the deposition rate as the manipulated input. The deposition process includes adsorption and migration processes and it is modeled via kinetic Monte Carlo simulation on a triangular lattice with vacancies and overhangs allowed to develop inside the film. A distributed parameter (partial differential equation) dynamic model is derived to describe the evolution of the surface height profile of the thin film accounting for the effect of deposition rate. The dynamics of film porosity, evaluated as film site occupancy ratio, are described by an ordinary differential equation. The developed dynamic models are then used as the basis for the design of a model predictive control algorithm that includes penalty on the deviation of film thickness, surface roughness and film porosity from their respective set-point values. Simulation results demonstrate the applicability and effectiveness of the proposed modeling and control approach in the context of the deposition process under consideration.     

An ordered hydrophobic P6mm mesoporous carbon with graphitic pore walls and its application in aqueous catalysis

A hydrophobic ordered mesoporous carbon with hexagonal arrays of rods was synthesized by a nanocasting process by using silica SBA-15 as a template and 2,3-dihydroxynaphthalene as a fused-aromatic carbon precursor. Impregnation of 2,3-dihydroxynaphthalene and its subsequent conversion into carbon occurred inside the mesopores of the silica template through a dehydration reaction between the surface silanols and hydroxyl groups of the carbon source and mild carbonization under inert atmosphere. After silica removal, X-ray scattering, transmission electron microscopy, pore size analysis and Raman spectroscopy showed that the resulting material was a negative replica of the silica template with a 2D-hexagonal P6mm ordered structure, possessing a large surface area (724 m² g⁻¹), a monomodal pore size distribution (3.4 nm) and a relative hydrophobic surface with graphitic pore walls. These features give the system substantial advantages to play a beneficial role in aqueous organometallic catalysis. The material appeared to be an excellent mass transfer promoter to enhance the overall reaction rate of the palladium-catalyzed cleavage reaction of water-insoluble allylundecylcarbonate (Tsuji–Trost reaction).     

Confining grains of textured Cu2O films to single-crystal nanowires and resultant change in resistive switching characteristics

By confining columnar grains of textured oxide film using anodized aluminum oxide template, we could obtain a grain-boundary-free (GB-free) cuprous oxide (Cu(2)O) nanowire arrays with a narrow diameter distribution and a high density under the same electrochemical deposition condition. A two-terminal device fabricated using an individual GB-free nanowire and Au/Cr electrodes exhibits bipolar resistive switching contrary to the unipolar one of a textured film, and Schottky-like conduction. On the other hand, a nanowire device with Pt electrodes reveals non-switching behavior and Ohmic conduction. Thus, we can propose that the bipolar switching of a nanowire device with Au/Cr electrodes may result from the modulation of Schottky barrier at the interface by migration of oxygen vacancies while the unipolar one of a textured film may be defined as the bulky filamentary switching along the GBs in the GB-embedded texture films.     

利用铝阳极氧化膜电镀制备纳米材料

铝阳极氧化膜由于具有孔径分布均匀、空洞之间互相不连通、取向一致等特点,在纳米结构材料中获得广泛研究,对铝阳极氧化膜及其合成的纳米线表征,是开展铝阳极氧化膜研究的关键.首先制备了铝阳极氧化模板,随后通过电镀法制备了纳米线,并对铝阳极氧化模板和纳米线进行了表征.最后,文章对铝阳极氧化膜的研究前景进行了展望.     

Theoretical Computational Fluid Dynamics Study of the Chemical Vapor Deposition Process for the Manufacturing of a Highly Porous 3D Carbon Foam

Aerographite is a three‐dimensional carbon foam with a tetrapodal morphology. The manufacturing of aerographite is carried out in a chemical vapor deposition (CVD) process, based on a zinc oxide (ZnO) template, in which the morphology is replicated into a hollow carbon shell. During the replication process, the template is reduced by the simultaneous formation of the carbon structure. The CVD process is one of the most efficient methods for the manufacturing of various carbon nanostructures, such as graphene or carbon nanotubes (CNTs). Based on the growth mechanism of aerographite, a computational fluid dynamics model is presented for the fundamental investigations of the temperature and flow/microflow behavior during the replication process. This allows a deeper process understanding and further optimizations.     

Predicting the deposition spot radius and the nanoparticle concentration distribution in an electrostatic precipitator

Abstract

Deposition of aerosol nanoparticles using an electrostatic precipitator is widely used in the aerosol community. Despite this, basic knowledge regarding what governs the deposition has been missing. This concerns the prediction of the size of the particle collection zone, but also, perhaps more importantly, prediction of the nanoparticle concentration distribution on the substrate, both of which are necessary to achieve faster and more precise deposition. In this article, we have used COMSOL Multiphysics simulations, experimental depositions, and two analytical models to describe the deposition. Based on that, we propose a simple equation that can be used to predict the size of the deposition spot as well as the particle concentration on the substrate. The equation we derive concludes that the size of the deposition spot only depends on the gas flow rate into the precipitator, and on the constant drift velocity of a particle in an electric field. The equation also displays that the deposited particle concentration is independent of the gas flow rate. Our general mathematical analysis has great applicability, as it can be used to model different geometries and different types of deposition methods than the one described in this article. We can therefore also propose that the drift velocity in this model easily could be replaced by another velocity acting on the particles at other deposition conditions, for instance, the thermophoretic velocity during thermophoretic deposition. This would result in the same dependence as presented in this article. Finally, we demonstrate analytically and through experiment that the particle distribution inside the spot will be homogenous and follows a top hat profile.