微流控分析芯片的两种液相传质模式及其应用*

微流控分析芯片的微米级结构不仅显著增大内部流体的比界面积,同时缩短微通道内不同溶液间的传质距离,使传质效率相比于宏观体系有显著提高,从而可实现试样分析检测前的高效扩散分离和萃取富集等。本文综述了微流控分析芯片中两种液相传质模式——互溶液相间扩散分离分析、不互溶液相间萃取分离分析的研究进展,讨论了上述传质模式在微芯片装置和功能的集成化方面的应用;并讨论了相关研究的难点和发展趋势。     

电场作用下金属锌在薄液膜下的腐蚀电化学研究

采用薄液膜实验装置,测量了外加直流电场作用下锌在薄液膜体系中的腐蚀电位、阴极极化电流以及阴极极化曲线等. 研究了外加直流电场对锌在薄液膜下腐蚀行为的影响. 结果表明,外电场的作用可以使锌电极的腐蚀电位负移,也可以使锌电极在阴极极化条件下的阴极电流增加. 分析结果表明,外电场与薄液膜体系中锌电极电化学过程中的相关因素发生了协同作用,改变了锌电极的阴极过程.     

平板夹心型支撑液膜萃取体系中La^3＋的迁移行为

在含ＨＥＨ（ＥＨＰ）的平板夹心型支撑液膜萃取Ｌａ＾３＋的体系中，研究了体系传质过程中的渗透系数ｐ及其影响因素。实验证明夹心型与单型支撑液膜的传质理论模型以及料液酸度和反萃液酸度对传质渗透系数的影响基本一致。当体系料液的ｐＨ在３．５￣４．２之间时，体系的渗透系数ｐ趋于稳定；ｐ随反萃液酸度的增加而增大，当反萃液酸度大于４．０ｍｏｌ／Ｌ时，ｐ趋于恒定；比较了用不同材料和厚度的夹心型支撑液膜体系萃取ｌａ２     

薄层液/液界面电子转移动力学的研究进展

薄层循环伏安法是研究液/液界面电荷转移的一种新方法,具有简单、快速、易操作的优点。文章回顾了液/液界面电化学的发展历史,介绍了薄层法的实验原理,对其在电化学中的应用和研究进展进行了评述,总结了界面驱动力与电子转移速率的关系。     

纳米金/碳纳米管复合材料修饰电极催化鲁米诺电致发光体系的研究

制备了纳米金/多壁碳纳米管(MWNT)复合材料修饰电极,并将此电极应用于鲁米诺电化学发光体系.电化学发光实验表明,此复合材料修饰电极同时具备了纳米金和碳纳米管的催化性能.此外通过电极活性表面积测算、电化学交流阻抗实验等方法研究了纳米金和碳纳米管在此体系催化过程中的作用.纳米金/碳纳米管修饰电极具有良好的重现性,可以广泛应用于鲁米诺电化学发光测定体系.     

苯-N-甲酰吗啉体系膜基吸收传质过程全微分模型研究

根据双膜理论建立了全微分传质动力学模型, 以苯-N-甲酰吗啉(NFM)水溶液体系为代表, 研究了聚丙烯PP疏水性微孔膜接触器的传质过程, 并通过理论模拟及实验考察了气液相流速、气液相进口浓度、液相N-甲酰吗啉浓度、气液流动方式及膜接触器形态对苯传质通量及去除效率的影响. 结果表明, 模拟值与实验值吻合良好, 误差控制在20%以内. 当气相流量或气相进口浓度较低时, 气相传质为控制步骤, 而随着气相流量和气相进口浓度升高, 液相流量对传质过程的影响显著增加. 传质通量随气液相流量和气相进口浓度的增大而增大. 液相进口浓度及膜丝内径的增大显著降低传质通量. 另外, 较薄的膜丝壁厚有利于传质的进行, 气液逆向流方式较同向流方式可获得更高的传质通量.     

中空纤维管夹心型支撑液膜萃取体系中La^3＋的迁移行为

设计了含２－乙基己基膦酸单２－乙基己基酯的中空纤维管夹心型支撑液膜体系，并研究了Ｌａ＾３＋在该体系中的迁移行为。实验得出该体系液膜传质渗透系数ρ的数学表达式，测定体系中Ｌａ＾３＋传质渗透系数ρ及其影响因素；该体系在料液ｐＨ≥４时，Ｌａ＾３＋的传质渗透系数ρ趋于稳定，随着体系反萃酸度的增加，ρ值略有增加。与同类中空纤维管支撑液膜体系相比，该体系对稀土元素有较强的富集能力，且稳定性较好。     

面向储能应用的多尺度电极材料结晶设计

电化学储能过程包含固/气/液界面反应、分层次的传质和电荷传递过程,并涉及微观-介观-宏观的跨尺度问题等.电极材料的宏观电化学性能是不同尺度影响因素的综合表现.结晶是电极材料合成的重要过程,与电极材料的功能特性紧密相关,涉及原子分子成核和晶体生长过程,具有多尺度、多因素、多层次特征.本文从结晶角度,在微观、介观、宏观尺度...     

钠型斜发沸石Na+-K+离子交换特性研究(Ⅱ)--过程传质模型及动力学特性研究

利用浅床实验法研究查明了钠型斜发沸石Na -K 离子交换过程以液膜扩散为主的控制机理,依据传质膜理论,推导出液膜控制下的离子交换传质速率模型,并测定了离子交换动力力学曲线和过程传质系数.研究结果表明:钠型斜发沸石Na -K 离子交换速率与溶液流速、温度和溶液的K 浓度成正比,与溶液粘度和沸石粒径成反比,过程总传质系数的模型计算值 与实验值拟和较好.     

硫化物在铂电极上电氧化时空动力学的模型模拟和分析(英文)

根据铂电极上硫化物电催化氧化的反应机理,本文提取动力学模型并利用数值模拟研究了N型负微分阻抗(N-NDR)振荡区域的电极表面时空反应动力学.在均相体系模拟中观察到电流简单振荡和复杂振荡,其来源于双电层电势自催化与传质限制和毒化物种吸附负反馈的相互耦合.为了更接近于真实体系,在模型中考虑了平行和垂直于电极表面两个方向的传质过程.模拟结果发现了与实验现象具有相同演化行为的复杂斑图,如行波和闪烁波;同时在传质耦合体系模拟中观察到双电层电势双臂螺旋波.本研究工作促进对电化学体系时空斑图的理解和预测.     

Direct Visualization of Nanoconfinement Effect on Nanoreactor via Electrochemiluminescence Microscopy

Nanoconfinement in mesoporous nanoarchitectures could dramatically change molecular transport and reaction kinetics during electrochemical process. A molecular-level understanding of nanoconfinement and mass transport is critical for the applications, but a proper route to study it is lacking. Herein, we develop a single nanoreactor electrochemiluminescence (SNECL) microscopy based on Ru(bpy)₃²⁺-loaded mesoporous silica nanoparticle to directly visualize in situ nanoconfinement-enhanced electrochemical reactions at the single molecule level. Meanwhile, mass transport capability of single nanoreactor, reflected as long decay time and recovery ability, is monitored and simulated with a high spatial resolution. The nanoconfinement effects in our system also enable imaging single proteins on cellular membrane. Our SNECL approach may pave the way to decipher the nanoconfinement effects during electrochemical process, and build bridges between mesoporous nanoarchitectures and potential electrochemical applications.     

Electrochemical pressure impedance spectroscopy for investigation of mass transfer in polymer electrolyte membrane fuel cells

Mass transfer phenomena in membrane fuel cells are complex and diversified because of the presence of complex transport pathways including porous media of very different pore sizes and possible formation of liquid water. Electrochemical impedance spectroscopy, although allowing valuable information on ohmic phenomena, charge transfer and mass transfer phenomena, may nevertheless appear insufficient below 1 Hz. Use of another variable, that is, back pressure, as an excitation variable for electrochemical pressure impedance spectroscopy is shown here a promising tool for investigations and diagnosis of fuel cells.     

Mn3+/Mn2+氧化还原体系的旋转圆盘电极法性能

氧化还原液流电池的独特性能受到关注[1～4]。本文综合运用循环伏安法,旋转圆盘电极法研究锰离子浓度较高(0 25～0 35mol·L-1、转速范围较宽(400～4200rpm)、同时考虑过电位的条件下Mn(Ⅲ)/Mn(Ⅱ)电对在RDE铂盘电极上的电极过程动力学并确定有关的动力学参数,了解其影响因素,为该电对作为氧化还原液流电池正极活性材料提供动力学依据。1　实验部分铂电极使用前在铬酸洗液中浸10min,水冲洗干净,蒸馏水淋洗,然后在6 3mol·L-1H2SO4中超声清洗10min,再用CHI660电化学工作站(美国CH仪器公司)控制,以0 05V/s的扫速在-1 0～1 2V之间扫…     

Electrochemical reduction of the iodinated contrast medium iomeprol: iodine mass balance and identification of transformation products

Potentiostatic-controlled electrochemical reduction of iomeprol was used to deiodinate iomeprol (IMP), a representative of the iodinated X-ray contrast media. The reduction process was followed by product analysis with liquid chromatography-electrospray ionization-tandem mass spectrometry and ion chromatography-inductively coupled plasma-mass spectrometry. The identification is mainly based on the interpretation of the mass fragmentation. The product analysis showed a rather selective deiodination process with the successive occurrence of IMP-I, IMP-2I, IMP-3I, and a transformation product (TP), respectively. The TP was formed from IMP-3I by a further cleavage of an amide bond and release of a (C = O)CHOH group from the side chain of IMP. The iodine mass balance on the basis of IMP and iodide showed a gap of about 26% at the beginning of the electrolysis process which could be completely closed by taking the intermediates IMP-I and IMP-2I into consideration. This means that the major intermediates and the TPs were considered and that the reduction process is a rather selective one to remove organically bound iodine from X-ray contrast media. An attractive application area would be the electrochemical deiodination of X-ray contrast media in urine of patients or hospital effluents.      

锂离子电池多孔电极理论的回顾与新思考

本文总结了Newman多孔电极理论的基本内容,提出若干改进思路. 提出基于离子-空穴耦合传输机制描述浓电解质中的离子输运过程,在此基础上引入离子-电子耦合转移反应的思想处理电极材料中的离子传输问题,并通过计算嵌锂材料的离子扩散系数验证其合理性. 总结了描述多孔电极多尺度结构的相关理论和技术,表明均质化方法和基于结构重建的介观模拟方法均能给出比较合理的有效输运参数,从而提高多孔电极理论模拟结果的准确性.     

Square wave voltammetry at disc microelectrodes for characterization of two electron redox processes

Analytical explicit solutions are presented for the use of square wave voltammetry (SWV) at disc microelectrodes to study two-electron reversible redox processes. This combines the advantages of SWV (minimization of capacitative effects, peak-shaped response and quick experiments) with those of microelectrodes (reduction of capacitative and ohmic drop effects, enhanced mass transport and measurements of small volumes). Further, the analytical expressions are very easy to implement in comparison with the numerical methods usually employed for simulation of electrochemical experiments at microdisc electrodes. From the theory, the effects of the technique parameters (frequency, pulse amplitude) are examined and procedures are given for the characterization of the redox system from the values of the peak current, peak potential and half-peak width. Finally, the theory is applied to the experimental study of the two-electron reduction of anthraquinone-2-sulfonate in aqueous media. For this system, the formal potentials of the redox centres in aqueous solutions can be tuned by means of the electrolyte cation.     

A stochastic model in liquid penetration through fibrous media

The statistical genesis of the process of liquid penetration through fibrous media can be regarded as the interaction and the resulting balance among media and liquid cells that comprise the ensemble. A stochastic method, Ising's model, combined with Monte Carlo simulation, can therefore be employed in the study of liquid penetration through fibrous media. This process is driven by the difference of energy of the system after and before a liquid moves from one cell to the other. The energy of the system comprises the internal energy, work done by external force to the system, and the mechanical energy. For experimental verification, the process of water penetration through isotropic fiber mats, both spontaneously and under pressure, is examined. Simulation results are in good agreement with the experiments, indicating a good prospect of the method to be applied in this area.     

Eccentric phenomena at liquid mercury electrode/solution interfaces: upward, downward, and circular motions

The present paper describes a visualization of unidirectional and circular motions triggered by an electrochemical redox reaction at a charged, bent, and streamed liquid electrode/liquid solution interface. The novel circular motion that induces a conversion of electrochemical energy into mechanical energy could be visualized for the first time at a hanging mercury drop electrode (HMDE)/dimethyl sulfoxide (DMSO) solution interface via the electrochromic reaction of 2,1,3-benzothiadiazole (BTD) by using a CCD-color video camera. The observed motions are self-insisting in nature and are tunable into upward, downward, clockwise, and anticlockwise ones by an appropriate choice of the experimental conditions. This circular motion is visualized for the first time as the cause of the well-known cyclic voltammetric anodic current oscillation at the HMDE. Several small perturbations, for example, surface tension, surface motion, bulk motion, diffusional mass transport, and surface electrochemical potential are considered to be endlessly amplified by their coupling in a cyclic chain, resulting in such macroscopic motions at the electrode/solution interface. All of the phenomena can be explained on the basis of the modern theory proposed by Aogaki et al. for the polarographic streaming maxima of the first kind.     

Mass transfer model of triethylamine across the n-decane/water interface derived from dynamic interfacial tension experiments

This publication presents a detailed experimental and theoretical study of mass transfer of triethylamine (TEA) across the n-decane/water interface. In preliminary investigations, the partition of TEA between n-decane and water is determined. Based on the experimental finding that the dissociation of TEA takes place in the aqueous and in the organic phase, we assume that the interfacial mass transfer is mainly affected by adsorption and desorption of ionized TEA molecules at the liquid/liquid interface. Due to the amphiphilic structure of the dissociated TEA molecules, a dynamic interfacial tension measurement technique can be used to experimentally determine the interfacial mass transport. A model-based approach, which accounts for diffusive mass transport in the finite liquid bulk phases and for adsorption and desorption of ionized TEA molecules at the interface, is employed to analyze the experimental data. In the equilibrium state, the interfacial tension of dissociated TEA at the n-decane/water interface can be adequately described by the Langmuir isotherm. The comparison between the theoretical and the experimental dynamic interfacial tension data reveals that an additional activation energy barrier for adsorption and desorption at the interface has to be regarded to accurately describe the mass transport of TEA from the n-decane phase into the aqueous phase. Corresponding adsorption rate constants can be obtained by fitting the theoretical predictions to the experimental data. Interfacial tension measurements of mass transfer from the aqueous into the organic phase are characterized by interfacial instabilities caused by Marangoni convection, which result in an enhancement of the transfer rate across the interface.     

Formation of negative oxidation states of platinum and gold in redox ionic liquid: Electrochemical evidence

The electrochemical reduction of noble metal electrodes in the presence of redox ionic liquid, 1-ferrocenylethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [FcEMIM][TFSI], was investigated by cyclic voltammetry. Our experiments suggest the formation of metal with negative oxidation states, in the cases of platinum and gold electrodes [M_n⁻, FcEMIM⁺]. By analogy with the previous work, the formation of these phases is concomitant with the insertion of the supporting electrolyte; which correspond in our experimental condition to the redox cation of the ionic liquid. As an exciting result, the electrochemical investigations of the reduced electrode in electrolytic solution, containing solvent and supporting electrolyte, evidence the presence of the ferrocene groups at the electrode surface. Moreover, the reduced electrode exhibits the presence of the ferrocene even after, contact with air, after ultrasound, and after physical polishing, highlighting the large stability of this organo-metallic phases formed in this media. The AFM investigations demonstrate the morphological change of the platinum surface after the reduction process. Finally, our works bring a formal electrochemical proof of the presence of the ionic liquid cation inside the electrode material after the cathodic treatment in this media.