Application of pulse methods to the determination of the electrochemical characteristics of lithium intercalates

The transfer processes proceeding in insertion electrodes with surface control on the application of a potential or current step are considered theoretically. The theoretical relationships have been verified by the determination of the kinetic and diffusion parameters of electrochemical lithium intercalation into thin carbon films. The overall electrode polarization is divided, both theoretically and experimentally, into the kinetic component, related to hindered ion transfer in the passive surface layer, and the diffusion one, related to decelerated lithium diffusion in the carbon matrix. The polarization dependence of kinetic current is shown to obey the same regularities that the current-potential function of the lithium electrode. The concentration dependences of the surface layer parameters and the diffusion coefficient of lithium in carbon have been determined.     

Aniline and Anilinium Ion Ozonation in Aqueous Solution

The ozonation of aniline and anilinium ion in aqueous solution is investigated by determining the product distributions at different degrees of ozonation. Results indicate that anilinium ion, although less reactive than aniline, still has a remarkable reactivity towards ozone. The high anilinium ion reactivity and the observed product distributions are explained by assuming a radical mechanism for anilinium ion ozonation, whereas the behavior of aniline appears to be regulated mainly by the electrophilic ozonolysis mechanism.     

CO2在全氟羧酸离子交换膜内促进传质特性的研究

本文以全氟羧酸离子交换膜为支撑体、乙二胺(EDA)为活性络合剂、制备促进传质膜。在常用的工业条件下,测定了纯CO_2以及CO_2/N_2二元混合物在该膜内的渗透通量。实测结果表明,此膜对CO_2的促进因子可达13.8,而对CO_2/N_2的分离因子高达316。本文假设促进传质过程的控制步骤为气体在膜相的扩散,据此导出了相应的机理模型,该模型与实测结果吻合良好。     

From clay- to organoclay-film modified electrodes: tuning charge selectivity in ion exchange voltammetry

The surface of two natural smectite-type clay samples was chemically modified by covalent grafting of amine groups, by reaction with γ-aminopropyltriethoxysilane, which were easily protonated in HCl medium. Multisweep cyclic voltammograms of clay-film modified glassy carbon electrodes made of either the raw clays or the propylammonium-functionalized samples exposed to Ru(NH₃)₆³⁺ or Fe(CN)₆³⁻ electroactive probes were obtained. The results indicated a permselective behavior of these clay and organoclay-films based on either favorable or unfavorable electrostatic interactions. The cation-exchanging raw clay film modified electrodes exhibited accumulation properties for Ru(NH₃)₆³⁺ species while rejecting Fe(CN)₆³⁻, whereas the anion-exchanging organoclay coatings acted as a barrier against Ru(NH₃)₆³⁺ while increasing dramatically the concentration of Fe(CN)₆³⁻ species at the electrode surface. Strong binding of the probe to the organoclays resulted in a potential shift of ca. 0.1 V of the voltammetric signals characteristic of the Fe(CN)₆^3−/4− couple in the anodic direction. Their good preconcentration efficiency at low analyte concentration highlighted their interest for electroanalytical applications.     

Modeling of protein adsorption to DEAE sepharose FF: Comparison of data with model simulation

The equilibrium and kinetic characteristics of the adsorption of human serum albumin (HSA) and ovalbumin (OVA) to the DEAE Sepharose FF weak anion exchanger were experimentally determined. The rate for protein adsorption was simulated with two different models, the first being based on a single lumped kinetic parameter, while the second includes the individual mass transfer processes occurring prior to the adsorption intervention, i.e., diffusion across the liquid film surrounding individual particles and diffusion within the ion exchanger particle itself. The actual adsorption of OVA to DEAE Sepharose FF in fully mixed stirred vessels and in packed bed columns was consistent with both models. In the case of HSA, however, the adsorption profile in an agitated vessel was consistent only with the pore diffusion model and neither model could correctly predict the latter part of the breakthrough profile observed in packed bed experiments.     

流动床离子交换工艺在己二酸催化剂回收中的应用

介绍流动床离子交换装置回收催化剂的生产工艺，从交换装置的选择到运行，分析了流动床的优点、影响因素以及生产中应注意的问题和要求。     

Imaging and probing catalytic surface reactions on the nanoscale: Field Ion Microscopy and atom-probe studies of O2–H2/Rh and NO–H2/Pt

We present dynamic studies of surface reactions using video-Field Ion Microscopy (FIM) along with Pulsed Field Desorption Mass Spectrometry (PFDMS). Catalytic water formation is followed using rhodium and platinum 3D field emitter crystals for the oxidation of hydrogen with either oxygen (Rh) or NO (Pt). Strongly non-linear dynamics are observed with nanoscale spacial resolution. For both reactions quasi-oscillatory behaviour exists under certain conditions of temperatures and partial pressures. An influence of the probing electric field is observed and possibly essential in establishing oscillatory behaviour. Local chemical probing of selected surface areas with up to 400 atomic surface sites proves catalytic water formation to take place. Since water ions (H₂O⁺/H₃O⁺) cause image formation of the O₂–H₂ reaction on Rh, respective videos provide space-time resolved information on the catalytically active sites. Atom-probe data also reveal that the surface of the Rh sample reversibly switches from a metallic to an oxidized state during oscillations. As to the NO–H₂ reaction on Pt, fast ignition phenomena are observed to precede wave fronts. After catalytic water formation, NO molecules diffuse into emptied areas and cause high image brightness. Depending on the size of the Pt crystal, the reaction may ignite in planes or kinked ledges along the <100> zone lines. Thus FIM provides clear experimental evidence that kinks are more reactive than steps in the catalytic NO + H₂ reaction. Pt surface oxidation occurs and has probably been underestimated in previous FIM studies.     

固体酸催化环氧丙烷醇解反应活性研究

讨论了工业化生产中使用杂多兰催化剂的方法和产率,以及氢型离子交换树脂,固体超强酸也可作为此反应催化剂的效果,并与直接溶解在反应液中杂多兰催化活性进行了比较,得出相关结论.     

电解质溶液热力学性质的研究进展

从电解质溶液的经典理论、半经验模型和统计力学3方面综述了电解质溶液热力学性质的研究进展,并对各种理论和模型在理论与实践方面的局限性作了相关评述。从分子、离子角度对电解质溶液的热力学性质进行研究比较,探讨了其宏观热力学性质与微观结构的相关性。展望了电解质溶液热力学理论近期研究的热点和未来的发展方向。     

Electrochemical micromachining using a solid electrochemical reaction at the metal/β″-Al2O3 microcontact

A simple solid state technique for electrochemical micromachining of metal substrates using a metal ion conductor (Na-β″-Al₂O₃) was proposed. The fundamental solid electrochemical cell consists of a (anode) metal substrate (M = Ag, Cu, Zn, and Pb)/pyramidal Na-β″-Al₂O₃/Ag (cathode) system, where the contact diameter between M/Na-β″-Al₂O₃ was extremely small, on the order of a few micrometer. Under an applied electric field, the metal substrate was electrochemically oxidized to metal ions (Mⁿ⁺) at the M/Na-β″-Al₂O₃ microcontact. These Mⁿ⁺ ions migrated into the Na-β″-Al₂O₃. As a result of continuous electrolysis, the metal substrate was locally consumed at the microcontact, and thus solid state electrochemical micromachining was accomplished. As expected, the machining size or depth depended on the electrolysis conditions (current, operating time) and the apex configuration of pyramidal Na-β″-Al₂O₃. Moreover, the scanning of the Na-β″-Al₂O₃ pyramid during electrolysis produced a fine patterned metal substrate. In the present paper, solid state electrochemical micromachining was performed for several metal substrates, and its advantages and disadvantages vis-a-vis the conventional electrochemical micromachining method are discussed in detail.