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。     

表面能与晶体生长/溶解动力学研究的新动向

界面现象使物质在结晶过程中出现了临界现象.但最近的研究指出在物质溶解过程中,在表面能量的控制下也存在着临界现象以及尺寸效应.实验发现,当晶体自身小到一 定的程度时(通常在纳米尺度上并和临界蚀坑的大小相近),在溶解过程中其速度会自发降 低,反应被抑制乃至停止.尽管在热力学上表面能的因素可以赋予小颗粒晶体较大的溶解度 ,但表面能却也能通过对临界条件的控制而使这些微粒在动力学上不被溶解.这个发现不仅 解决了纳米颗粒在水溶液中稳定性的问题,而且还从动力学的角度解释了生物矿物选择纳米 尺度作为其基本构成单元的原因.由于表面能和晶体生长/溶解的动力学有着密切的关系, 我们可以通过对表面能的调节来修改它们的动力学速度和晶体的形貌.反过来,也可以用动力学的方法来测定表面能及表面吸附/脱附常数等.相对于常规的界面研究手段,通过生 长和溶解动力学途径所得的数据有着很好的可靠性及重复性.我们认为,晶体生长和溶解的 动力学和表面能的研究相结合,不仅为界面研究提供了新的思路和方法,而且也会推动晶体生长和材料科学的发展.     

Dynamic Study of Gemini Surfactant and Single-chain Surfactant at Air／Water Interface

Molecular dynamics (MD) simulation are used to study the properties of gemini surfactant of ethyl-α,ω-bis(dodecyldimethylammonium bromide) (C12C2C12) and dodecyl-trimethylammonium bromide (DTAB) at the air/water interface, respectively. In the two systems,t he surfactant concentrations are both 28 wt.%, and other conditions are also the same. After reaching the thermodynamic equilibrium, the concentration profiles, the radial distributions functions (RDF) and the mean squared displacement (MSD) are investigated. The results reveal that the surface activity of C12C2C12 surfactant is higher than DTAB surfactant.     

Effects of Amplitude of the Radiofrequency Electromagnetic Radiation on Aqueous Suspensions and Solutions

The effects of radiofrequency (RF) (1–4) and magnetic fields (5–9) on the behavior of aqueous solutions and suspensions have been a popular subject in recent years. The mechanism of the magnetic “water memory” effect, though, is still largely unknown (5). In this work, we present evidence that the primary “receptor” of the electromagnetic radiation is a gas/liquid interface. Gas can be either already present in water or produced by the effects of electromagnetic fields. Perturbed gas/liquid interfaces require hours to equilibrate. Certain RF and magnetic signals also produce reactive oxygen and hydrogen species (superoxide, hydrogen peroxide, hydrogen, atomic hydrogen). The perturbed gas/liquid interface modifies the hydrogen bonding networks in water and also the hydration of ions and interfaces. Careful outgassing removes all of the effects of the electromagnetic fields, including the magnetic memory effect. The amplitude of the applied field influences the observed effects. Different amplitudes of RF radiation perturb the interfacial water in different ways and consequently affect the behavior of colloids and ions in specific manners. For instance, the bulk and template precipitation of calcium carbonate, zeta potentials of suspended colloids, rate of dissolution of colloidal silica, and attachment of colloidal silica to metal surfaces are modified in specific ways with the low amplitude or high amplitude RF treatments described in this paper. The solubility/diffusivity of gas species is also modified in a different manner, and it is probably at the core of the specificity of the RF amplitude effects.     

毛细管电色谱-质谱联用技术进展

毛细管电色谱-质谱联用技术结合了毛细管电色谱高分离性能和质谱强定性能力的特点，近年来得到较快的发展。本文系统综述了CEC/MS接口技术及在复杂样品分离分析中应用的最新进展。引用文献45篇。     

Mineral–water interfacial structures revealed by synchrotron X-ray scattering

Chemical reactions occurring at the mineral–water interface are controlled by an interfacial layer, nanometers thick, whose properties may deviate from those of the respective bulk mineral and water phases. The molecular-scale structure of this interfacial layer, however, is poorly constrained, and correlations between macroscopic phenomena and molecular-scale processes remain speculative. The application of high-resolution X-ray scattering techniques has begun to provide substantial new insights into the molecular-scale structure of the mineral–water interface. In this review, we describe the characteristics of synchrotron-based X-ray scattering techniques that make them uniquely powerful probes of mineral–water interfacial structures and discuss the new insights that have been derived from their application. In particular, we focus on efforts to understand the structure and distribution of interfacial water as well as their dependence on substrate properties for major mineral classes including oxides, carbonates, sulfates, phosphates, silicates, halides and chromates. We compare these X-ray scattering results with those from other structural and spectroscopic techniques and integrate these to provide a conceptual framework upon which to base an understanding of the systematic variation of mineral–water interfacial structures.     

碳氟链与碳氢链表面活性剂在固液界面上的吸附

全氟辛酸及其钠盐和十二烷基硫酸钠在R972上的吸附等温线均为S型或LS型，指示固液界面吸附过程中有表面疏水缔合物生成．碳氟表面活性剂的饱和吸附量显著高于碳氢表面活性剂的饱和吸附量．加电解质于液相使各体系吸附量上升．对于碳氟表面活性剂，甚至引起吸附等温线类型变化．例如，不加电解质时全氟辛酸在R972上的吸附等温线为S型，而加入HCl（c＝0．05mol·dm－3）使吸附等混线变成LS型．全氟辛酸比全氟辛酸钠在R972上的吸附更强．几种表面活性剂在R972上的吸附均随温度升高而减少。应用两阶段吸附模型及通用吸附等温线公式可以很好地解释所得实验结果．     

Ternary surface complexes by theE(%)-pH curve method

A new method for the study of ternary surface complexes at liquid-solid interface, theE(%) -pH curve method, was proposed. Four types ofE(%)-pH curves, namely, phenomenon of left-right shifts of S-shaped curve, V-shaped curve, monodirection shift curve and X-shaped curve, were discovered. Correspondingly, apart from type (I) ternary surface complex and type (II) ternary surface complex , a new type of ternary surface complex was discovered. Project supported by the National Natural Science Foundation of China and the Fund of Doctoral Degree’s Spot.     

Variable Mott-Schottky plots acquisition by potentiodynamic electrochemical impedance spectroscopy

Potentiodynamic electrochemical impedance spectroscopy provides extraction of potential-dependent space charge layer capacitance from potentiodynamic impedance spectra of non-stationary semiconductor–electrolyte interface. The new technique has been applied for acquisition of Mott-Schottky plots of cathodically treated TiO₂ anodic films. Cathodic treatment in 1 M H₂SO₄ increases donor density and flat band potential of TiO₂. Freshly doped films show hysteresis in the space charge layer capacitance in cyclic potential scans. The subsequent cycling eliminates the hysteresis but preserves the greater part of the doping effect. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, 13–16 March 2005     

Adsorption Behavior of a Water-soluble Porphyrin at the Glass-water Interface as Studied by Synchronous Total Internal Reflection Fluorescence Spectroscopy

Total imernal reflection fluorescence spectroscopy (TIRF) and synchronous scanning technique were combined to study the adsorption behavior of the meso-tetrakis (4-sulfonatophenyl)porphyrin (TPPS) at the glass-water interface without any surfactant. The pH dependence of synchronous fluorescence signal at the interface was analyzed. Both unprotonated (TPPS^4-) and diprotonated (H2TPPS^2-) forms of TPPS were observed at the interface. But the interface favored the adsorption of. The apparent estimated pKa2 value shifted from 5.00 in the bulk solution to 2.7 at the interface. STIRF provides a good technique to study multi-component systems at the interface.