The Electrochemistry of Tetraphenyl Porphyrin Iron(III) Within Immobilized Droplets Supported on Platinum Electrodes

For the first time, the voltammetry of an ensemble of immobilized benzonitrile microdroplets containing 5,10,15,20‐tetraphenyl‐21H,23H‐porphine iron (III) chloride, TPPFeCl immobilized at platinum electrodes immersed in various aqueous electrolytes has been explored. The reduction of TPPFeCl was observed with the voltammetric response seen to be highly dependent on the nature of ions in the surrounding aqueous phase. Unlike voltammetry in purely homogeneous solution the nature of the aqueous electrolyte can influence the voltammetry in the droplet phase. The electrochemical reduction of TPPFeCl contained within tetrabutylammonium chloride (TBACl) supported benzonitrile (PhCN) microdroplets immersed into an aqueous solution of TBACl was first studied. During TPPFeCl reduction the resulting [TPPFeCl]^? species is stabilized due to the excess of chloride anions inside the oil droplet. Voltammograms of homogeneous solutions of PhCN supported with TBACl show similar chemically reversible process which is also attributed to the stable [TPPFeCl]^? species. This anion stabilization was not observed when the oil droplets were supported with tetrabutylammonium perchlorate (TBAP) or when the PhCN solution bathing the microdroplet ensemble was supported with TBAP resulting in a chemically irreversible process. The voltammetry of unsupported droplets immobilized on a platinum electrode immersed in different aqueous electrolytes was also explored and the fate of the [TPPFeCl]^? species formed considered during the reduction sweep. Similarities and difference to voltammetry in purely homogeneous media are noted and the use of droplet voltammetry provides complimentary information.     

Effects of amino acids on crystal growth of CaC2O4 in reverse microemulsion

Crystal growth of calcium oxalate (CaC2O4) in bulk aqueous solution, reverse microemulsion of p-octyl polyethylene glycol phenylether (OP)/iso-octyl alcohol (IOA)/cydohexane/water and above microemulsions containing different kinds of amino acids, such as aspartic acid (Asp), tyrosine (Tyr) and tryptophan (Trp) were studied. The results indicated that different crystallization types of the crystals, which were calcium oxalate monohydrate (COM), calcium oxalate dihydrate (COD) and calcium oxalate trihydrate (COT), existed in bulk aqueous solution. But CaC2O4 growth mainly paralleled with (1 01) plane of COM in reverse microemulsion because of the induction of surfactant at water/oil interface. After adding amino acids into microemulsions, the growth of CaC2O4 crystals mainly influenced by the varieties of amino acids and the pH values of the amino acid aqueous solution. When pH values of the solutions was higher than isoelectric points of amino acids, CaC2O4 crystal paralleled with (1 01) plane of COM more easily with the addition of Trp, Tyr, Asp in turn; however, when pH of the solutions was lower than isoelectric points of Trp, CaC2O4 crystal growth paralleled with (020) face of COM. It is obviously that amino acids, pH values of the solutions and surfactant played important roles in the process of crystal growth of CaC2O4 in the microemulsions. The formation mechanism of CaC2O4 was also discussed in different microemulsions at last.     

Cr,Fe,Cu/Al2O3界面化学结构的光电子能谱

应用Ｘ－射线光电子能谱，通过离子刻蚀，原位研究第四周期过渡金属与氧化铝所形成界面的化学状态，结果表明，Ｃｒ，Ｆｅ在界面处有不同程度的氧化，氧化程度Ｃｒ＞Ｆｅ，而Ｃｕ则无明显氧化。化学成份的定量分析表明，界面过渡层的厚度与界面化学反应强弱直接相关。     

Surface film formation on a graphite electrode in Li‐ion batteries: AFM and XPS study

The formation of a passivation film (solid electrolyte interphase, SEI) at the surface of the negative electrode of full LiCoO₂/graphite lithium‐ion cells using LiPF₆ (1M ) in carbonate solvents as electrolyte was investigated by means of x‐ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The analyses were carried out at different potentials of the first and the fifth cycles, showing the potential‐dependent character of the surface‐film species formation. These species were mainly identified as Li₂CO₃ up to 3.8 V and LiF up to 4.2 V. This study shows the formation of the SEI during charging and its partial dissolution during discharge. Copyright © 2005 John Wiley & Sons, Ltd.     

Qualitative supercritical fluid extraction coupled to capillary gas chromatography

The usefulness and ease of utilizing supercritical fluid extraction (SFE) directly coupled to capillary gas chromatography (GC) as quantitative or qualitative analytical problem-solving tools will be demonstrated. As an alternative to conventional liquid solvent extractions, SFE presents itself as a means to achieve high extraction efficiencies of different compounds in complex solid matrices in very rapid tims frames. Moreover, SFE has an additional advantage of being able to achieve distinct extraction selectivities as a function of the solubilizing power of the supercritical fluid extracting phase. For on-line SFE/GC, the extraction effluent is directly transferred to the analytical chromatograph. On-line SFE/GC involves the decompression of pressurized extraction effluent directly into a heated, unmodified capillary split injection port of the GC. In this respect, SFE introduction into GC can be used as an alternative means of GC injection, comparable to such modes of injection as pyrolysis and thermal desorption. This paper will show applications of SFE/GC where mass spectrometric detection together with flame ionization detection was used for component identification from environmental, tobacco, and petroleum matrices.     

A review on experimental studies of surfactant adsorption at the hydrophilic solid-water interface

The progresses of understanding of the surfactant adsorption at the hydrophilic solid-liquid interface from extensive experimental studies are reviewed here. In this respect the kinetic and equilibrium studies involves anionic, cationic, non-ionic and mixed surfactants at the solid surface from the solution. Kinetics and equilibrium adsorption of surfactants at the solid-liquid interface depend on the nature of surfactants and the nature of the solid surface. Studies have been reported on adsorption kinetics at the solid-liquid interface primarily on the adsorption of non-ionic surfactant on silica and limited studies on cationic surfactant on silica and anionic surfactant on cotton and cellulose. The typical isotherm of surfactants in general, can be subdivided into four regions. Four-regime isotherm was mainly observed for adsorption of ionic surfactant on oppositely charged solid surface and adsorption of non-ionic surfactant on silica surface. Region IV of the adsorption isotherm is commonly a plateau region above the CMC, it may also show a maximum above the CMC. Isotherms of four different regions are discussed in detail. Influences of different parameters such as molecular structure, temperature, salt concentration that are very important in surfactant adsorption are reviewed here. Atomic force microscopy study of different surfactants show the self-assembly and mechanism of adsorption at the solid-liquid interface. Adsorption behaviour and mechanism of different mixed surfactant systems such as anionic-cationic, anionic-non-ionic and cationic-non-ionic are reviewed. Mixture of surface-active materials can show synergistic interactions, which can be manifested as enhanced surface activity, spreading, foaming, detergency and many other phenomena.     

应用扫描电化学显微镜研究电子在室温离子液体与1,2-二氯乙烷混合溶液/水相界面上的转移反应

应用扫描电化学显微镜研究了室温离子液体(Omim·Tf2N)与1,2-二氯乙烷(DCE)混合溶液/水界面上的电子转移反应. 在保持共同离子(Tf2N-)的浓度比恒定及异相电子转移反应由界面电势差所决定的条件下, 研究了离子液体和DCE混合溶液中二茂铁(Fc)与水相中亚铁氰化钾[K4Fe(CN)6]之间异相电子转移反应. 探讨了混合溶液中离子液体的体积分数(xRTIL)的变化对混合溶液/水界面上电子转移反应的影响. 结果表明, 随着xRTIL的减小(从1减小到0.1), Fc在混合溶液中的扩散系数单调递增(从2.730×10-7 cm2·s-1增加到9.131×10-6 cm2·s-1); 而异相电子转移反应速率常数(k)则先逐渐减小(从8.0 mol-1·cm·s-1减小到0.32 mol-1·cm·s-1), 之后又略有增大(从0.32 mol-1·cm·s-1增大到0.48 mol-1·cm·s-1). 对这种现象可能的原因进行了较详细探讨.     

Adsorption of oligooxypropylenated amines at the aqueous solution—air interface: Homologous series of piperidine and morpholine derivatives

The surface tension isotherms for pure oligooxypropylenated piperidine and morpholine at the aqueous solution—air interface were determined and interpreted. The surface excess concentration, Γ, the surface area per molecule, A, and the standard free energy of adsorption, ΔG°, were calculated according to a new empirical adsorption equation. The standard free energy contribution for the oxypropylene group (PO) in morpholine derivatives,ΔG° (PO) = −3.34 kJ mol⁻¹, is substantially lower than that for the PO group located in the piperidine derivatives, i.e. ΔG° (PO)= −3.12 kJ mol⁻¹.     

Dynamic surface elasticity of polymer solutions

The surfaces of surfactant solutions exhibit viscoelastic dilational behavior which may be investigated by modern optical and mechanical methods. The present study focuses on the dynamic dilational properties of the polymer solution — gas interface. Linear flexible polymer chains at the surface are considered as consisting of trains, lying on the surface, and loops and tails that protrude into the liquid. The Rouse model is used to describe the inner dynamics of the trains, whereas their motion relative to their neighbors on the surface can be described with the help of the reptation conception. An expression for the complex dynamic dilational surface elasticity has been derived. Although, in general, the relaxation of the surface tension is characterized by an infinite series of relaxation times, it is shown that for many systems the dynamics of the surface layer can be described approximately by only two main relaxation times. The dispersion equation, which was obtained earlier for solutions of conventional surfactants, is shown to be fulfilled for polymer solutions also.     

Influence of nano-structure on electrolytic properties in CeO2 based system

Doped ceria (CeO₂) compounds are fluorite type oxides that show oxygen ionic conductivity higher than yttria stabilized zirconia, in oxidizing atmosphere. In order to improve the conductivity, the effective index was suggested to maximize the oxygen ionic conductivity in doped CeO₂ based oxides. In addition, the true microstructure of doped CeO₂ was observed at atomic scale for conclusion of conduction mechanism. Doped CeO₂ had small domains (10-50 nm) with ordered structure in a grain. It is found that the electrolytic properties strongly depended on the nano-structural feature at atomic scale in doped CeO₂ electrolyte. This revised version was published online in August 2006 with corrections to the Cover Date.