焦绿石型复合氧化物对氧电极反应的催化作用

前文介绍了新型双功能氧电极材料Pb_2[Ru_(2-x-g)Sb_xPb_y]O_(7-z)焦绿石型复合氧化物(简称Pb-Sb-Ru氧化物)的合成及其性能。本文介绍氧在该氧化物上还原及析出的动力学特性。 1 实验方法 1.1 材料的制备 Pb-Sb-Ru氧化物的制备、检测方法同文献中的材料4~#。     

Adatom Hypothesis as a Predominant Mechanism of Surface Enhanced Raman Scattering: A Review of Experimental Argumentation

A contemporary review of research concerning the mechanism of surface enhanced Raman scattering (SERS) is presented and it is stated that this problem is yet to be solved. The necessity to yet once again analyze some of the familiar experimental observations and the deep-rooted beliefs and revise quantitative evaluations of SERS enhancement via major mechanisms (electromagnetic and chemical) with allowance made for most important experimental characteristics of SERS is substantiated. The characteristics are enumerated and the role they play in the above evaluations is sketched. Attention is focused mainly on electrochemical aspects of SERS problem, which to a large extent define the content and salient features of SERS and provide basic experimental justification for the so-called adatom hypothesis.__________Translated from Elektrokhimiya, Vol. 41, No. 8, 2005, pp. 899–935.Original Russian Text Copyright © 2005 by Lazorenko-Manevich.In memory of Vladislav Vladimirovich Marinyuk     

In situ and online monitoring of hydrodynamic flow profiles in microfluidic channels based upon microelectrochemistry: optimization of electrode locations.

Herein, we extend our previous approach concerning the reconstruction of profiles of pressure-driven hydrodynamic flow in microfluidic channels based on current measurements at band electrode(s) [see the preceding paper ChemPhysChem 2005, 6, 1581]. We address the central issue of optimization of geometrical parameters describing the electrode(s) assembly (a single band and two bands working in generator-collector mode) within the channel flow cell to enhance the speed and precision of the flow profile reconstruction method.     

Photo‐Induced Electron Transfer Between Photosystem 2 via Cross‐linked Redox Hydrogels

Photosystem 2 (PS2) that catalyses light driven water splitting in photosynthesis was ‘wired’ to electrode surfaces via osmium‐containing redox polymers based on poly(vinyl)imidazol. The redox polymer hydrogel worked as both immobilization matrix and electron acceptor for the enzyme. Upon illumination, the enzymatic reaction could be switched on and a catalytic current was observed at the electrode. The catalytic current is directly dependent on the intensity of light used for the excitation of PS2. A typical current density of 45 μA cm^?2 at a light intensity of 2.65 mW cm^?2 could be demonstrated with a significantly improved operational stability.     

A 100-kW three-phase AC plasma furnace for spheroidization of aluminum silicate particles

A 100-kW three-phase ac plasma furnace with sheathed copper electrodes (sheathing gas: air) is presented. It is used for spheroidizing chamotte (refractory-fired clay) particles having a smooth, pore-free surface. A simple, one-dimensional numerical model for the heat transfer to the particles explains the maximum processing rate and the detrimental influence of an inhomogeneous particle size distribution.     

Diamond like carbon coated films for enzyme electrodes; characterization of biocompatibility and substrate diffusion limiting properties

The biocompatibility and substrate diffusion limiting properties for a range of diamond like carbon (DLC) coated microporous polycarbonate and DLC coated dialysis (haemodialysis) membranes have been studied. This characterisation builds upon previous findings where DLC coated membranes imparted enhanced enzyme electrode performance. In this study electrode linear ranges have been extended from 10 mM glucose for a 0.01 μm pore size membrane to 160 mM. These findings correlated with the duration of DLC deposition and associated reductions in permeability for glucose. Permeability coefficient ratios for both microporous and dialysis membranes were also found to be important with low glucose/O₂ permeability ratios imparting extensions in glucose linear response range. DLC coated membranes employed within enzyme electrodes have also been shown to exhibit enhanced haemocompatibility as determined by both sensitivity change and surface deposition of blood components examined by scanning electron microscopy. Correlations are made between the reduced losses in sensor response to biofouling/ working electrode passivation processes, and extended linear ranges that DLC coated membranes may impart to enzyme electrode performance. Particular reference is made to the determination of glucose levels within whole blood.     

Clays as architectural units at modified-electrodes

Since Ghosh and Bard [80] first established the field of clay-modified electrodes some 15 years ago, great strides have been made in understanding the nature of the clay structural units and their impact on transport of a variety of electroactive probes (anions, neutrals, small cations, large cations, and compounds with distributed charge). Great strides have also been made in understanding the nature of the layered material in creating access of interlayer sites (size, charge, iron content, pillaring, and organic tailoring). In the last five years several successful applications of clay-modified electrodes have been achieved. Given the explosive growth in tailoring and construction of novel clay structures it seems reasonable to predict further significant advances in applications involving clay-modified electrodes.     

Response behavior of sodium-selective electrodes modified by surface attachment of the anticoagulant polysaccharides heparin and chondroitin sulfate

Two different polysaccharides with anticoagulant activities, heparin and chondroitin sulfate, were used to modify the surface of sodium-selective electrodes based on asymmetric cellulose triacetate (CTA) membranes. The membranes were formulated with sodium ionophore X, anionic additive, and o-nitrophenyl octyl ether. The response behavior of the surface-modified sodium electrodes was compared with that of control CTA, as well as poly(vinyl chloride) (PVC)-based sodium-selective electrodes. It was found that the selectivity coefficients obtained with the surface modified CTA membrane electrodes were slightly higher than those of the control, but in the case of heparin-modified electrodes they still met the requirements for analysis of sodium in physiological fluids within an error of <1%; the corresponding error for chondroitin sulfate-modified electrodes was also <1% except for the case of potassium ion in which the error was 1.3%. Likewise, it was found that other response characteristics, such as detection limit, linear range, slope of the response plot, selectivity pattern, and response time were comparable in both the control and the polysaccharide-modified electrodes. Therefore, the surface modification does not significantly alter the response behavior of the sensors.     

Measuring the solubilities of ionic liquids in water using ion-selective electrodes

Polyvinyl chloride-plasticized membrane ion-selective electrodes (ISE) based on conventional ion-exchangers have been proposed as a cheap universal tool to measure the solubilities of ionic liquids (ILs) in water. They are applicable for ILs with a wide range of solubilities in water, since the linear range of a potentiometric response spans several orders of magnitude. As an example, we have fabricated and tested ISEs for widely used alkylimidazolium ionic liquids. The aqueous solubilities of four typical ILs have been determined at 21 °C: 0.075±0.001 mol l^–1 (1-butyl-3-methylimidazolium, BMIm, hexafluorophosphate); 0.018±0.001 mol l^–1 (BMIm bis(triflylimide)); 0.054±0.007 mol l^–1 (1-butyl-2,3-dimethylimidazolium, BDMIm, hexafluorophosphate); 0.014±0.001 mol l^–1 (BDMIm bis(triflylimide)).