Methanol Oxidation at Platinum in Alkaline Media: A Study of the Effects of Hydroxide Concentration and of Mass Transport

The hydroxide ion concentration dependence of the methanol oxidation reaction at Pt was studied using microelectrode voltammetry and rotating disk electrode voltammetry. Both methods suggest that the rate of methanol oxidation is limited by hydroxide mass transport at low hydroxide concentrations, while it is inhibited by hydroxide adsorption at high concentrations. It was possible to shift from the transport-limited regime to the inhibitory regime by varying the bulk concentration of hydroxide or by varying mass transport to the electrode. Rotating ring-disk electrode voltammetry was employed to qualitatively assess changes in the diffusion layer pH. The results indicated a decrease in the surface pH during methanol oxidation, as expected, but also that the pH reached a steady state during hydroxide transport limited methanol oxidation.     

Effect of an Alkylsulfo Compound on the Chromium Electrodeposition Rate

Effect of an alkylsulfo compound (ASC) on the cathodic process in chromate solutions is studied at 20–70°C. Below 40–50°C, ASC reduces the current efficiency for chromium (CE). Above 40–50°C, CE rises and then remains invariant with temperature. The ASC effect on the Cr deposition rate is attributed to variations in the sulfate concentration near the cathode, which are caused by the presence of ASC and its hydrolysis.     

Cl-对Zn-Fe族元素二元合金共沉积的催化作用

在氯化物电解液中以定电量（10C.cm^-2),恒温40℃电沉积Zn-Fe族元素二元合成,沉积产物用原子吸收光谱分析,根据分析结果,作出相应的电流效率、百分含量及部分极化曲线,镀层形貌采用扫描电镜（SEM）观察,发现：Zn-Fe族元素合金的共沉积为异常共沉积,Cl^-对铁族元素有催化作用,随着Cl^-浓度的增加,降低了铁族元素的过电位,促进铁族元素金属的沉积。     

镁在DMF中电沉积机理的研究

自本世纪初始,人们一直试图在非水体系中电沉积镁,迄今尚未见到令人满意的报道。此外,有关镁在非水体系中,在固态电极上电沉积机理的研究工作也未见系统报道。本工作首先确证了在高氯酸镁的DMF溶液中、在光亮铂电极上能电沉积出金属镁。在此基础上初步研究了这一电沉积过程的动力学特征,提出了在该体系中镁电沉积的机理。     

熔盐电沉积稀土金属及其合金的研究：中山大学电化学研究工作介绍

熔盐电沉积稀土金属及其合金的研究——中山大学电化学研究工作介绍①杨绮琴（中山大学化学与化学工程学院广州５１０２７５）稀土金属及其合金具有许多优异的特殊性能，在国民经济中的应用日益广泛，是发展现代高新科学技术不可缺少的材料，例如磁性、磁光、超导、贮氢、...     

Determining Role of the Chain Mechanism in the Temperature Dependence of the Gas-Phase Rate of Combustion Reactions

It is shown that the strong dependence of the rate of gas-phase combustion reactions on temperature is determined by the high values of the reaction rate constants of free atoms and radicals. It is established that with a branched chain mechanism, a special role in the reaction rate temperature dependence is played by positive feedback between the concentrations of active intermediate species and the rate of their change. The role of the chemical mechanism in the temperature dependence of the process rate with and without inhibitors is considered.     

Dependence of the self-bias on the plasma parameters and on the electrode areas in RF plasma reactors

From the current-voltage characteristics for the collisionless sheath the dependence of the self-bias on the plasma parameters (electron temperature, ratio of electron temperatures and electron densities at the two electrodes), on the applied external voltage, and on the ratio of the electrode areas is investigated. Sinusoidal (is well as periodic rectangular and triangular time dependences of the voltage are considered. The integral equation for the self bias voltage is solved numerically. For large external RF voltages in comparison to the floating potential, simple analytical formulas result for the dependence of the bias voltage on the plasma parameters and the dimensions of the electrodes, which can be useful in practice.     

Ozone reduction at Nafion modified Au electrode and the measurement of ozone concentration in highly resistive solutions

The mass transport and charge transfer kinetics of ozone reduction at Nafion coated Au electrodes were studied in 0.5 mol/L H2SO4 and highly resistive solutions such as distilled water and tap water. The diffusion coefficient and partition coefficient of ozone in Nafion coating are 1.78×10-6 cm2·s-1 and 2.75 at 25℃ (based on dry state thickness), respectively. The heterogeneous rate constants and Tafel slopes for ozone reduction at bare Au are 4.1×10-6 cm·s-1, 1.0×10-6 cm·s-1 and 181 mV, 207 mV in 0.5 mol/L H2SO4 and distilled water respectively and the corresponding values for Nafion coated Au are 5.5×10-6 cm·s-1, 1.1×10-6 cm·s-1 and 182 mV, 168 mV respectively. The Au microelectrode with 3 μm Nafion coating shows good linearity over the range 0-10 mmol/L ozone in distilled water with sensitivity 61 μA·ppm-1 ·cm-2, detection limit 10 ppb and 95% response time below 5 s at 25℃. The temperature coefficient in range of 11-30℃ is 1.3%.     

常温下从离子液体电解液中电沉积金属钴

研究了离子液体镀液中Co、Zn的共沉积行为。ZnCl2-EMIC -CoCl2电解液的循环伏安曲线上出现了三个电流峰,对应的电极电位分别为250mV、50mV、-200mV（vs. Zn2+/Zn）。结合EDS成分分析,可断定这三个电流峰分别对应着Co的电沉积、Co电极上Zn的欠电位沉积和Co-Zn合金的电沉积。恒电位沉积表明,当控制阴极电位在100 mV（vs. Zn2+/Zn）左右时,可得到高纯度的钴镀层;若进行恒电流沉积,则当电流密度为85mA/cm2左右时能够得到高纯度的钴镀层。对Co、Zn的共沉积机理研究表明,Co的电沉积过程和Zn 在Co上的欠电位沉积过程均受扩散过程控制。     

Efficient Intermolecular Charge Transport in Self-Assembled Fibers of Mono- and Bithiophene Bisurea Compounds

Hydrogen bonds between urea units allow self-organization of π systems in mono- and bithiophenes into fibers as shown schematically. In these fibers there is a surprisingly high mobility of charge carriers as determined by pulse-radiolysis time-resolved microwave conductivity measurements.     

5-羟色胺在碳纤维微电极上的电化学测定及伏安行为研究

本文研究了5 羟色胺在Na2HPO4 KH2PO4(pH6.0)缓冲溶液中,于自制的碳纤维微电极上的伏安行为。在此缓冲溶液中5 羟色胺有一对氧化还原峰,峰电位分别为0.2V和0.4V。峰电流与5 羟色胺的浓度分别在4.0×10-6～4.0×10-5mol/L和5.0×10-6～5.0×10-5mol/L范围内呈良好的线性关系,检出限分别为4.70×10-6mol/L和1.76×10-6mol/L。同时利用多种电化学方法求出了动力学参数。     

p型Se的电沉积及其转化为n型CdSe的机理研究

利用线性电位扫描光伏安法等技术研究钛基体上Se半导体薄膜的电化学形成及转化过程.实验结果表明,在H_2SeO_3溶液中进行电沉积可获得p型Se薄膜,它可在酸性CdSO_4溶液中阴极转化为n型CdSe.讨论了Se的电沉积动力学及其转化为CdSe的可能机理.所述原理可望用于p-n异质结的电化学制备.     

质量、热量传递过程中的Marangoni效应*

由质量、热量传递引发,表面张力梯度驱动的Marangoni效应不但对化学工程、材料工程和热能工程等领域里的一系列过程具有重要的影响,而且具有非线性耗散系统理论研究的一个具有实际意义的课题。对Marangoni效应的实验及理论研究有助于增进对微观传热、传质机理的理解,它的合理利用也可以提高某些过程的效率。迄今为止,对Marangoni效应的认识还不能满足理论研究和工程应用的要求。按期在各相关领域内对Marangoni的研究十分活跃,本文回顾了这些研究成果。     

温度对PbO2电沉积形核生长过程的影响研究

为了探讨温度对PbO₂电沉积形核生长过程的影响,在25℃、35℃、45℃、55℃、65℃使用电化学工作站测试了PbO₂在玻碳电极上沉积过程的循环伏安曲线、计时电位曲线及计时电流曲线,并对不同温度下电沉积的PbO₂镀层进行了SEM和XRD分析. 结果表明,在不同温度下PbO₂都经历了成核和核生长过程. 温度的升高没有改变PbO₂电沉积三维连续成核的模式,降低了沉积过程溶液阻力,对成核和晶体生长速率均有促进作用,在晶核密度达到饱和晶核密度以前,是以促进成核速率为主,减小PbO₂颗粒尺寸. 达到饱和晶核密度后,电沉积后期以促进晶体生长速率为主,不利于形成细小PbO₂颗粒.高温使得析氧速率提高,能耗增大.由实验结果得出,在55℃时得到的PbO₂镀层粒径最小.     

The Temperature Dependence of the Resistivity and Thermopower in Some Polyvalent Liquid Metals

Abstract

Calculations of the temperature dependence of the resistivity and thermopower of liquid indium, cadmium, thallium, lead and mercury are presented. The values of the thermopower are in better agreement with experiment than the results of previous calculations. The success and validity of the Ziman nearly-free-electron theory is discussed in connection with the results for the resistivity.     

Te,CdTe,HgCdTe的电沉积及其成核机理

应用自装微机联用恒电位系统研究了在玻璃碳或铁电极上Te、CdTe、HgCdTe的电沉积及其电结晶成核机理。结果表明,在酸性溶液中,HTeO_2~+的阴极还原符合4电子还原机理,其电结晶生长表现为由HTeO_2~+扩散控制的三维瞬时成核机理;CdTe沉积层的形成是亚碲酸还原的延续,其电结晶成核机理因电位阶跃值、沉积温度及溶液pH值的改变而由HTeO_2~+扩散控制的三维瞬时成核转变为二维瞬时成核机理;对HgCdTe,其电沉积过程的动力学步骤可设想为: Hg~(2+)+2e—→Hg,HTeO_2~++3H~++4e—→Te+2H_2O xHg+Te—→Hg_2Te,Hg_2Te+(1—x)Cd~(2+)+2(1—x)e—→Hg_2Cd_(1-2)Te 相关的结晶生长除受各种实验因素影响外,还与CdTe的成核过程有关。在本文实验条件下,大体遵循二维瞬时成核机理。     

Fast Fourier transformation with continuous cyclic voltammetry at an Au microelectrode for the determination of morphine in a flow injection system

For the fast morphine monitoring in flow injection systems a highly sensitive method is being introduced in this work. The fast Fourier transformation with continuous cyclic voltammetry (FFTCV) in a flowing solution as a detection system was applied for the prompt morphine monitoring. Here it should be stressed that this technique is simple, precise, accurate, time saving and economical. This research includes the observation of the effects of various parameters on the sensitivity of the detection system. Eventually, it was concluded that the best condition was obtained within the pH value of 2, scan rate value of 40 V s⁻¹, accumulation potential of 400 mV and accumulation time of 0.6 s.In detail, the noteworthy advantages which this method illustrates in comparison with other reported methods are the following; no necessity for the oxygen removal from the test solution, a sub-nano molar detection limit and the fast determination of any such compound in a wide variety of chromatographic methods.The method proved to be linear over the concentration range of 285-305,300 pg mL⁻¹ (r = 0.999) with a detection limit and a quantitation limit of 95.5 and 285 pg mL⁻¹, respectively. Consequently, the method illustrates the requisite accuracy, sensitivity, precision and selectivity to assay morphine in its tablets and biological fluids.     

Effect of Organic Solvents on the Electrodeposition of Copper from Acidified CuSO4

Using Guerbet tetradecyl alcohol C₁₄GA (synthesized by Guerbet reaction using 1-heptanol as raw material) as intermediate, sodium Guerbet tetradecyl polyoxyethylene ether sulfates [C₁₄GA(EO)_nS, n = 1, 2, 4] were obtained through following steps: synthesizing Guerbet tetradecyl polyoxyethylene ether alcohols [C₁₄GA(EO)_nH, n = 1, 2, 4] by Williamson reaction, then esterifying with chlorosulfonic acid so as to form Guerbet tetradecyl polyoxyethylene ether alcohol sulfates [C₁₄GA(EO)_nSO₃H, n = 1, 2, 4], and finally neutralizing with sodium hydroxide; while sodium Guerbet tetradecyl sulfate(C₁₄GAS) was synthesized only through esterifying and neutralizing reactions. The structures of these anionic surfactants were determined by infrared, nuclear magnetic resonance, and element analysis. The surface activity of these surfactants was studied by means of surface tension. The results have shown that these surfactants possess higher surface activity than the common surfactant C₁₂H₂₅OSO₃Na. Branched-tail structure coming from Guerbet alcohol makes the anionic surfactant (C₁₄GAS) have higher critical micelle concentration (CMC) and better effectiveness in lowering the interface tension between air and water than their linear counterpart (C₁₄H₂₉OSO₃Na). Introducing oxyethyene group into the place between head group and tail group of the surfactant molecule with branched tail can lower the CMC, γ_cmc, and Krafft point. And the effectiveness for reducing the CMC, γ_cmc, Γ_max, and Krafft point of surfactant increased with the increase of oxyethylene group number (n = 1, 2, 4). The relationship between the molecular structure and surface activity of surfactant is discussed.     

A New Method for Decreasing Mass Limit of Detection and Increasing Number of Theoretical Plates in Capillary Electrophoresis with Amperometric Detection

Much attention has been focused recently on pushing down the limit of detection (LOD)1-3. LOD in terms of amount is a combination of concentration LOD and the volume of sample required. The detection of small amount of sample can be achieved by reducing the sample volume, lowering the sample concentration LOD or a combination. Sampling with capillary can reduce sample volume to nL-pL level. To lower the concentration LOD is related to improve the signal-to-noise ratio. In the prese…     

Identifying Diffusion Limiting Current to Unravel the Intrinsic Kinetics of Electrode Reactions Affected by Mass Transfer at Rotating Disk Electrode

Rotating disk electrode systems are widely used to study the kinetics of electrocatalytic reactions that may suffer from insufficient mass transfer of the reactants. Kinetic current density at certain overpotential calculated by the Koutecky-Levich equation is commonly used as the metrics to evaluate the activity of electrocatalysts. However, it is frequently found that the diffusion limiting current density is not correctly identified in the literatures. Instead of kinetic current density, the measured current density normalized by diffusion limiting current density (j/j_L) has also been frequently under circumstance where its validity is not justified. By taking oxygen reduction reaction/hydrogen oxidation reaction/hydrogen evolution reaction as examples, we demonstrate that identifying the actual diffusion limiting current density for the same reaction under otherwise identical conditions from the experimental data is essential to accurately deduce kinetic current density. Our analysis reveals that j/j_L is a rough activity metric which can only be used to qualitatively compare the activity trend under conditions that the mass transfer conditions and the roughness factor of the electrode are exactly the same. In addition, if one wants to use j/j_L to compare the intrinsic activity, the concentration overpotential should be eliminated.