Polarization Characteristics of Porous Electrode Systems with Adsorbed Intermediates Participating in the Electrode Reaction

Current-potential relationships are derived for porous electrode systems following a homogeneous model and whenadsorbed intermediates participate in the electrode reaction. Limiting Tafel slopes were deduced and compared with thecorresponding behavior on planar electrode systems. The theoretical results showed doubling of Tafel slopes when theslow-step is a charge-transfer reaction and a nonlogarithmic current-voltage behavior when the slow-step is a chemical reaction.Comparison of the experimental results with theory for the case of oxygen reduction on carbon surfaces in alkalinemedia indicates that a slow chemical reaction following the initial charge-transfer reaction to be the likely rate-controllingstep. Theoretical relationships are utilized to determine the exchange current density and the surface coverage by the adsorbedintermediates during the course of oxygen reduction from alkaline solutions on "carbon." Tafel slope measurementson planar and porous electrodes for the same reaction are suggested as one of the diagnostic criteria for elucidatingthe mechanistic pathways of electrochemical reactions.

Digital simulation of galvanostatic current-potential data for gas-diffusion electrodes and estimation of electrodekinetic parameters

A computerized non-linear-least-squares regression procedure to analyse the galvanostatic current-potential data for kinetically hindered reactions on porous gas-diffusion electrodes is reported. The simulated data fit well with the corresponding measured values. The analytical estimates of electrode-kinetic parameters and uncompensated resistance are found to be in good agreement with their respective values obtained from Tafel plots and the current-interrupter method. The procedure circumvents the need to collect the data in the limiting-current region where the polarization values are usually prone to errors. The polarization data for two typical cases, namely, methanol oxidation on a carbon-supported platinum-tin electrode and oxygen reduction on a Nafion-coated platinized carbon electrode, are successfully analysed.

Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and CoNi alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co-Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdOx in methanol. The kinetics of the hydrogen evolution reaction ( HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade(-1) for the Tafel slope, suggesting that the HER follows the Volmer-Heyrovsky mechanism. The values of exchange current density (i(o)) are in the range 1-10 mA cm(-2) for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i(o)) and energy transfer coefficient (alpha) have been calculated by employing a nonlinear least square-fitting program.

Process and properties of electroless Ni-Cu-P-ZrO2 nanocomposite coatings

Electroless Ni-Cu-P-ZRO(2) composite coating was successfully obtained on low carbon steel matrix by electroless plating technique. Coatings with different compositions were obtained by varying copper as ternary metal and nano sized zirconium oxide particles so as to obtain elevated corrosion resistant Ni-P coating. Microstructure, crystal structure and composition of deposits were analyzed by SEM, EDX and XRD techniques. The corrosion behavior of the deposits was studied by anodic polarization, Tafel plots and electrochemical impedance spectroscopy (EIS) in 3.5% sodium chloride solution. The ZRO(2) incorporated Ni-P coating showed higher corrosion resistance than plain Ni-P. The introduction of copper metal into Ni-P-ZRO(2) enhanced the protection ability against corrosion. The influence of copper metal and nanoparticles on microhardness of coatings was evaluated. (C) 2011 Elsevier Ltd. All rights reserved.

Morphological and electrochemical characterization of electrodeposited Zn-Ag nanoparticle composite coatings

Silver nanoparticles with an average size of 23 nm were chemically synthesized and used to fabricate Zn-Ag composite coatings. The Zn-Ag composite coatings were generated by electrodeposition method using a simple sulfate plating bath dispersed with 0.5, land 1.5 g/l of Ag nanoparticles. Scanning electron microscopy, X-ray diffraction and texture co-efficient calculations revealed that Ag nanoparticles appreciably influenced the morphology, micro-structure and texture of the deposit. It was also noticed that agglomerates of Ag nanopartides, in the case of high bath load conditions, produced defects and dislocations on the deposit surface. Ag nanoparticles altered the corrosion resistance property of Zn-Ag composite coatings as observed from Tafel polarization, electrochemical impedance analysis and an immersion test. Reduction in corrosion rate with increased charge transfer resistance was observed for Zn-Ag composite coatings when compared to a pure Zn coating. However, the particle concentration in the plating bath and their agglomeration state directly influenced the surface morphology and the subsequent corrosion behavior of the deposits. (C) 2013 Elsevier Inc. All rights reserved.

The design of polyaniline based sensor for the qualitative estimation of malonaldehyde

The detection of contaminated food in every stage of processing required new technology for fast identification and isolation of toxicity in food. Since effect of food contaminant are severe to human health, the need of pioneer technologies also increasing over last few decades. In the current study, MDA was prepared by hydrolysis of 1,1,3,3-tetramethoxypropane in HCl media and used in the electrochemical studies. The electrochemical sensor was fabricated with modified glassy carbon electrode with polyaniline. These sensors were used for detection of sodium salt of malonaldehyde and observed that a high sensitivity in the concentration range similar to 1 x 10(-1) M and 1 x 10(-2) M. Tafel plots show the variation of over potential from -1.73 V to -3.74 V up to 10(-5) mol/L indicating the lower limit of detection of the system. (C) 2013 Elsevier Ltd. All rights reserved.

Effect of TiN particulate reinforcement on corrosive behaviour of aluminium 6061 composites in chloride medium

In the present investigation, the corrosive behaviour of Al 6061-TiN particulate composites prepared by liquid metallurgy has been studied in chloride medium using electroanalytical techniques such as Tafel, cyclic polarization and electrochemical impedance spectroscopy (EIS). Surface morphology of the sample electrodes was examined using scanning electron micrography and energy dispersive X-ray methods. X-ray diffraction technique was used to confirm inclusion of TiN particulates in the matrix alloy and identify the alloying elements and intermetallic compounds in the Al 6061 composites. Polarization studies indicate an increase in the corrosion resistance in composites compared to the matrix alloy. EIS study reveals that the polarization resistance (R (p)) increases with increase in TiN content in composites, thus confirming improved corrosion resistance in composites. The observed decrease in corrosion rate in the case of composites is due to decoupling between TiN particles and Al 6061 alloy. It is understood that after the initiation of corrosion, interfacial corrosion products may have decoupled the conducting ceramic TiN from Al 6061 matrix alloy thus eliminating the galvanic effect between them.

Equiatomic ternary chalcogenide: PdPS and its reduced graphene oxide composite for efficient electrocatalytic hydrogen evolution

The layered ternary chalcogenide, palladium phosphorous sulphide (PdPS), and its composite with reduced graphene oxide are shown to be efficient hydrogen evolution electrocatalysts. The Tafel slope and the exchange current density values associated with hydrogen evolution reaction are determined to be 46 mV dec(-1) and 1.4 x 10(-4) A cm(-2) respectively.

Electrochemical behavior of Zn-graphene composite coatings

A Zn-graphene composite coating was electrodeposited on mild steel. The graphene was synthesized by electrochemical exfoliation of graphite. Electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffraction techniques were used to characterize the coatings. Compared to a pure Zn coating, the Zn-graphene coating exhibited reduced grain size, reduced surface defects, hillock structures over the coating surface and an altered texture. The corrosion behavior of the coatings was examined by Tafel polarization and electrochemical impedance spectroscopic methods. A significant improvement in the corrosion resistance in terms of reduction in corrosion current and corrosion rate and increase in polarization resistance was noted in the case of the Zn coating containing graphene.

In Situ Crystallographic Probing on Ameliorating Effect of Sulfide Additives and Carbon Grafting in Iron Electrodes

Beneficial effects of carbon grafting into the iron active material for rechargeable alkaline-iron-electrodes with and without Bi2S3 additive is probed by in situ X-ray diffraction in conjunction with Extended X-ray Absorption Fine Structure (EXAFS) and electrochemistry. EXAFS data unravel that the composition of pristine active material (PAM) for iron electrodes comprises 87% of magnetite and 13% of alpha-iron while carbon-grafted active material comprises 60% of magnetite and 40% of alpha-iron. In situ XRD patterns are recorded using a specially designed electrochemical cell. XRD data reflect that magnetite present in PAM iron electrode, without bismuth sulfide additive, is not reduced during charging while PAM iron electrode with bismuth sulfide additive is partially reduced to alpha-Fe/Fe(OH)(2). Interestingly, carbon-grafted-iron electrodes with bismuth sulfide exhibit complete conversion of active material to alpha-Fe/Fe(OH)2. The ameliorating effect of carbon grafting is substantiated by kinetic parameters obtained from steady-state potentiostatic polarization and Tafel plots. The mechanism for iron-electrode charge - discharge reactions are discussed in the light of the potential - pH diagrams for Fe - H2O, S - H2O and FeSads - H2O systems and it is surmised that carbon grafting into iron active material promotes its electrochemical utilization. (C) The Author(s) 2015. Published by ECS. All rights reserved.

Electrically conducting palladium selenide (Pd4Se, Pd17Se15, Pd7Se4) phases: synthesis and activity towards hydrogen evolution reaction

Electrically conducting, continuous films of different phases of palladium selenides are synthesized by the thermolysis of single source molecular precursors. The films are found to be adherent on flat substrates such as glass, indium tin oxide and glassy carbon and are stable under electrochemical conditions. They are electrocatalytically active and in particular, for hydrogen evolution reaction. Catalytic activities with low Tafel slopes of 50-60 mV per decade are observed.

Electrochemical deposition of manganese oxide-phosphate-reduced graphene oxide composite and electrocatalysis of the oxygen evolution reaction

A composite of manganese oxide and reduced graphene oxide (rGO) is prepared in a single step electrochemical reduction process in a phosphate buffer solution for studying as an electrocatalyst for the oxygen evolution reaction (OER). The novel composite catalyst, namely, MnOx-Pi-rGO, is electrodeposited from a suspension of graphene oxide (GO) in a neutral phosphate buffer solution containing KMnO4. The manganese oxide incorporates phosphate ions and deposits on the rGO sheet, which in turn is formed on the substrate electrode by electrochemical reduction of GO in the suspension. The OER is studied with the MnOx-Pi-rGO catalyst in a neutral phosphate electrolyte by linear sweep voltammetry. The results indicate a positive influence of rGO in the catalyst. By varying the ratio of KMnO4 and GO in the deposition medium and performing linear sweep voltammetry for the OER, the optimum composition of the deposition medium is obtained as 20 mM KMnO4 + 6.5% GO in 0.1 M phosphate buffer solution of pH 7. Under identical conditions, the MnOx-Pi-rGO catalyst exhibits 6.2 mA cm(-2) OER current against 2.9 mA cm(-2) by MnOx-Pi catalyst at 2.05 V in neutral phosphate solution. The Tafel slopes measured for OER at MnOx-Pi and MnOx-Pi-rGO are similar in magnitude at about 0.180 V decade(-1). The high Tafel slopes are attributed to partial dissolution of the catalyst during oxygen evolution. The O-2 evolved at the catalyst is measured by the water displacement method and the positive role of rGO on catalytic activity of MnOx-Pi is demonstrated.

导电高分子在防腐领域的应用及其相关机理研究

本论文研究了聚苯胺与常用涂料的共混行为，针对本征态和掺杂态聚苯胺各自的特点，开发出本征态聚苯胺/环氧树脂和掺杂态聚苯胺/聚氨酯两种共混防腐体系：利用线性极化和Tafel曲线等电化学方法对两个体系的防腐性能进行了监测：采用EIS和XPS等技术对聚苯胺防腐机理进行了探讨。以有机胺为桥梁率先开发出无溶剂本征态聚苯胺/环氧树脂共混防腐体系，用SEM研究发现该体系中聚苯胺分散的非常好，达到纳米级分散，并且同环氧树脂形成相互交叉的网状结构。有机胺对聚苯胺既有一定的溶解作用又有一定的降解作用。用IR和UV-Vis研究发现聚苯胺在有机胺中的降解产物基本上保持了聚苯胺的性质，但是其分子量变小了，部分可以溶于乙醇中，而且该苯胺低聚物对于酸碱的敏感程度大大降低，只有浓酸才能将其掺杂。有机酸掺杂的聚苯胺可以很好地分散在聚氨酯中形成掺杂态聚苯胺/聚氨酯共混防腐体系。用SEM观察发现掺杂态聚苯胺在聚氨酯中形成了很好的网状结构。同时对于影响掺杂态聚苯胺在聚氨酯中分散的各种因素(掺杂比例、温度，溶剂量等)进行了分析。指出聚氨酯乙组份中的多元醇对已经分散在聚氨酯中的掺杂态聚苯胺有稳定作用。利用线性极化和Tafel曲线对本征态聚苯胺/环氧树脂和掺杂态聚苯胺/聚氨酯共混体系的防腐性能进行了监测，发现聚苯胺的加入使得常用涂料的自然腐蚀电位E_(corr)正向移动；相应的自然腐蚀电流i_(corr)明显降低；共混膜的极化电阻R_p比空白样品的极化电阻显著增大。利用EIS技术对本征态聚苯胺/环氧树脂和掺杂态聚苯胺/聚氨酯共混体系进行了阻抗分析，并结合XPS结果提出聚苯胺防腐涂料具有良好防腐效果的关键是聚苯胺和铁相互作用，在两者界面处形成了一层致密的氧化膜。该层氧化膜的存在可以大大提高防腐涂层的孔阻R_(pore)和最大值阻抗Z_(max)，从而使得聚苯胺防腐涂层具有很好的阻挡腐蚀介质渗透的作用。同时利用断点频率f_b分析了个涂层附着力的变化趋势以及剥离面积A_d的大小。在文献总结和实验积累的基础上分别提出了本征态聚苯胺/环氧树脂和掺杂态聚苯胺/聚氨酯共混体系的等效电路，并利用非线性最小二乘法(NLCN)对所得Nyquist和Bode谱进行了模拟，给出了比较好的拟合曲线。从各等效元件的拟合值可以直接比较各膜的R_(pore)的大小，并且可以看出界面氧化膜电阻R_(ol)对于聚苯胺膜阻抗值的贡献。

PH值、氯离子浓度和监酸浓度对于铁的腐蚀电化学行为的影响

本文研究了Armco铁在盐酸溶液中的腐蚀电化学行为，探讨了ψ~-离子和PH值对铁的阳极溶解过程的影响，并进而讨论了ψ~-离子浓度和PH值对铁的腐蚀电化学行为的影响之间是否存在交互效应。在本工作中，作者提出了两个新的研究方法：(a) 从单支弱极化曲线测定腐蚀电流和阴、阳极反应的Tafep斜率；(b)根据交流方波电流扰动的响应函数方程测定极化电阻Rp和界面电容C。设I_c、I_(2c)、I_(3c)及I_(4c)分别为对应于弱极化区内极化电位为ΔE、2ΔE、3ΔE和4ΔE的极化电流，且令a = I_(2c)/I_c, b = I_(3c)/I_c, c = I_(4c)/I_(2c), 而(4b-3a~2)~(1/2)、(3c-2b)~(1/2)、(2c-a~2)~(1/2)则以S_j表示之，则可得到：I_(corr) = I_c/S_j b_c = ΔE/lg((a+s_j)/2) b_a = -ΔE/lg((a-s_j)/2)为了方便，准确地求出动力学参数，可选用一系列的ΔE值，得出相应的极化电流I_λ，求出S_λ，应用统计方法处理数据，可得：I_(corr) = ∑ from i=1 to n I_λ/∑ from i=1 ton S_λ b_c = ∑ form λ to n ΔE_λ/∑ form i=1 to n lg ((a_λ+S_λ)/2) b_a = ∑ form i=1 ton ΔE_λ/∑ form i=1 to n lg ((a_λ-S_λ)/2)在线性极化区间内向腐蚀金属电极体系施加一交流方波电流扰动讯号时，通过Laplace变换分析，得到相应的响应函数方程为：E_1(t) = λ_o(R_s+R_p) - 2λ_oR_p (e~(-(τ-λ)/RpC))/(1+e~(λ/RpC)) (o<τ<λ) E_2(t) = -λ_o(R_s+R_p) + 2λ_oR_p (e~(-(τ-λ)/RpC))/(1+e~(λ/RpC)) (λ<τ<2λ)由此方程可知，它们在E～λ坐标系统中的轨迹为对称兴致勃勃原点的两条直线。由此方程可进一步得到:ΔE = 2λ_oR_p (e~(λ/RpC)-1)/(e~(λ/RpC)+1) = 2λ_oR_p t_(anh)(λ/(2RpC)) Δh = 2λ_o Rs式中ΔE为单支响应直线的长度，Δh则为两条直线最高点之间的距离。上述公式可进一步简化为：Rp =(ΔE)/(2λ_o) λ>>RpC (λ_o)/(ΔE) = C/λ + 1/(2Rp) λ<Tafel线段的数据分析而得到的离子反应级数和Tafel斜率值与弱极化区得到的结果是一致的。由此，讨论了铁的阳极溶解过程，提出了反应机理，由此机理推论而得出的有关的电化学参数的理论值与实验值符合得很好。最后，对PH值和ψ~-离子浓度对铁的腐蚀电化学行为的影响之间是否存在交互效应进行了探讨。由实验数据的分析得到，PH值和ψ~-离子浓度的效应之间不存在交互效应，或者交互效应不大。

Cr(III)盐在Pt电极和PbO_2电极上阳极氧化为络酸盐的机理的研究

关于Cr(III)阳极氧化为Cr(VI)的过程，在工业应用方面已有许多工作，但对机理尚不清楚。本文对Pt电极和PbO_2电极上的这一过程进行了动力学的研究，首次得到了Cr(VI)在这两种电极上阳极形成的真实动力学数据，并提出了与实验基本相符的反应机理。用“分解极化曲线法”和稳态极化曲线的测量，得到了[H_2SO_4]和[SO_4~=]恒定的不同浓度Cr_2(SO_4)_3溶液中Cr(VI)在光滑Pt电极上阳极形成的真实动力学数据，可用如下方程式来表达：在较低电位下φ = a + 0.25 log i_2 - 0.23 log [Cr(III)]在较高电位下φ = a' + 0.48 log i_2 - 0.44 log [Cr(III)]同时得到了氧的阳极发生的动力学数据，Tafel线性区的斜率接近于2.303 RT/ΔF (Δ ≈ 0.5)。动力学方程式的推导与实验的比较表明，在光滑Pt电极上Cr(VI)是由Cr(II)通过“活性氧”的氧化形成的，提出了如下反应机理：H_2O → (OH)_(ad) + H~+ + e~- 2(OH)_(ad) → (O)_(ad) + H_2O 2(O)_(ad) →O_2 (OH)_(ad) + [Cr(H_2O)_6]~(3+) → (CrO_2)_(ad) + 3H~+ + 5H_2O (CrO_2)_(ad) + H_2O → (CrO_3~-)_(ad) + 2H~+ + e~- (CrO_3~-)_(ad) + H_2O → HCrO_4~- + H~+ + e~- 2HCrO_4~- <-> Cr_2O_7~(2-) + H_2O 在[H_2SO_4]和[SO_4~(2-)]恒定的不同浓度Cr_2(SO_4)_3溶液中，测得了Cr(VI)在Δ-PbO_2电极上阳极形成的动力学数据：在较低电位下φ = a + 0.28 log i_2 - 0.30 log [Cr(III)]在较高电位下φ = a' + 0.55 log i_2 - 0.51 log [Cr(III)]氧的极化曲线的Tafel线性区斜率也为2.303RT/ΔF (Δ approx= 0.5)。PbO_2电极和Pt电极上分解极化曲线的比较表明，Cr(VI)在前一电极上阳极形成的过电位远低于在后一电极上，这可能是两电极上电流效率显著差别的原因。测得了PbO_2电极上不同过电位下电极反应的有效活化能，其数值均在10 Kcal mol~(-1)以上，且随着极化的增大而减小，据此在动力学处理中可以忽略扩散的作用，交流阻抗的研究进一步证实了这一点。溶液pH的增大或[H_2SO_4]的减小会降低Cr(VI)阳极形成的过电位，使反应加速。在[H_2SO_4]和[SO_4~(2-)]恒定的不同浓度Cr_2(SO_4)_3溶液中，测得了在不同电位极化下PbO_2电极的阻抗频谱。在较高电位下阻抗谱呈现明显的两个半圆，表明电极过程包括了中间吸附物的形成。求得的吸附电容Cad比双层电容Cd大1-2个数量级；Cd比通常光滑电极表面的Cd大得多，这可能与SO_4~(2-)，HCrO_4~-, Cr_2O_7~-以及[_((SO_4))~((H_2O)_2) Cr_((SO_4))~((OH)_2) Cr_((SO_4))~((OH_2)_2)]~(2-)等阳离子的特性吸附有关。从动力学的推导与实验的比较得出，在PbO_2电极上Cr(VI)也按“活性氧”机构形成，可能的机理如下：H_2O → (OH)_(ad) + H~+ + e~- (OH)_(ad) + H_2O → (O)_(ad) + H_3O~+ + e~- 2(O)_(ad) → O_2 [Cr(H_2O)_6]~(3+) + (O)_(ad) → (CrO_3~-)_(ad) + 4H~+ + 4H_2O (CrO_3~-)_(ad) + H_2O → HCrO_4~- + H~+ +e~- 2HCrO_4~- <-> Cr_2O_7~(2-) + H_2O.