Electrochemical behavior of Cu(Ⅱ) reduced in CH3OH and DMSO

The cyclic voltammetry and the potential-time curve after galvanostatic electrolysis were used to study the electrode processes of Cu(Ⅱ) in CH3OH solution and DMSO solution. The electroreduction of Cu(Ⅱ) to Cu on a Pt electrode proceeds in two steps: Cu(Ⅱ) + e = Cu(Ⅰ); Cu(Ⅰ) + e = Cu. The reduction potential of Cu(Ⅱ) in DMSO solution is more negative than that in CH3OH solution, and the diffusion coefficient of Cu(Ⅱ) ion in DMSO solution is larger than that in CH3OH solution because the polarity of DMSO is larger than that of CH3OH observably and has a stronger solvating power.     

Electrochemical behavior of Cu(II) reduced in CH3OH and DMSO

The cyclic voltammetry and the potential-time curve after galvanostatic electrolysis were used to study the electrode processes of Cu(n) in CH3OH solution and DMSO solution. The electroreduction of Cu(Ⅱ) to Cu on a Pt electrode proceeds in two steps: Cu(Ⅱ) + e = Cu(Ⅰ); Cu(I) + e = Cu. The reduction potential of Cu(n) in DMSO solution is more negative than that in CH3OH solution, and the diffusion coefficient of Cu(Ⅱ) ion in DMSO solution is larger than that in CH3OH solution because the polarity of DMSO is larger than that of CH3OH observably and has a stronger solvating power.     

Crystal structure and electrochemical behaviors of Pt/mischmetal film electrodes

The Ml(La-rich mischmetal0films with a thin Pt layer on the substrate of chemically coarse ITO glass or silicon slices were prepared by magnetic sputtering tchnique.The crystal structure and surface morphology of the films were investigated by X-ray diffraction(XRD)analysis and atomic force microscopy(AFM),respectively, The electrochemical hydridation/dehydridation behaviors of the films in KOH solution were studied by using cyclic voltammagraph and electrochemical impedance spectrum(EIS)as well.The AFM results show that the Pt cover layer on the M1 films is of island structure with a grain of 150-200nm in size.The presence of a thin Pt layer can provide sufficient high electrocatalytic activity for the electrochemical charge-transfer reaction.The electrochemical reduction and oxidation reaction occur on the Pt layer,and the diffusion of H into the Ml film is the rate-controlled step.The Pt coatings also act as protective layers,preventing oxidation and/or poisoning of the underlying Ml films in air.     

Experimental and Quantum Studies on Adsorption and Corrosion Inhibition Effect on Mild Steel in Hydrochloric Acid by Thiophene Derivatives

The inhibition effect of synthesized diethyl 3,4-bis(4-methoxybenzylideneamino) thieno[2,3-b]thiophene-2,5-dicarboxylate(Inh I) and diethyl 3,4-bis(benzylideneamino) thieno[2,3-b]thiophene-2,5-dicarboxylate(Inh Ⅱ),on corrosion of mild steel in 15%HC1 solution was investigated using weight loss measurements,electrochemical polarization,and electrochemical impedance spectroscopy techniques.The experimental results show that the inhibition efficiency of studied inhibitors increased with the increase of inhibitors concentration but decreased with the increase of temperature.Corrosion inhibition efficiencies of 94.5%and 92.1%were obtained with 250 ppm of Inh I and Inh Ⅱ at 303 K,respectively.The potentiodynamic polarization measurements indicate that the studied inhibitors act as mixed inhibitor.The thermodynamic parameters of the corrosion and adsorption processes were calculated and evaluated.The adsorption of these inhibitors was found to obey Langmuir adsorption isotherm.Scanning electron microscopy was used to characterize the surface morphology of the mild steel specimens in presence and absence of inhibitors.The mechanism of the inhibition process was discussed in the light of the chemical structure and quantum-chemical calculations of the investigated inhibitors.     

Electrochemical reduction behavior of Hf(Ⅳ) in molten NaCl–KCl–K_2HfCl_6 system

The electrochemical reduction mechanism of hafnium ion(Ⅳ) was studied in NaCl–KCl–K_2HfCl_6 melts on a molybdenum electrode. The cyclic voltammetry study shows that Hf(Ⅳ) is reduced to hafnium metal in double two-electron process, that is: Hf(Ⅳ)+2e~-→Hf(Ⅱ) and Hf(Ⅱ)+2e~-→Hf, and the electrochemical reduction of Hf(Ⅳ) process was diffusion-controlled. The diffusion coefficients were calculated at several temperatures, and the results obey the Arrhenius law. According to the relationship of lnD versus 1/T,the corresponding activation energy was determined to be 158.8 kJ ·mol~(-1). The square wave voltammetry results further confirm the reduction mechanism of hafnium.     

Thermal decomposition kinetics of antimony oxychloride in air

The DTA and XRD techniques were employed to study thermal decomposition mechanism of antimony oxychloride SbOCl in the air. The thermal decomposition reaction occurs in four steps, and the former three steps as: SbOCl (s)→Sb4O5Cl2(s) SbCl3(g)→Sb8O11Cl2(s) SbCl3 (g)→Sb2O3 (s) SbCl3(g). The forth step is the oxidation of Sb2O3 by air, Sb2O3(s) O2→Sb2O4(s). The activation energy and the order of the thermal decomposition reaction of antimony oxychloride in three steps presented in DTA curves were calculated according to Kinssinger methods from DTA curves The values of activation energy and the order are respectively 91.97kJ/mol, 0.73 in the first step,131.14 kJ/mol, 0.63 in the second step and 146.94 kJ/mol, 1.58 in the third steP.     

Al-Si/Al_2O_3 in situ composite prepared by displacement reaction of CuO/Al system

Al2O3 particle-reinforced ZL109 composite was prepared by in situ reaction between CuO and Al.The microstructure was observed by means of OM,SEM and TEM.The Al2O3 particles in sub-micron sizes distribute uniformly in the matrix,and the Cu displaced from the in situ reaction forms net-like alloy phases with other alloy elements.The hardness and the tensile strength of the composites at room temperature have a slight increase as compared to that of the matrix.However,the tensile strength at 350 ℃ has reached 90.23 MPa,or 16.92 MPa higher than that of the matrix.The mechanism of the reaction in the CuO/Al system was studied by using of differential scanning calorimetry(DSC) and thermodynamic calculation.The reaction between CuO and Al involves two steps.First,CuO reacts with Al to form Cu2O and Al2O3 at the melting temperature of the matrix alloy,and second,Cu2O reacts with Al to form Cu and Al2O3 at a higher temperature.At ZL109 casting temperature of 750-780 ℃,the second step can also take place because of the effect of exothermic reaction of the first step.     

Reaction process of monazite and bastnaesite mixed rare earth minerals calcined by CaO-NaCl-CaCl2

The decomposition reactions of monazite and bastnaesite mixed rare earth minerals calcined by CaO-NaCl-CaCl2 were studied by means of TG-DTA and XRD. The results show that the process of the minerals decomposed by CaO involves two steps. The first step occurs in the temperature range of 425-540 ℃, and the main reactions are bastnaesite decomposition, i.e. REOF reacts with CaO to produce RE2O3 and CaF2, and Ce2O3 is oxidized to CeO2. During this step, CaCO3 is formed at about 500 ℃. The second step takes place in the temperature range of 610-700 ℃, and the reactions are monazite decomposition into RE2O3, Ca5F（PO4）3 and Ca3（PO4）2 by CaO and CaF2. In this process, the decomposition ability is improved because CaO from CaCO3 decomposing has high chemical activity. In calcining process, the new formed Ca5F（PO4）3 restrains fluorine that can escape in form of gaseous compound. The decomposition ratio of the mixed rare earth minerals reaches 90.8% at 700 ℃.     

Electrochemical Behavior of Er(Ⅲ）In N,N-dimethylformamide

The cyclic voltammetry, current-time curve at potential step and potential-time curve of galvanostatic method were used to investigate the electrochemical behavior of Er(Ⅲ) in ErCl3-LiClO4-DMF(N, N-dimethylformamide) system on Pt and Cu electrodes. Results indicate that the electroreducation of Er(Ⅲ) to Er(0) is irreversible on Pt and Cu electrodes, the diffusion coefficient and electron transfer coefficient of Er(Ⅲ) in 0.01mol/L ErCl3-0.1mol/L LiClO4-DMF system at 303K are 1.96×10-6 cm2*s-1 and 0.081 respectively. The Er metal film was prepared by galvanostatic electrolysis on Cu electrode in ErCl3-LiClO4-DMF system at 40A*m-2(current density). The deposites composed of Er over 95%(mass fraction) were obtained.     

4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-1,3,5-triazine modified carbon paste electrode for trace Cu(Ⅱ) determination by differential pulse volt-ammetry

A differential pulse voltammetric method was developed for the sensitive and selective determination of Cu(Ⅱ) at 4-methoxy-2,6-bis(3,5-dimethylpyrazoyl)-l,3,5-triazine modified carbon paste electrode in 0.05 mol/L KHC8H4O4 solution (pH = 4.02). The oxidation peak of Cu(Ⅱ) was observed at 0.065 V(vs Ag/AgCl) by scanning the potential in positive direc-tion. The analysis procedure consisted of an open circuit accumulation step in stirred sample solution. It was followed by medium exchange to a clean solution and subsequently an anodic potential scan was affected to obtain the voltammetric peak. The current was proportional to the concentration of the Cu(Ⅱ) ion in a range of 1× 10-7-1×10-4 mol/L for 6 min accumulation; the most of metal ions did not interfere with the determination. The developed method was applied to Cu(Ⅱ) determination in coal-ash sample, the results agreed with that of atomic adsorption spectroscopy(AAS).     

Electrochemical and Kinetic Behaviors of Fe(Ⅱ) Ion in DMSO, DMF and CH_3CN

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Electrochemical and Kinetic Behavior of Ni(Ⅱ)Ion in DMF

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弱碱性溶液中硫砷铜矿的电化学氧化过程及表面相构成

采用循环伏安(CV)和X射线光电子能谱(XPS)对硫砷铜矿在pH值为9.2溶液中的电化学氧化过程以及电位对硫砷铜矿表面氧化相的构成影响进行研究。结果表明:硫砷铜矿在电位0.17 V(氧化峰A1电位范围)氧化,主要发生Cu部分离开矿物表面进入溶液形成缺铜硫化物(Cu3 xAsS4)的初步氧化过程,表面不存在Cu(Ⅱ)的氧化相,S氧化形成少量的S2 n,As不发生氧化。当氧化电位提高到0.3 V(氧化峰A2电位范围),大量的Cu离开矿物表面进入溶液,表面仍然不存在Cu(Ⅱ)的氧化相,可能存在少量的CuSO4,但处于检测下限,表面存在一定量的Sn^2-,不存在As的氧化相。当电位提高到0.5 V(氧化峰A2电位范围),发生Cu和As的氧化沉积过程,分别在矿物表面形成Cu(Ⅱ)氧化相(Cu(OH)2,CuSO4)和As2O3氧化相。此外,表面还存在一定的Sn^2-相。当电位提高到0.8V(氧化峰A3电位范围),表面形成一定量的Cu(Ⅱ)氧化相(Cu(OH)2和CuSO4),As仍然以As2O3的形式存在,S除形成CuSO4外,部分仍以Sn^2-的形式存在。     

碱性锌酸盐体系中Zn的电沉积行为研究简

通过循环伏安、计时电位及电化学阻抗谱技术研究了碱性锌酸盐体系中Zn的阴极还原历程,采用计时电流法结合扫描电镜(SEM)研究了Zn的电化学成核机理。结果表明:溶液中Zn主要以Zn(OH)42-形式存在,Zn(OH)42-通过前置转化反应生成Zn(OH)2;Zn(OH)2在阴极界面上分两步放电,第一步放电后生成Zn(OH)ad吸附在电极表面,而后经第二步放电还原为Zn,两步均不可逆。外加电位为-1.40~-1.50 V时,体系中仅发生Zn(OH)2的第一步放电反应;电位负移至-1.60 V时,Zn(OH)2经历了两步放电过程,但Zn仅吸附在电极表面,电沉积过程处于一种非稳态;当电位负移至-1.70~-1.80 V时,吸附态Zn才持续进入晶格形成完整镀层。体系中Zn的电结晶过程遵循三维连续形核方式。     

The role of oxygen in the interaction of emeraldine base polyaniline with Cu(II) or Fe(III) ions in NMP solution

The influence of molecular oxygen in the interactions of emeraldine base form of polyaniline (EB-PANI) with Fe(III) or Cu(II) ions in 1-methyl-2-pyrrolidinone (NMP) solutions has been investigated by UV–vis–NIR, resonance Raman and electron paramagnetic resonance (EPR) spectroscopies. Through the set of spectroscopic results it was possible to rationalize the role of O₂ and to construct a scheme of preferential routes occurring in the interaction of EB-PANI with Fe(III) or Cu(II). Solutions of 4.0 mmol L⁻¹ EB-PANI with 0.8, 2.0 and 20 mmol L⁻¹ Fe(III) or Cu(II) ions in NMP were investigated and the main observed reactions were EB-PANI oxidation to pernigraniline (PB-PANI) and EB-PANI doping process by pseudo-protonation, or by a two-step redox process. In the presence of O₂, PB-PANI is observed in all Fe(III)/EB solutions and EB-PANI doping only occurs in solutions with high Fe(III) concentrations through pseudo-protonation. On the other hand, emeraldine salt (ES-PANI) is formed in all Fe(III)/EB solutions under N₂ atmosphere and, in this case, doping occurs both by the pseudo-protonation and two-step redox mechanisms. In all Cu(II)/EB solutions PB-PANI is formed both in the presence and absence of O₂, and only for solutions with high Cu(II) concentrations doping process occurs in a very low degree. The most important result from EPR spectra was providing evidence for redox steps. The determined Cu(II) signal areas under oxygen are higher than under N₂ and, further, the initial metal proportions (1:2:20) are maintained in these spectra, indicating that Cu(I) formed are re-oxidized by O₂ and, so, Cu(II) ions are being recycled. Consistently, for the solutions prepared under nitrogen, the corresponding areas and proportions in the spectra are much lower, confirming that a partial reduction of Cu(II) ions actually occurs.     

The aqueous chemistry and electrochemistry of polyacetylene, (CH)x

Polyacetylene, (CH)_x, is p-doped (oxidized) to the metallic regime by (i) gaseous oxygen in aqueous 48% (7.4M) HBF₄, (ii) aqueous HClO₄ and H₂SO₄ and (iii) electrochemical methods to give highly conducting materials that are remarkably stable in the aqueous solutions in which they are synthesized. The chemical doping reactions are consistent with the reduction potentials of polyacetylene in its various oxidation states and with the reduction potentials of the oxidizing agents. Polyacetylene can act as an electrocatalytic, ‘fuel-cell type’ electrode and also as an electrode-active cathode in rechargable battery cells in certain aqueous acid solutions.     

Supercapacitor characteristic of La-doped Ni(OH)_2 prepared by electrodeposition

Samples of lanthanum-doped nickel hydroxide were prepared by electrodeposition method. The structure and electrochemical properties of the samples were studied by X-ray diffraction and a home-made open three-electrode cell system,respectively. The results show that the deposition process of Ni(OH)2 and La(OH)3 is mainly controlled by electrochemical polarization,which makes it easy to form uniform fine crystals. In addition,La(OH)3 is not a separate phase and lanthanum ions are doped into Ni(OH)2 crystal la...     

铜铝层状复合板中性盐雾腐蚀行为研究

采取模拟大气环境的室内中性盐雾腐蚀实验,探讨了铜铝层状复合材料的腐蚀行为。通过扫描电镜(SEM)观察腐蚀后铜铝界面形貌,结合X射线衍射仪(XRD)和能谱仪(EDS)分析腐蚀产物成分,并通过电化学检测分析试样经过不同时间盐雾腐蚀后的表面腐蚀状态,探讨铜铝复合板在服役环境下的腐蚀机制。结果表明:铜铝复合板在盐雾环境下铜铝构成腐蚀原电池,Al为阳极铜为阴极,阴阳极面积比越大,腐蚀速率越大。随着腐蚀的不断进行,铜铝界面的Cu一侧发生腐蚀,且靠近界面的位置腐蚀最为严重,随着腐蚀时间延长,铝基体出现严重的剥蚀现象,Cu几乎无变化。腐蚀产物成分为Al2O3,Al(OH)3和AlO(OH),电化学结果显示:铜铝复合板在腐蚀的过程中,腐蚀速率呈现先增加后减小再增加的趋势。     

Cu单掺杂和Cu/Al复合掺杂纳米氢氧化镍的结构和电化学性能(英文)

采用超声波辅助沉淀法制备Cu单掺杂和Cu/Al复合掺杂的纳米Ni(OH)2样品,测试样品的晶相结构、粒径、形貌、振实密度及电化学性能。结果表明,样品均具有α相结构且其平均粒度的分布范围窄,Cu单掺杂的纳米Ni(OH)2呈现不规则形态,而Cu/Al复合掺杂的纳米Ni(OH)2呈准球状且具有更大的振实密度。将纳米样品以8%的比例掺入到商业用微米级球形镍中制成混合电极。充放电和循环伏安测试结果表明,Cu/Al复合掺杂纳米Ni(OH)2的电化学性能优于Cu单掺杂的纳米Ni(OH)2的,前者的放电比容量最高达到330mA·h/g(0.2C),比Cu单掺杂样品的高12mA·h/g,比纯球镍电极的高91mA·h/g。此外,Cu/Al复合掺杂纳米样品的质子扩散系数比Cu单掺杂样品的高52.3%。