酸性介质中丙烯基硫脲对铜阳极溶出和阴极沉积过程影响的EQCM研究

采用循环伏安(CV)和电化学石英晶体微天平(EQCM)方法研究了酸性介质中铜阳极溶出和阴极沉积过程以及丙烯基硫脲(AT)对该过程的影响. 结果表明, 铜阳极溶出和阴极沉积过程的M/n分别为32.0和34.2 g/mol, 都是两电子过程, 其间未检测到Cu(Ⅰ)中间产物. AT改变了铜阳极溶出和阴极沉积的历程. 在含AT的溶液中, 铜阳极溶出和阴极沉积过程的M/n分别为61.9和65.4 g/mol, 可指认铜阳极溶出产物为CuAT+, 并提出了AT存在下Cu阳极溶出和阴极沉积过程的反应机理; 从电极表面质量定量变化的角度提供了Cu阳极溶出和阴极沉积过程的新数据.     

Electrochemical reactions at a copper electrode in copper-conducting solid electrolytes

Potentiostatic measurements are used to show that, depending on the overvoltage sign, either electrochemical deposition or dissolution of copper occurs at the Cu/Cu₄RbCl₃I₂ interface at overvoltages η > 8–10 mV. At η = 10–100 mV, the reaction rate is limited by the formation and expansion of dissolution centers at the copper surface during anodic polarization and crystallization centers, during cathodic polarization. At η > 120 mV, the reaction rate is limited by charge transfer; the exchange current density is 2.7 mA cm^?2 and the anodic transfer coefficient is ～0.45. Under anodic polarization, formation of electron holes in the electrolyte occurs in parallel with the copper anodic dissolution. Therefore, nonstoichiometry of the electrolyte emerges in the near-electrode layer and divalent copper accumulates there.     

Study of the copper electrodeposition process from low molecular weight polymer electrolyte media

The characteristics of the copper deposition process from electrochemical cells using a solution of Cu(CF₃SO₃)₂ in low molecular weight poly(ethylene glycol), PEG, have been investigated by cyclic voltammetry, potential steps and impedance spectroscopy. The results suggest that under non-equilibrium at the cathodic side the process mainly involves the reduction of Cu(II) ions to copper metal while at the anodic side a chemical reaction competes with the electrochemical dissolution.     

CO2-3对羟基乙叉二膦酸镀铜液的影响

研究羟基乙叉二膦酸(HEDPA)镀铜液中CO2-3含量对电沉积时阴、阳极过程及镀层的择优取向的影响. 通过分析阴、阳极的动电位极化曲线, 发现镀液中逐渐加入的CO2-3提高了阴极的极化, 使电结晶晶粒细化, 直至达到稳定; 同时促进了铜阳极的溶解. 而X射线衍射(XRD)结果表明, 铜镀层的晶面择优取向从(222)逐渐向(111)转变. 通过镀液中固体络合物的红外光谱分析表明, CO2-3的加入以第二配体的方式进入该镀液的放电络合离子结构中, 参与Cu2+的络合, 形成更稳定的络合物, 从而导致铜沉积电位负移, 镀层(111)晶面取向增强.     

Copper oxides: kinetics of formation and semiconducting properties. Part I. Polycrystalline copper and copper-gold alloys

The anodic formation of Cu(I) and Cu(II) oxides on polycrystalline copper and copper-gold alloys (4 and 15 at% Au) in deoxygenated 0.1 M KOH was examined by voltammetry, chronoamperometry, and chronopotentiometry with a synchronous registration of photocurrent and photopotential, in situ spectroscopy of photocurrent as well as XPS and SEM measurements. The band gap of p-Cu₂O is 2.2 eV for indirect optical transitions independent of the concentration of gold in Cu-Au alloy. It grows on CuOH or n-Cu₂O underlayer. The increase of anodic potential results in a thickening of oxide film which is a mixture of Cu(I) and Cu(II) oxides. The latter is a p-type semiconductor with a low photosensitivity. The rate of oxide formation on the alloys is lower than on copper. The structure-dependent properties of the oxide phase on the alloys and copper are different. Copper is prone to corrosive oxidation even in deoxygenated alkaline solution by the traces of molecular oxygen. The corrosive growth of Cu(I) oxide film occurs according to the parabolic law. After the cathodic polarization, the surface of copper remains free of corrosive oxide no longer than 15–20 min. The preliminary anodic formation even of a thin Cu₂O film as well as the alloying of copper with gold suppresses the corrosive oxidation of copper.     

The electrochemistry of gold in acetonitrile solutions containing thiocyanate ions

Gold dissolves anodically in acetonitrile solutions containing dissolved NaSCN, at 25°C. The reaction yields Au(I) and Au(III) complex ion species which can be cathodically electroplated. The voltammetric experiments indicate that the anodic dissolution is preceded by a partial surface saturation with the intermediate initially discharged, followed by a diffusion controlled process which depends on the SCN^? ion concentration. The electrochemical behaviour of the anodic and cathodic processes is comparable to that of gold in aqueous solutions containing Au-complex ions.     

Electrosynthesis of Cu-Se films on copper electrodes in alkaline media: a voltammetric, electrochemical quartz crystal microbalance and I/t transient study

The electroformation of Cu-Se phases, obtained by selenizing a thin film of copper deposited on the quartz/gold electrode system, was studied with an electrochemical quartz crystal microbalance (EQCM) and by cyclic voltammetry (CV) in an alkaline solution (0.05 M Na(2)B(4)O(7)) containing selenide ion. Potentiodynamic parameters showed that the formation of the initial Cu-Se phases (Cu(2-x)Se/Cu(3)Se(2)) is ruled by an irreversible diffusion controlled mechanism, where a first electron transfer is the rate-determining step. A CV study was also performed with a bulk copper electrode in 1 M NaOH solution containing selenide ion. The deconvolution of the anodic and cathodic I/E profiles corresponding to the electroformation and electroreduction of the Cu-Se film formed allowed us to establish that, depending on the anodic potential limit of the potentiodynamic scan, the Cu-Se phases formed were either a mixture of Cu(2)(-x)Se/Cu(3)Se(2) or Cu(2-x)Se/Cu(3)Se(2)/CuSe. An EQCM study showed that, during the initial stage of Cu-Se phase electroformation, water molecules were released from the electrode. In advanced stages of the process, when the electrode was completely covered by Cu-Se compounds, selenide anions were adsorbed on the formed phase. When the anodic potential limit was extended to -0.2 V, copper oxide compounds were formed. The analysis of the cathodic charge related to Cu-Se phase electroreduction and Energy Dispersive X-ray Spectroscopy (EDXS) analysis confirmed that when the anodic limit was -0.8 V, a mixture of different Cu-Se phases was formed. A I/t transient study performed with a bulk copper electrode in alkaline solution containing selenide established that the nucleation and growth mechanism (NGM) of the Cu-Se phases takes place through an initial bidimensional-instantaneous nucleation (IN2D), followed by four bidimensional-progressive nucleations (PN2D). These results and atomic force microscopy (AFM) experiences supported that the growth of the Cu-Se films occurs through a layer-by-layer mechanism.     

Copper Corrosion in Acid Chloride Solutions: A Quartz Microgravimetry Study

Making use of the quartz microgravimetry method allows one to in situ obtain the m vs. t curves simultaneously with the E _cor vs. t curves (m is the weight of a dissolved or deposited substance, t a time period, E _cor a corrosion potential), which gives one a chance to determine the corrosion rate and its dependence on the concentration of copper ions and chloride ions in solution to within a good accuracy. The corrosion rate increases with increasing concentration of ions of divalent copper in solution, while an increase in the concentration of chloride ions does not lead to its change. The formation of a salt film of an intermediate compound of univalent copper during the copper dissolution process in solutions diluted with respect to chloride ions (0.1 M NaCl, 0.03 M CuCl₂) is discovered experimentally. In the m vs. t curves, the formation of the film manifests itself in the form of an increase in the electrode weight, while the corrosion potential transients reflect but weakly the occurring complex surface conversions. Techniques for the identification of intermediate solid species are proposed. The coefficients of mass transfer with respect to ions of divalent copper are determined. Explanations for variations in the system's behavior following a decrease in the concentration of chloride ions in solution are offered.     

Direct evidence of initial pitting corrosion

The chloride ion (Cl⁻) is known as an aggressive species in the aqueous solutions that adsorbs to the imperfect sites on the metal surfaces, such as defects, impurities and second-phase particles. This adsorption process could change the chemical composition and properties, such as ion conductivity, of the passive film. As a result, the passive film becomes less protective and breaks down at some places where the underlying metals are exposed to the electrolyte and dissolved through anodic reaction forming a pit. In the meantime, the hydrolysis (cathodic reaction) occurs inside the pit giving rise to a lower pH and leading to an increased dissolution rate of the metals. Subsequently, more chloride ions migrate into the pit in order to maintain electrical neutrality and adsorb onto the pit surface. The repeating of such process causes the pitting propagation. However, anodic polarization allows the chloride ions to migrate into the passive film more easily. With growth of the pit, more corrosion products make both in plane diffusion across the sample surface and out-of-plane diffusion to bulk solution from the pit mouth [M.G. Fontana, N.D. Greene, Corrosion Engineering, second ed., McGraw-Hill, New York, 1978].     

An electrochemical study on interaction of copper ions with three isomers,picolinic, nicotinic and isonicotinic acids at physiological pH

The electrochemical behaviors of copper ions complexed with picolinic, nicotinic and isonicotinic acids (2-, 3- and 4-pyridinecarboxylic acids) in Britton–Robinson buffer (pH 7.4) was studied by polarographic and voltammetric techniques on a mercury electrode. This study showed that the reduction of complexed copper ions in the presence of nicotinic acid (NA) was carried out in two one-electron steps [Cu(II)/Cu(I) and Cu(I)/Cu(0)] whereas this cathodic process in the presence of picolinic acid (PA) or isonicotinic acid (INA) occurred in one two-electron step [Cu(II)/Cu(0)]. The stability of the Cu(I) complex can be sourced from the positions of carboxylate substituents on these isomeric ligands, binding to the copper center.     

Initial stages of copper electrocrystallization from sulfate electrolytes: Cyclic voltammetry on a platinum ring-disk electrode

Initial stages of copper electrocrystallization on platinum rotating and stationary ring-disk electrodes are studied in sulfate electrolytes of different acidities by cyclic voltammetry with a variable cathodic limit. In a weakly acid sodium sulfate solution of pH 3.7, copper deposition occurs at a higher rate than in a sulfuric acid electrolyte, which is due to an acceleration of the discharge of copper ions caused by local electrostatic effects that occur during the specific adsorption of sulfate anions and hydroxyl ions and to alterating nature of electroactive species. The mechanism of the formation of intermediate species (ions Cu⁺) during the deposition and dissolution of copper in solutions of different acidities is established.     

Effect of applied curent on copper sulphide-based ion-selective electrodes

The properties of precipitate-based copper sulphide electrodes are investigated. Solid-phase studies wre done by x-ray photoelectron spectroscopy and solution-phase studies by combined potentiometric and atomic absorptioni spectrometric techniques. The predominant valence state of copper in the copper sulphide samples is shown to be Cu(I), but Cu(II) can also be identified at the surfaces. The oxidation of the membrane surface results in dissolution of copper ion and a decrease in the Cu/S ratio in the solid phase; reduction of the surface causes sulphide dissolution and an increase in the Cu/S ratio. Application of anodic or cathodic curents was used to study the redox behaviour of the copper suphide memebrane.     

Electrochemical detection of Cu(I) and Cu(II) in styrene media

A method is described to detect Cu(II) and Cu(I) added as bromide simultaneously in styrene solution containing tetrahexylammoniumperchloraat (THAP) as supporting electrolyte. It was found that Cu(II) and Cu(I) behave similarly in styrene and in aqueous solution. Reduction of Cu(II) and Cu(I) to metallic copper, as well as oxidation of Cu(I) to Cu(II) and the dissolution of a deposited metallic copper layer are observed. Ohmic drop problems were circumvented by adding THAP to the styrene solution and using ultramicro electrodes. The simultaneous detection of Cu(II) and Cu(I) is based on recording a cyclic voltammetric curve in a mixture of these compounds and calculating their concentration from the cathodic limiting current obtained at −0.80 V vs. RE and the anodic stripping peak corresponding to the dissolution of metallic copper. A detection limit of 2.0×10⁻⁴ mol l⁻¹ was obtained for both Cu(II) and Cu(I) and reproducible results were obtained concerning sensitivity and stability of the calibration curves.     

A comparative evaluation on the anodic behavior of Cu and Ag electrodes in non-aqueous fluoride and fluoroborate media

The voltammetric responses of copper and silver had been extensively studied and compared in a variety of non-aqueous solvents such as acetonitrile (AN), propylene carbonate (PC) and sulfolane containing two different supporting electrolytes namely triethylaminetrishydrogen fluoride (TEA.3HF) and tetrabutylammonium tetrafluoroborate (TBABF₄). The dissolution rate and surface transformation on the electrode surfaces as a result of anodic polarization was investigated using atomic absorption spectroscopy (AAS) and scanning electron microscopy (SEM), respectively. In solvent-free TEA.3HF medium, the copper electrode shows high charge recovery ratio (Q _c/Q _a), and the difference between the initial anodic and cathodic potentials, obtained at a current density of 2 mA cm⁻², is around 0.11 V, suggesting that in this medium, Cu can certainly serve as reference electrode. On the other hand, on Ag electrode, substantial dissolution was observed leading to very high anodic (Q _a) and cathodic (Q _c) charges, and the surface morphology after the cyclic polarization results in roughened surface with large pores. The effects of incorporating AN and water as additives in TEA.3HF on the solubility and stability of these metal fluoride films are also reported. The dissolution pattern and film formation behavior of these two metals in the different solvents containing fluoride and fluoroborate ionic species have several qualitative similarities, as noted from cyclic voltammetry responses and SEM morphology. Anodic dissolution and precipitation process for both Cu and Ag depends significantly on the nature of supporting electrolytes as well as solvents. In AN containing 0.1 M TEA.3HF, the dissolution of Cu and Ag electrodes was very high. Fluoride salts of Cu show lesser solubility than Ag in those solvents, while fluoroborate salts exhibit the reverse trend. The AAS data suggest that for a particular salt, which may be either fluoride or fluoroborate of Cu and Ag, the relative solubility decreases in the order AN > PC > sulfolane.     

Anodisation of copper in thiourea- and formamidine disulphide-containing acid solution.: Part I. Identification of products and reaction pathway

The anodic behaviour of copper in aqueous 0.5 M sulphuric acid containing different amounts of dissolved thiourea or formamidine disulphide was investigated at 298 K, combining data from electrochemical polarisation, chemical analysis, UV–vis spectroscopy, XPS and EDAX analysis, and structural information on copper–thiourea complexes. The main reactions depend on the applied potential and initial thiourea concentration. In the potential range −0.30≤E≤0.075 V (versus SCE), the electro-oxidation of thiourea to formamidine disulphide, the formation of Cu(I)–thiourea soluble complexes, and Cu(I)–thiourea complex polymer-like films, are the most relevant processes. The formation of this film depends on certain critical thiourea/copper ion molar concentration ratios at the reaction interface. At low positive potentials, the former reaction is under intermediate kinetic control, with the diffusion of thiourea from the solution playing a key role. For E≥0.075 V, soluble Cu(II) ions in the solution are formed and the anodic film is gradually changed to another one consisting of copper sulphide and residual copper. The new film assists the localised electrodissolution of copper. A complex reaction pathway for copper anodisation in these media for the low and high potential range is advanced.     

Corrosion of copper in aerated acidic pickling solutions and its inhibition by 3-amino-1,2,4-triazole-5-thiol

Corrosion of copper in aerated acidic chloride pickling (0.5 M HCl) solutions and its inhibition by 3-amino-1,2,4-triazole-5-thiol (ATT) have been investigated using electrochemical techniques and weight-loss measurements, along with Raman spectroscopy. Electrochemical measurements for copper after varied immersion periods of 0, 24, and 48 h showed that the presence of ATT and the increase of its concentration significantly decrease cathodic, anodic, corrosion (j(Corr)) currents and corrosion rates (K(Corr)), as well as the dissolution currents at 300 mV vs Ag/AgCl, while increasing polarization resistance (Rp), degree of surface coverage (theta) and inhibition efficiency (IE%) to a great extent. Weight-loss measurements after different immersion periods of 6 to 48 h revealed that the dissolution of copper decreased to a minimum and the corresponding IE% increased with increasing ATT concentration. The detection of ATT molecules on the copper surface by Raman spectroscopy indicated that inhibition of copper corrosion is achieved by strong adsorption of ATT molecules onto the copper surface.     

Copper electrodeposition into ion-exchange materials

Electrodeposition of copper into spherical granules of ion-exchange materials KU-23 and KU-2 out of acid sulfate solutions is studied by a method of cyclic voltammetry. It is discovered that the discharge of copper ions in an ion-exchange matrix is characterized by a cathodic overvoltage that is higher than the overvoltage of the same process on a graphite substrate by 0.08 V, which is most probably connected with a limited mobility of ions localized at fixed groups [RSO ₃ ^? ]. The cyclic voltammogram exhibits an additional cathodic peak in the potential region corresponding to the reduction of single-charged copper ions that form as a result of their accumulation inside pores of the ion-exchange matrix during anodic dissolution of metal deposited previously. It is fixed microscopically that the process of deposition begins at the graphite substrate/ion-exchanger interface and passes into bulk upon the formation of an electron-conducting layer saturated with copper. Preliminary saturation of the ion-exchanger by copper deposited chemically facilitates uniform electrodeposition of copper over the entire volume of pores of the ion-exchange matrix.     

酸性化学镀镍磷合金的动力学机理

通过极化曲线研究了3种不同溶液（阴极液、阳极液和完整镀液）的电化学行为,测定了主盐、还原剂浓度以及镀液pH和体系温度对化学镀镍沉积速率的影响. 与直接在镁合金上化学镀镍并使用重量分析法得到的沉积速率相比较发现,完整镀液体系的极化曲线才能真实地反映化学镀镍的沉积过程,其过程不能简单视为由彼此完全独立毫无关联的阴阳极半反应构成. 根据Butler-Volmer公式,本化学镀液体系的化学镀镍过程属混合控制,其表观反应活化能为42.89 kJ·mol^-1.     

Differential pulse cathodic stripping voltammetry of the copper complexes of glycyl-L-histidyl-glycine at a hanging mercury drop electrode

The behaviour of the copper complexes of glycyl-L-histidyl-glycine (GHG) was investigated using cyclic voltammetry and differential pulse voltammetry after their adsorptive accumulation on the surface of a hanging mercury drop electrode (HMDE). The nature of the observed cathodic and anodic peaks was established and optimum conditions were found for the differential pulse cathodic stripping voltammetric detemination of GHG at the 1 x 10(-8)M concentration level using adsorptive accumulation at -0.20 V vs. Ag/AgCl reference electrode and the cathodic stripping peak around -0.4 V (pH 8.3). This peak corresponds to the reduction of the Cu(I)-GHG complex formed at the HMDE surface as an intermediate in the reduction of Cu(II)-GHG to Cu(O)amalgam.     

The electrochemistry of gold in acid aqueous solutions containing chloride ions

Results obtained with differently prepared gold electrodes in acid solutions containing chloride ion at temperatures ranging from 22 to 65°C are reported. Potentiostatic techniques and rotating disc electrodes were employed. The anodic dissolution, the onset of passivity and the cathodic deposition of the metal are investigated under different experimental conditions. The anodic dissolution of Au is discussed in terms of possible reaction mechanisms involving the participation of different adsorbed species. The onset of passivation is related to the depletion of chloride ion at the reaction interface. The experimental voltammograms can be reporduced by means of an equation which considers the diffusion of chloride ion, the activation polarization related to the dissolution of Au and the establishment of passivity.