Electro-assisted fabrication of layer-by-layer assembled poly(2,5-dimethoxyaniline)/phosphotungstic acid modified electrode and electrocatalytic oxidation of ascorbic acid

Multilayer films, consisting of poly(2,5-dimethoxyaniline) (PDMA) and phosphotungstic acid (PTA) as alternative layers are assembled on a glassy carbon (GC) electrode to obtain (PDMA/PTA)_n layer-by-layer (LBL) film, (where n = number of layers of PDMA/PTA) through electrochemical polymerization and chemical treatment with PTA. The film assembly, electrochemical property as well as the electroactivity of GC/(PDMA/PTA)_n toward oxidation of ascorbic acid (AA) were investigated. The enhanced electrocatalytic activity of LBL (PDMA/PTA)_n film towards AA was attributed to the existence of tungsten atoms in the interlayer of PDMA that augments the electron transfer processes.     

铂微粒修饰聚2，5－二甲氧基苯胺电极对甲醇的电催化作用

将以铂微粒修饰玻碳电极（ＧＣ）为基体的聚２，５－二甲氧基苯胺膜（ＰＤＭＡ）形成修饰电极（Ｐｔ／ＰＤＭＡ／ＧＣ）．循环伏安实验表明，Ｐｔ／ＰＤＭＡ／ＧＣ电极对甲醇氧化比分散于玻碳电极上的铂催化活性更大。讨论了ＰＤＭＡ膜厚度、铂微粒含量及甲醇浓度对催化活性的影响。这种电极在酸性甲醇溶液中具有良好的稳定性。     

Electrooxidation and Amperometric Detection of Ascorbic Acid at GC Electrode Modified by Electropolymerization of N,N‐Dimethylaniline

The polymer film of N,N‐dimethylaniline (DMA) is deposited on the electrochemically pretreated glassy carbon (GC) electrode by continuous electrooxidation of the monomer. This poly N,N‐dimethylaniline (PDMA) film‐coated electrode can be used as an amperometric sensor of ascorbic acid (AA). The polymer film (thickness (?): 0.3±0.02 μm) having positive charge in its backbone attracts the anionic species AA. Thus, the anodic peak potential (350 mV vs. Ag|AgCl|NaCl_(sat)) for the oxidation of AA at the bare electrode is largely shifted to the negative value (150 mV) at this electrode. The PDMA film‐coated electrode is stable in acidic, alkaline and neutral media and can sense AA at different pH's. The diffusion coefficients of AA in solution (D) and in film (D_s) were estimated by rotating disk electrode voltammetry: D=(5.5±0.1)×10^?6 cm² s^?1 and D_s=(6.3±0.2)×10^?8, (6.0±0.2)×10^?8 and (4.7±0.2)×10^?8 cm² s^?1 for 0.5, 1.5 and 3.0 mM AA, respectively. A permeability of AA through the PDMA film was found to decrease with increasing the concentration of AA in the solution. In the chronoamperometry, the current response for the oxidation of AA at different times elapsed after potential‐step application is linearly increased with the increase in AA concentration in a wide range of its concentration from 25 μM to 1.65 mM. In the hydrodynamic amperometry, a successive addition of 10 μM AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.178 μA cm^?2 μM^?1. So, the fouling of the electrode surface caused by the oxidized product of AA is markedly eliminated at this PDMA film‐coated electrode. A flow injection analysis based on the present electrode was performed to estimate the concentration of vitamin C in fruit juice.     

Decomposition and Detection of Hydrogen Peroxide Using δ‐MnO2 Thin Film Electrode with Self‐Healing Property

A thin film of δ‐type MnO₂ grown cathodically has been investigated with respect to the ability toward anodic decomposition of H₂O₂ and durability. With polarization at less positive potentials than +0.4 V vs. Ag/AgCl, the film was dissolved exclusively as a result of reduction of Mn⁴⁺ sites in the oxide by H₂O₂ to soluble Mn²⁺. At +0.9 V, MnO₂ remained unchanged and decomposed H₂O₂ in solution. At +0.8 V, the film was once dissolved in the initial stage; however, it was self‐healed via reoxidation of the liberated Mn²⁺ ions. Amperometric flow‐injection analysis of H₂O₂ was carried out with the δ‐MnO₂ film.     

The effect of the change in the microscopic structures of the iron on corrosion resistance and passivated properties

The passive film of iron showed n‐type semiconductor characteristic in borate buffer solution, and its donor concentration increased slightly after tensile strain in the present study. However, comparing with solution‐annealed sample, the anodic passive film formed on tensile‐strained one was highly protective. The more dislocations on tensile‐strained sample promoted the diffusion of iron and oxygen vacancy. Moreover, more donor density (mainly oxygen vacancies) promoted the diffusion of oxygen. They all facilitated tensile‐strained sample to form Fe₂O₃ and thicker passive film on the surface. More Fe₂O₃ and thicker passive film on the surface of tensile‐strained iron could improve corrosion resistance. Copyright © 2014 John Wiley & Sons, Ltd.     

Online Monitoring of Electrochemical Carbon Corrosion in Alkaline Electrolytes by Differential Electrochemical Mass Spectrometry

Carbon corrosion at high anodic potentials is a major source of instability, especially in acidic electrolytes and impairs the long‐term functionality of electrodes. In‐depth investigation of carbon corrosion in alkaline environment by means of differential electrochemical mass spectrometry (DEMS) is prevented by the conversion of CO₂ into CO₃^2?. We report the adaptation of a DEMS system for online CO₂ detection as the product of carbon corrosion in alkaline electrolytes. A new cell design allows for in situ acidification of the electrolyte to release initially dissolved CO₃^2? as CO₂ in front of the DEMS membrane and its subsequent detection by mass spectrometry. DEMS studies of a carbon‐supported nickel boride (Ni_xB/C) catalyst and Vulcan XC 72 at high anodic potentials suggest protection of carbon in the presence of highly active oxygen evolution electrocatalysts. Most importantly, carbon corrosion is decreased in alkaline solution.     

Experimental and theoretical studies of acridine orange as corrosion inhibitor for copper protection in acidic media

The corrosion process commonly limits the use of copper in practical applications. The use of corrosion inhibitors is one of the effective methods to reduce the corrosion rate of copper. In this research, the inhibition effect of acridine orange (3,6-bis(dimethylamine)acridine) (AcO) for the protection of copper in 0.5 ?M ?H₂SO₄ solution was studied. For this aim, the change of open circuit potential with exposure time (E_ocp-t), electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), anodic and cathodic potentiodynamic polarization measurements (PP) and chronoamperometry (CA) techniques were used. Some quantum chemical parameters (E_HOMO, E_LUMO and dipole moment) were calculated and discussed. The AcO film formed over the copper surface was examined by SEM, EDX, AFM and contact angle measurements. The electrochemical data showed that AcO is an effective corrosion inhibitor even at low concentrations (ranging between 99.1% and %99.4 ?at concentrations from 0.01 ?mM to 1 ?mM). The corrosion rate of copper decreases in the presence of the inhibitor by reducing both anodic and cathodic rates, which is depended on its concentration. This compound behaves as mixed-type corrosion inhibitors with predominantly cathodic type. Its adsorption on the copper surface obeys Langmuir adsorption isotherm. The value of adsorption equilibrium constant (K_ads) and the standard free energy of adsorption were ΔG_ads 1.298 x 10³ ?M^?1 and -27.71 ?kJ/mol in the case of 0.5 ?M ?H₂SO₄ solution containing 1.0 ?mM AcO, which shows the adsorption is high and spontaneous. The adsorbed inhibitor film over the metal increase contact angle of the surface, which suggests the more hydrophobic properties of the surface are increasing coming from the orientation of hydrophobic sites to the electrolyte. The zero charge potential (E_pzc) studies showed that the surface charge of the metal is positive in the corrosive media containing the inhibitor. Quantum chemical calculations showed that the binding of inhibitor molecules to the metal surface takes place through N atoms of the inhibitor.     

Comparative EIS study of a paste electrode containing zinc powder in neutral and near neutral solutions

The corrosion and passivation of Zn powder particles dispersed in a paste electrode immersed in 0.5 M Na₂SO₄ and 5×10^–3 M Na₂HPO₄ solutions were studied mainly by electrochemical impedance spectroscopy. The role played by diffusion in the mechanism of anodic oxidation of zinc powder particles has been shown. It was demonstrated that the anodic reactionof Zn powder in neutral or near neutral media involves at least two adsorbed intermediates. By simulating the porous structure of the electrode, some information about porous nature of zinc electrode could be extracted. Electronic Publication     

Corrosion analysis,and use of an inhibitor in oil wells

When oil fields enter a period of high water content the downhole string becomes severely corroded, which not only affects normal oil field production but also necessitates high maintenance and replacement costs. The corrosion is mainly caused by such substances as H₂S, CO₂, O₂, and Cl^?, and by bacteria. According to test results from analysis of well fluid, average CO₂, H₂S, dissolved O₂, and Cl^? content were 28.4, 29.33, 0.43, and 21162.8 mg/L, respectively. Corrosion mechanisms involve an autocatalytic effect caused by pitting of, or formation of films on, the metal surface, destruction of the passivation film by Cl^?, and the synergetic effect of O₂ on H₂S and CO₂ corrosion; all of these combine to increase the rate of corrosion of metallic materials. On the basis of the mechanism and causes of serious corrosion of the oil well downhole string during production, the corrosion inhibitor YC-JTHSJ, suitable for high water-content oil wells, was developed. The weight-loss method showed that corrosion was reduced by 87.04 % by this inhibitor, and the average iron content of oil well liquid dropped by more than 85 % when 80 ppm YC-JTHSJ was added. This result showed that application of this well-specific inhibitor can reduce the rate of wellbore corrosion, the time required for pump inspection and maintenance, replacement of tubing and sucker rod, and thus production costs.     

Fabrication of AAO films with controllable nanopore size by changing electrolytes and electrolytic parameters

In this paper, we fabricate two kinds of anodic aluminum oxide (AAO) films with controllable nanopore size by changing electrolytes and electrolytic parameters. The first AAO film with a four-layer structure was fabricated by sequential anodization of aluminum in aqueous solution of H₂SO₄, H₂C₂O₄, malonic acid, and tartaric acid at different anodic oxidation voltages. The average pore diameter of the as-prepared AAO film is 25 nm in the first layer, 54 nm in the second layer, 68 nm in the third layer, and 88 nm in the fourth layer, respectively. The pore densities of each layer decrease downwards to Al substrate, which are 300?×?10⁸, 100?×?10⁸, 21?×?10⁸, and 6.9?×?10⁸ cm^?2, respectively. Furthermore, another AAO film with periodically changed pore diameter was fabricated by alternating anodization of aluminum in aqueous solution of H₃PO₄ and tartaric acid under galvanostatic mode. The anodization processes present approximately identical best ordering voltage (195 V) in H₃PO₄ and tartaric acid under galvanostatic mode. The pore diameter with periodic change can be enlarged through a pore-widening treatment. Both AAO films with special nanopore structures can be used not only as templates for preparing nano-array materials whose pore diameter presents periodic change or gradual increase, but also as nanofilters to separate materials in some special media.     

Surface characteristics of AZ91D alloy anodized with various conditions

Anodic oxidation of an AZ91D magnesium alloy was carried out in an attempt to increase the corrosion resistance. The alloy was placed in an electrolyte containing 0.1 M sodium silicate (Na₂SiO₃), 2.0 M sodium hydroxide (NaOH) and 0.1 M sodium phosphate (Na₃PO₄), and treated with a current density of 100–400 mA/cm² for 1 to 4 min. After the anodic oxidation treatment, the surface characteristics were analyzed by SEM, X‐ray diffraction (XRD) and a surface roughness tester. The corrosion resistance was determined by measuring the corrosion potential and corrosion current density using potentiodynamic polarization in a 3.5 wt% NaCl electrolyte solution. Although the anodic oxidation treatment with the base electrolyte resulted in an arrival voltage ranging from 60 to 70 V, the addition of silicate tended to reduce this arrival voltage by approximately 10–20 V and decrease the critical voltage required for the formation of a porous oxide film. The pore size and film thickness increased with increasing applied current and treatment time. The addition of silicate to the electrolyte resulted in films with a homogeneous pore size and a film thickness increasing with the increasing applied current and treatment time. XRD showed the formation of a new MgO and Mg₂SiO₄ phase. The formation of Mg₂SiO₄ was attributed to the presence of SiO₄^4? in the film. After the addition of silicate, the corrosion potential increased and corrosion current decreased, resulting in improved corrosion resistance. Copyright © 2008 John Wiley & Sons, Ltd.     

Electrochemically Polymerized N,N-Dimethylaniline Films Containing Tris-(Bathophenanthroline Disulfonato)Iron(II/III) Complexes

The electropolymerization of N, N-dimethylaniline (DMA) was carried out in an aqueous CF₃COONa solution (pH 1.0) containing DMA in the presence of tris(bathophenanthroline disulfonato)iron(II), Fe(bphen)₃ ^4-. Poly(N, N-dimethylanilinium trifluoroacetate) (PDMA) film was formed on electrode surfaces and, at the same time, Fe(bphen)₃ ^4- ions were stably confined in the formed PDMA film by electrostatic interaction between them and the positively charged quaternary ammonium sites of the PDMA film. The PDMA-Fe(bphen)₃ ^4-/3- film thus prepared displayed well-defined reversible electroactivity and electrochromic properties ascribable to those of the Fe(bphen)₃ ^4-/3- couple confined in the film. The PDMA-Fe(bphen)₃ ^4- film is red, and the PDMA-Fe(bphen)₃ ^3- film is colorless. The response rate of the color change to a potential pulse was found to be correlated with the kinetic parameters characterizing the rate of the overall charge-transfer reaction at the PDMA-Fe(bphen)₃ ^4-/3- film-coated electrode, that is, the apparent diffusion coefficient (D _app) for the homogeneous charge-transport process within the film and the standard rate constant (k) of the heterogeneous electron-transfer reaction at the electrode/film interface. For the PDMA-Fe(bphen)₃ ^4-/3- film with larger k° and D _app values, the response rate of the color change was larger, Further, k°, D _app, and response rate depended on the concentration (C°) of the Fe(bphen)₃ ^4- (or Fe(bphen)₃ ^3-) confined in the PDMA film; and at a given film thickness, the lower C°, the higher were k°, D _app, and response rate. At a given C°, the thinner the film thickness, the greater was the response rate.     

Versatile 2,5‐Pyridinedicarboxylate in Linking Transition‐Metal Atoms into 1D and 2D Coordination Polymers and Concomitant Polymorphs

By employing one bridging ligand, 2,5‐pyridinedicarboxylate (2,5‐pda^2?), in the presence or absence of another bridging ligand, 4,4′‐bipyridine (4,4′‐bpy), one one‐dimensional (1D) {[Co₂(2,5‐pda)(2,5‐Hpda)₂(4,4′‐bpy)(H₂O)₃]·6H₂O}_∞ ( 1 ) and two two‐dimensional (2D) coordination polymers, {[Cu₃(2,5‐pda)₃(H₂O)₃]·6H₂O}_∞ ( 2 ) and {[Co(2,5‐pda)(H₂O)]·2H₂O}_∞ ( 3 ) were synthesized. Complexes 2 and 3 are characterized as concomitant polymorphs from a one‐pot reaction at ambient temperature. A comparison of the coordination geometries of all neutral and anionic coordination polymers containing {M_x(2,5‐pda)_y(H₂O)_z}_∞ available to date is presented.     

Factors influencing the growth behaviour of nanoporous anodic films on iron under galvanostatic anodizing

The growth behaviour of nanoporous anodic films on iron during galvanostatic anodizing in ethylene glycol electrolytes containing NH₄F and H₂O is examined at various current densities, H₂O concentrations in electrolytes and temperatures. The film morphology is mainly controlled by the formation voltage, regardless of anodizing conditions. Relatively regular cylindrical pores are formed at formation voltages less than 50 V, while rather disordered pores are formed above 100 V. The decrease in the H₂O concentration suppresses chemical dissolution of anodic films in addition to the increased growth efficiency, resulting in the formation of anodic films with a steady thickness of ～7 μm. The cell size of the anodic films depends upon the H₂O concentration as well as the formation voltage, but not upon the current density. Findings in this study will be useful for controlled growth of the anodic films on iron.     

The effects of film thickness and incorporated anions on pitting corrosion of aluminum with barrier-type oxide films formed in neutral borate and phosphate electrolytes

The pitting corrosion behavior of high-purity aluminum covered with barrier-type anodic films, which are formed in neutral borate and phosphate electrolytes, has been examined in 0.5 mol dm^?3 NaCl solution at an applied potential of ?0.6 V versus Ag/AgCl, which is slightly nobler than the pitting potential of ?0.64 V in the same solution. The pitting current density, i _p, increased with time after an incubation time, t _i. The double logarithmic plot of i _p and polarization time, t, reveal two straight lines, which are separated at the time, τ. The slope becomes larger after τ for the specimens anodized in the phosphate electrolyte, while it becomes smaller for those in the borate electrolyte. Both the t _i and τ increase with the thickness of the anodic films, and at the similar film thickness, they are much larger for the anodic films formed in the phosphate electrolyte than for those in the borate electrolyte. The corrosion process can be divided into three stages: the incubation period up to t _i, the pit nucleation period before τ, and the pit growth period after τ. We have discussed the different pitting corrosion behavior of the aluminum specimens covered with the anodic films formed in the borate and phosphate electrolytes in terms of ion selectivity of the anodic films.     

The influence of Ce3+ ions on the corrosion rate of stainless steel in acidic solutions of different pH-values

The corrosion resistance of AISI 420 stainless steel in 0.1 mol L^?1 H₂SO₄ + 0.1 mol L^?1 Na₂SO₄ solutions at different pH-values and the inhibiting effect of Ce³⁺ ions was studied using electrochemical polarization methods. The results reveal decreasing of the corrosion rate with an increasing the pH of the solution, which demonstrates the progressive protective character of the inhibitor used. At pH lower than 3.33, the corrosion inhibition was most probably a result of the competitive adsorption of Ce³⁺ with H⁺ ions on the cathodic sites of the electrode surface, and it was found to be dependent on the relative concentration of H⁺/Ce³⁺. The peroxide generated from the oxygen reduction reaction at pH 3.33 was found to be capable oxidize trivalent cerium (Ce) to the tetravalent state. As obtained hydroxide precipitates act as diffusion barrier hindering the corrosion processes, whereafter a spontaneous passivity occurs on the steel surface at this pH.     

Computational Design of Iron Diphosphine Complexes with Pendant Amines for Hydrogenation of CO2 to Methanol: A Mimic of [NiFe] Hydrogenase

Inspired by the active‐site structure of the [NiFe] hydrogenase, we have computationally designed the iron complex [P^tBu₂N^tBu₂)Fe(CN)₂CO] by using an experimentally ready‐made diphosphine ligand with pendant amines for the hydrogenation of CO₂ to methanol. Density functional theory calculations indicate that the rate‐determining step in the whole catalytic reaction is the direct hydride transfer from the Fe center to the carbon atom in the formic acid with a total free energy barrier of 28.4 kcal mol^?1 in aqueous solution. Such a barrier indicates that the designed iron complex is a promising low‐cost catalyst for the formation of methanol from CO₂ and H₂ under mild conditions. The key role of the diphosphine ligand with pendent amine groups in the reaction is the assistance of the cleavage of H₂ by forming a Fe?H^δ????H^δ+?N dihydrogen bond in a fashion of frustrated Lewis pairs.     

Corrosion and corrosion inhibition characteristics of bulk nanocrystalline ingot iron in sulphuric acid

The corrosion and corrosion inhibition of bulk nanocrystalline ingot iron (BNII) fabricated from conventional polycrystalline ingot iron (CPII) by severe rolling was studied in 0.5 M H₂SO₄ solution using electrochemical impedance spectroscopy and potentiodynamic polarization techniques. The results indicate that BNII was more susceptible to corrosion in the acidic environment essentially because of an increase in the kinetics of the anodic reaction. An amino acid cysteine (cys) was employed as a corrosion inhibitor at concentrations of 0.001 and 0.005 M. Tests in inhibited solutions revealed that cys reduced the corrosion rates of both metal specimens by different mechanisms. For CPII cys inhibited the cathodic reaction but had a stimulating effect on the anodic process at low concentration and a trivial effect at higher concentration. For BNII, cys inhibited both the cathodic and the anodic reactions, although the former effect was more pronounced. Iodide ions improved the inhibitive effect of cys without altering the inhibition mechanism.     

Rotating-disc electrode studies of the anodic oxidation of iodide in concentrated iodine + iodide solutions

The anodic oxidation of iodide on platinum in concentrated iodine + iodide solutions has been investigated using a rotating disc electrode. The conventional limiting diffusion current, which is produced by the diffusion of iodide ions towards the electrode, was not observed due to the formation of an iodine film on the electrode. On the other hand, the steady-state anodic current after a current/time transient is the genuine limiting diffusion current in the anodic oxidation due to diffusion of iodine species from the electrode surface towards the bulk solution. Thus, the dissolution-diffusion control mechanism of the iodine film is confirmed. This is interesting as a typical example of an anodic process in a redox system governed by diffusion of the anodic product species from the electrode surface towards the bulk solution. When an iodine film is formed on the electrode, the maximum driving force of the iodine species is Δm_I2,max, which is defined as the extent of unsaturation of the iodine, and the limiting current of the anodic oxidation of iodide is always directly proportional to Δm_I2,max, regardless of the forms of iodine species in the solution, which may be I₂, I⁻₃, i₅⁻, etc. δm_I2,max is clearly determined by the solution composition and temperature, and it is different in definition and value from the usual degree of unsaturation of iodine.