Quantized spectroelectrochemical behaviour of monolayer-protected gold cluster films assessed by reflectance spectroelectrochemical quartz crystal microbalance

The spectral changes occurring in multilayer films of hexanethiolate monolayer-protected Au₁₄₇ clusters (C6–Au₁₄₇ MPCs) as a consequence of quantized MPC core charging have been investigated in aqueous solutions using a multiresponse technique, UV–vis reflectance spectroelectrochemical quartz crystal microbalance (SEQCM). The joint technique, a combination of UV–vis near-normal incidence reflectance spectroelectrochemistry and electrochemical quartz crystal microbalance, has enabled us to follow both reflectance and gravimetric changes taking place in the MPC film concurrently with each single electron transfer event. Reversible film reflectance drops were observed upon anodic MPC charging, which were linearly dependent on the MPC charge state. The values of the formal potential and number of electrons transferred in each charging step, determined from the potential dependence of the reflectance changes, proved that the spectral features were induced by the discrete charging of the MPCs. Simultaneously, the gravimetric signal monitored with EQCM yielded values of the number of MPC-bound electrolyte ions as a function of the MPC redox state, both during voltammetric and potential step charging of the MPC films. Additionally, the dynamics of electron transfers in these multilayer MPC films has been investigated by electrochemical impedance spectroscopy (EIS). Thus, the film capacitance, the resistance to charge transfer, and the electron-transfer rate constant for MPC oxidation have been estimated.     

Biosensor for Hepatitis B Virus DNA PCR Product and Electrochemical Study of the Interaction of Di(2,2′‐bipyridine)osmium(III) with DNA

The strategy for electrochemical detection of HBV DNA PCR product (181 bps) was designed by covalently immobilizing single‐stranded HBV DNA on preoxidized glassy carbon electrode surface. The immobilization of single stranded DNA was verified by AC impedance spectra. The following hybridization reaction on surface was evidenced by electrochemical methods using [Os(bpy)₂Cl₂]⁺ as an electroactive indicator. The interactions of [Os(bpy)₂Cl₂]⁺ with calf thymus single and double stranded DNA immobilized on preoxidized glassy carbon electrodes were studied. [Os(bpy)₂Cl₂]⁺ could bind preferentially to the duplex DNA by intercalating to base pairs. The intrinsic binding constant of [Os(bpy)₂Cl₂]⁺ with calf thymus DNA was calculated to be 1.21×10⁴ M^?1. Using [Os(bpy)₂Cl₂]⁺ as an electrochemical hybridization indicator, the HBV DNA sensor has been used to detect qualitatively target HBV DNA in solution with high sensitivity and selectivity.     

Electrochemical Behaviour of Iron in a Third‐Generation Ionic Liquid: Cyclic Voltammetry and Micromachining Investigations

The electrochemical behaviour of Fe in 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([Emim]⁺Ntf2^?) and mixtures with Cl^? is studied with the aim of investigating the applicability of ionic liquids (IL) for the electrochemical machining of iron. Whereas in pure IL iron could not be significantly dissolved, the addition of Cl^? enables the active dissolution with anodic current densities up to several mA cm^?2. Although several anodic peaks appear in the cyclic voltammograms (CV), the distinct assignment of those electrochemical processes remain difficult. In particular no proof for the formation of FeCl_x^2?x complexes during Fe dissolution are deduced from the CV, although such complexes are shown to be stable in the employed electrolyte. In addition, we present electrochemical drilling experiments with short potential pulses, which demonstrate that electrochemical machining of Fe is, in principle, possible in IL based electrolytes, even though hampered by slow machining speed.     

Pitting Corrosion Mechanisms and Characteristics of Aluminum in Solar Heating Systems

The complex characteristics and mechanisms of aluminum pitting corrosion in a solar heating system were studied by the chemical immersion method and electrochemical techniques as well as fractal theory. The results showed that pitting corrosion of Al occurred in a tap water environment due to the local enrichment of Cl^? ions. The higher the Cl^? ions concentration, the more negative the critical pitting potential (E_b) of Al. A linear relationship between E_b and the logarithm of Cl^? ions concentration was observed. The pitting corrosion mechanism of Al in neutral water was explained in terms of complexation corrosion theory. The corrosion surface images of aluminum immersed in tap water were captured and analyzed by image processing technique and box‐dimension method. The fractal characteristics of pit distribution, described by fractal dimension, have been identified. The fractal dimension of the pit distribution increased with the increase of immersion time and had the same trend as that of the weight loss. Fractal dimension can, thus, be used as an important parameter for quantitative evaluation of pitting corrosion of aluminum.     

Electrochemiluminescence Quenching by Halide Ions at Bipolar Electrodes

Quenching of Ru(bpy)₃²⁺ electrochemiluminescence (ECL) by Cl^?, Br^?, and I^? ions was studied as a function of halide concentration in a bipolar electrochemical cell. All of the halides investigated showed similar qualitative behavior: above a critical concentration, ECL intensity was found to decrease linearly as the halide ion concentration was increased, due to dynamic quenching of Ru(bpy)₃²⁺ ECL. Stern‐Volmer slopes (K_SV) of 0.111±0.003, 4.2±0.3, and 6.2±0.3 mM^?1 were measured for Cl^?, Br^? and I^?, respectively. The magnitude of K_SV correlates with halide ion oxidation potential, consistent with an electron transfer quenching mechanism. Using the bipolar platform described herein, aqueous, halide‐containing solutions could be quantified rapidly using the sequential standard addition method. The lower detection limit is determined by a complex mechanism involving the competitive electrooxidation of halide ions and the ECL co‐reactants, as well as the passivation of the surface of the bipolar electrode, and was found to be 0.20±0.01, 0.08±0.01 and 10±1 mM, respectively, for I^?, Br^?, and Cl^?. The performance of the bipolar ECL quenching assay is comparable to previously published fluorescence quenching methods for the determination of halide ions, while being much simpler and less expensive to implement.     

Ultrasensitive amperometric immunosensor for the determination of carcinoembryonic antigen based on a porous chitosan and gold nanoparticles functionalized interface

An immunosensor has been fabricated for direct amperometric determination of carcinoembryonic antigen. It is based on a biocompatible composite film composed of porous chitosan (pChit) and gold nanoparticles (GNPs). Firstly, a pChit film was formed on a glassy carbon electrode by means of electrodeposition. Then, thionine as a redox probe was immobilized on the pChit film modified electrode using glutaraldehyde as a cross-linker. Finally, GNPs were adsorbed on the electrode surface to assemble carcinoembryonic antibody (anti-CEA). The surface morphology of the pChit films was studied by means of a scanning electron microscope. The immunosensor was further characterized by cyclic voltammetry and electrochemical impedance spectroscopy. The electrochemical behaviors and factors influencing the performance of the resulting immunosensors were studied in detail. Results showed that the pChit films can enhance the surface coverage of antibodies and improve the sensitivity of the immunosensor. Under optimal conditions, the immunosensor was highly sensitive to CEA with a detection limit of 0.08 ng·mL^?1 at three times the background noise and linear ranges of 0.2～10.0 ng·mL^?1 and 10.0～160 ng·mL^?1. Moreover, the immunosensor exhibited high selectivity, good reproducibility and stability.     

A study by voltammetry and the photocurrent response method of copper electrode behavior in acidic and alkaline solutions containing chloride ions

The electrochemical behavior of Cu electrodes in Cl⁻ solutions was studied in a wide range of pH. The results were compared with those obtained in solutions containing F⁻, Br⁻, I⁻ and So²⁻₄ ions at pH 8.5, and discussed in terms of the competitive formation of Cu₂O and CuCl films on the Cu surface and the influence of CuCl on the properties of Cu₂O. At pH 8.5 or higher, Cu₂O was formed first, whereas at pH 5.7 or lower the Cu₂O film was formed on the Cu surface under the CuCl layer which was formed initially. It is believed that the Cu₂O films doped with Cl⁻ ions exhibited poor protective properties against Cu corrosion.     

Automated chromatographic separation coupled on-line to ICP-MS measurements for the quantification of actinides and radiostrontium in soil samples

The uranium (III) ions behaviour in fused 3LiCl–2KCl eutectic versus the Cl^?/Cl₂ reference electrode in the temperature range of 723–823 K on the liquid cadmium electrode by transient electrochemical techniques on the tungsten or molybdenum electrodes was studied. The mechanism of electrochemical reduction on cadmium cathode and the influence of temperature, cathode current density and the duration of electrolysis were studied. The activity coefficients and the base thermodynamic properties of uranium in fused U–Cd/3LiCl–2KCl system were calculated.     

Quantised charging of monolayer-protected nanoparticles

Metal nanoparticles coated with an organic monolayer, so-called monolayer protected clusters (MPCs), can show quantised charging at room temperature due to their sub-attofarad capacitance arising from the core size and the nature of the protecting monolayer. In this tutorial review, we examine the factors affecting the energetics of MPC charging. In the first section, the underlying physics of quantised charging is outlined and we give an overview of the various methods that can be used to measure single electron transfer to nanoparticles. In the subsequent sections, we discuss how electrochemical measurements can be used to give information on the quantised charging of freely diffusing and films of immobilised MPCs. The predictions of models used to determine MPC capacitance are compared with experimental data from the literature.     

Electrochemically initiated chain polymerization of pyrrole in aqueous media

The electrochemical quartz crystal microbalance has been employed to investigate the electropolymerization of pyrrole in a variety of aqueous electrolytes. In contrast to the generally accepted cation–radical coupling process for the electropolymerization of pyrrole, an electrochemically initiated chain polymerization, featuring a high polymerization rate and involving little charge transport, was found under specific conditions in the presence of ClO^?₄, BF^?₄, and PF^?₆ electrolytes. The more typical cation-radical coupling mechanism, characterized by a constant polymerization charge to mass deposited ratio, is observed in the presence of Cl^?, NO^?₃, dodecyl sulfate, copper phthalocyanine tetrasulfonate, β-cyclodextrin tetradecasulfate, and poly(styrene sulfonate). Electrochemical characterizations of polypyrrole films prepared in aqueous ClO^?₄ electrolytes reveal that the polymer formed via chain polymerization exhibits the ability to transport both cations and anions during electrochemical switching between redox states, while the polymer synthesized through cation-radical coupling is only capable of transporting a single ionic species.     

Electrochemical studies of iodine in an aluminium chloride-butylpyridinium chloride ionic liquid part II. Neutral and basic solvent composition

The electrochemical behavior of iodine in an ambient temperature molten salt system, aluminum chloride-N-(1-butyl)pyridinium chloride (BuPyCl), have been studied in basic (excess BuPyCl) and neutral (1.0:1.0 AlCl₃: BuPyCI mole ratio) melt compositions. Acid-base interactions of iodine in different oxidation states with the ionic solvent are observed. High stability of triiodide ion in neutral butylpyridinium tetrachloroaluminate indicates relatively weak intermolecular interactions in this solvent. In basic solutions polyhalogen equilibria involving iodine in different oxidation states and chloride ions are established. In iodine and tetraethylammonium triiodide solutions a mixture of ICI₂^?, I₂Cl^?, I₃^? and I^? ions forms. The formation constants of I₂Cl^? and I₃^? and the equilibrium constant for I₂Cl^? disproportionation are estimated.     

457—The mechanism of low frequency a.c. electrochemical disinfection

The mechanism of low frequency a.c. electrochemical disinfection was studied. A random oriented graphite fiber-epoxy matrix composite material was employed to fabricate the electrodes. This material was found to have very good electrochemical stability when cycled anodically and cathodically in solutions containing NaCl or NaBr.The lethal species was identified as HClO and HBrO in solutions containing Cl^? and Br^?, respectively, although the free halogen molecule may contribute to the observed disinfection activity under certain experimental conditions.The efficiency of disinfection increases with increasing concentration of Cl^? (or Br^?) and with decreasing pH. Deaerating the solution decreases the efficiency of disinfection significantly. NaBr was found to be effective at much lower concentrations than NaCl at all pH values but the effect is enhanced at pH > 7 due to ionization of HClO.The unique advantage of the method described in this paper is that a high transient concentration (in time and space) of the lethal species is generated, enough to destroy the most resistant microorganisms, while the average concentration of active halogen in the effluent liquid remains well below the objectionable level.     

An EQCM investigation of charging RuO2 thin films prepared by the polymeric precursor method

An electrochemical quartz crystal microbalance (EQCM) study of RuO₂ thin films, prepared by the sol-gel precursor method, is presented. The X-ray diffraction (XRD) analysis demonstrates that RuO₂ films were crystallized in the rutile phase and scanning electron microscopy investigations indicated the formation of a smooth surface. Cyclic voltammetry and EQCM studies were performed simultaneously in order to investigate the charging processes of the RuO₂ films in 0.1 M HClO₄. The voltammetric and mass versus potential responses present three well-defined regions associated with the RuO₂ redox couples. Based on these results and on the mass-charge relationships, the corresponding charging mechanisms are proposed. In the potential region governed by the Ru³⁺/Ru⁴⁺ redox couple, the mass-charge relation can be associated with the double-injection of protons and electrons. The other regions correspond to water release and oxyhydroxide species formation during charging.     

Electroreduction kinetics and mechanism of palladium(II) glycinate chloride complexes on rotating palladium disk electrode

The electroreduction kinetics of Pd(Hgly)₂Cl₂ on rotating palladium disk electrode was studied by means of cyclic voltammetry. The double layer range of the palladium charging curve showed a single wave with the diffusion limited current I _d, which yielded the diffusion coefficient of Pd(Hgly)₂Cl₂ complex D = 6 × 10⁻⁶ cm²/s. The plotted direct and reverse voltammetric curves were linearized in coordinates E, log[I/(I _d − I)]. The slope of this line gave b _k factor evidencing the slow electrochemical step. When [Cl⁻] decreased from 1 to 0.2 M, E _1/2 potential shifted to positive values. This was accounted for by reversible cleavage of Cl⁻ ion from Pd(Hgly)₂Cl₂ complexes before the irreversible electrochemical step. The pulse galvanostatic experiment resulted in the double electrical layer capacity and roughness factors f of electrolytic palladium deposits. The calculated values of f from 60 to 310 were attributed to adsorption of glycine particles on the electrodeposited palladium surface, which promotes to increasing number of palladium microcrystal growing centers.     

Thin films of metal dibenzotetraaza [14] annulene complexes.: Part 3. Dimerization and alternated dimerizations of γ-substituted Ni complexes

The electrochemical behaviour of some Ni γ-monosubstituted dibenzotetraaza [14] annulene complexes has been investigated. The oxidation in CH₂Cl₂ of the complex containing a 4-carboxybenzyl group leads to the corresponding γ-γ dimer whose electrochemical properties have been studied. The electrode surface can be coated by thin films of this dimer using CH₃CN instead of CH₂Cl₂; however, the resulting modified electrode is poorly stable. The oxidation of the complex containing 1-(4-carboxybenzyl)pyrrole as γ substituent involves γ-γ dimer formation before the formation of a regular polypyrrole film. The film displays reversible electrochemical reduction of the metal centre (Ni(II)/Ni(I)) and two successive oxidations of the macrocycle (Mc/Mc^•+ and Mc^•+/Mc²⁺). The complex containing a bromo(4-carboxybenzyl) group offers an unusual feature in that polymeric films can be obtained following an original procedure based on alternated dimerizations. This is a consequence of the formation of two different dimers obtained by anodic and cathodic processes.     

Optical,electrical, and electrochemical behavior of p-type nanostructured SnO<Subscript>2</Subscript>:Ni (NTO) thin films

The physical and electrochemical properties of sol-gel synthesized nickel-doped tin oxide (NTO) thin films were investigated. The X-ray diffraction results showed that NTO samples exhibited a tetragonal structure. The average crystallite size and the unit cell volume of the films were reduced by Ni increment, while the stacking fault probability was increased. Furthermore, the field-emission scanning electron microscopy images clearly displayed that the worm-like surface morphology of the SnO₂ thin films was altered to the spherical feature in 3 and 10 mol% NTO samples. Moreover, by virtue of Ni incorporation, the average transparency of the SnO₂ thin films rose up from 67 to 85% in the visible region; also, the optical band gap of the SnO₂ sample (3.97 eV) increased and the thin film with 3 mol% dopant concentration showed a maximum value of 4.22 eV. The blue/green emission intensities of photoluminescence spectra of SnO₂ thin film changed via Ni doping. The Hall effect measurements revealed that by Ni addition, the electrical conductivity of tin oxide thin films altered from n- to p-type and the carrier concentration of the films decreased due to the role of Ni²⁺ ions which act as electron acceptors in NTO films. In contrast, 20 mol% Ni-doped sample had the highest mobility about 9.65 cm² (V s)^?1. In addition, the cyclic voltammogram of NTO thin films in KOH electrolyte indicated the charge storage capacity and the surface total charge density of SnO₂ thin films enhanced via Ni doping. Moreover, the diffusion constant of the samples increased from 2?×?10^?15 to 6.5?×?10^?15 cm² s^?1 for undoped and 5 mol% dopant concentration. The electrochemical impedance spectroscopy of the NTO thin films in two different potentials showed the different electrochemical behaviors of n- and p-type thin films. It revealed that the 20 mol% NTO thin film had maximum charge transfer at lower applied potential.     

Enhancing effect of boron trifluoride diethyl etherate electrolytes on capacitance performance of electropolymerized poly[poly(<Emphasis Type="Italic">N</Emphasis>-vinyl-carbazole)] films

In this paper, poly[poly(N-vinyl-carbazole)] (PPVK) films electrodeposited in tetrahydrofuran (THF) containing 12 % boron trifluoride diethyl etherate (BFEE) were studied as electrode active material for supercapacitors. The morphology and thermal property were characterized by SEM, atomic force microscopy (AFM), and thermogravimetry (TG), respectively. The electrochemical capacitive behaviors of the PPVK films were also investigated by cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The electrochemical results showed that the specific capacitance of PPVK films in CH₃CN solution was about 126 mF cm^?2 at 1.5 mA cm^?2 and the capacitance retention was only 14.4 % after 1000 cycles. It was exciting to improve the specific capacitance up to 169.3 mF cm^?2 at 1.5 mA cm^?2 and to make the cyclic stability increase to 81.8 % capacitance retention after 5000 cycles when the equivalent BFEE was added into the CH₃CN solution containing 0.05 M Bu₄NBF₄ electrolyte. These results clearly demonstrated that BFEE was an efficient promoter for the enhancement of the capacitance performance of PPVK films. Therefore, with the help of BFEE electrolyte, the PPVK films have potential application as capacitive materials in high-performance energy storage devices.     

Reactive polythiophenes with zincke salt structure: Synthesis,polymer reactions,and chemical properties

Polythiophenes with reactive Zincke salt structure, such as PThThPy⁺DNP(Cl^?)Th , were synthesized by the oxidation polymerization of 3′‐(4‐N‐(2,4‐dinitrophenyl)pyridinium chloride)‐2,2′:5′,2″‐terthiophene ( ThThPy⁺DNP(Cl^?)Th ) with iron(III) chloride or copper(II) trifluoromethanesulfonate. The reaction of PThThPy⁺DNP(Cl^?)Th with R‐NH₂ (R = n‐hexyl (Hex) and phenyl (Ph)) substituted the 2,4‐dinitrophenyl group into the R group with the elimination of 2,4‐dinitroaniline to yield PThThPy⁺R(Cl^?)Th . Similarly, model compounds, ThThPy⁺R(Cl^?)Th (R = Hex and Ph), were also synthesized. In contrast to the photoluminescent ThThPyTh and PThThPyTh , the compounds PThThPy⁺DNP(Cl^?)Th , PThThPy⁺R(Cl^?)Th , and ThThPy⁺R(Cl^?)Th showed no photoluminescence because their internal pyridinium rings acted as quenchers. Cyclic voltammetry measurements suggested that PThThPy⁺DNP(Cl^?)Th received an electrochemical reduction of the pyridinium and 2,4‐dinitrophenyl groups and oxidation of the polymer backbone. PThThPy⁺DNP(Cl^?)Th was electrically conductive (ρ = 2.0 × 10^?6 S cm^?1) in the non‐doped state. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A study of ion exchange selectivity coefficient by cyclic voltammetric measurement

An equation to express ion exchange selectivity coefficient was derived and used for calculating that of PPY film with the results obtained by cyclic voltammetric measurement. PPY film was synthesized by electrochemical method in aqueous solution using K₄Fe(CN)₆ as supporting electrolyte, and the anions were doped into the film. Ion exchange behaviour of doped Fe (CN)₆^3-/4- in the PPY film with Cl^?, NO₃^? or F^? ions in solution has been studied, and the corresponding ion exchange selectivity coefficients were determined.     

Poly(vinylpyrrolidone)‐based films grown on copper surfaces

The influence of molecular weight and the amount of the poly(vinylpyrrolidone) (PVP) on the growth of poly(vinylpyrrolidone)–based films on copper surfaces was studied by electrochemical, infrared and electronic spectroscopy, and thermogravimetric methods. Complex polymer/metal ions were deposited onto a copper surface, as the result of the electrochemically generated reaction of copper cations with PVP and SCN^?, in sulfuric acid media. Spontaneous film growth on copper surfaces was generated and characterized as a Cu(II)/PVP/SCN^? complex. Infrared spectra and thermal gravimetric curves of the films generated at + 0.7 V were compared with the chemically synthesized complex, and show the same patterns. The oxidation process can be described as: Cu(0)→Cu(I) and Cu(I)→Cu(II), and the copper complex formed at more positive potentials was characterized as Cu(II)/PVP/SCN^?, with copper bonded to the oxygen atom of PVP and thiocyanate ligand N‐linked. This study focuses on the complex formation on a copper surface in acid media and its characterization through electrochemical and spontaneously generated reactions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2206–2214, 2009