Electrochemical Synthesis and Characterization of Conducting Copolymer: Poly(o-aniline-co-o-anisidine)

Copolymerization of o-anisidine and o-anisidine was achieved electrochemically in aqueous solution containing H₂SO₄ as supporting electrolyte. The copolymer compositions can be altered by varying the monomer feed ratios during electrosynthesis. The films were electropolymerized in solution containing monomers in various ratio (0.025–0.1 M) and 1 M sulphuric acid as electrolyte by applying sequential linear potential scan rate 50 mV/s between ? 0.2 to 1.0 V. versus Ag/AgCl electrode. The copolymers were characterized by cyclic voltammetric, conductivity measurement, UV-Visible spectroscopy, FT-IR spectroscopy, differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and CHN elemental analysis.     

Nanogravimetry study of the initial stages of anodic surface oxide film growth at Au in aqueous HClO4 and H2SO4 by means of EQCN

The dependence of the initial stages of anodic oxide film growth at Au on time or log time, τ_h, was investigated by means of nanogravimetry using a electrochemical quartz crystal nanobalance (EQCN) which provides a new dimension for such studies, complementary to voltammetry, chronoamperometry and ellipsometry. Films were formed potentiostatically in sulphuric or perchloric acids. The mass to charge ratio determined over the potential range corresponding to Au oxide formation is found to be ca. 6-7 g per mole of electrons, which is close to the value expected for formation of Au/O_ads on the electrode surface. The relations between charge and log τ_h, or mass and log τ_h, were evaluated. The charge for prior formation of O species, determined from reduction voltammetry, increases linearly with the log of the holding time. However, it is of special interest that the mass change in HClO₄ solutions does not increase linearly with the log of the holding time. This is interpreted in terms of co-adsorption of anions and displacement of water molecules. The results enable mechanisms of oxide film formation at Au to be critically appraised.     

Electrochemical supercapacitor material based on manganese oxide: preparation and characterization

A novel class of electrochemical supercapacitor electrode material has been electrochemically synthesized from a manganese halide complex in water-containing acetonitrile electrolyte at room temperature. This material has been physically and chemically characterized by scanning electron microscopy, X-ray photoelectron microscopy (XPS), FT-Raman microscopy and cyclic voltammetry. XPS and FT-Raman characterization suggest that this material is composed of manganese oxide with a chemical composition of Mn₃O₄ and containing a moderate amount of carbon. Cyclic voltammetric characterization indicates that this material has higher electronic conductivity than usually seen for manganese oxide and that it shows fast kinetics for the charge-discharge process in both aqueous and acetonitrile electrolytes. The material provides a large pseudocapacitance over a potential window of about 1 V in aqueous electrolyte and about 2 V in acetonitrile electrolyte. It is therefore a good candidate as a material for an electrochemical supercapacitor electrode.     

Stability of iodine on ruthenium during copper electrodeposition and its effects on the nucleation behavior of electrodeposited copper

Cyclic voltammetry, current-time-transient measurements, and X-ray photoelectron spectroscopy (XPS) have been used to study the nucleation behavior of electrochemically deposited Cu films on Ru substrates as a function of Ru pre-treatment. Pre-treatment consisted of cathodic polarization in either 1 M H₂SO₄ or in 1 M H₂SO₄ + 1 mM KI, followed by sample emersion and placement in a 1 M H₂SO₄ + 50 mM CuSO₄ plating bath. XPS measurements confirmed the presence of adsorbed I on the Ru surface following pre-treatment in the KI/H₂SO₄ solution. Cyclic voltammogram (CV) data for electrodes either as-received or pre-reduced in H₂SO₄ and then immersed in the plating solution exhibited a broad peak in the overpotential region consistent with oxide reduction followed by Cu deposition. No underpotential deposition (UPD) feature was observed for these electrodes. In contrast, the sample pre-reduced in I-containing electrolyte exhibited a narrow Cu deposition peak in the overpotential region and a UPD Cu feature centered at 80 mV vs. Ag/AgCl. Current-time-transient (CTT) measurements of Cu deposition on as-received electrodes or electrodes pre-reduced in I-free solution exhibited potential-independent kinetics that are not well described by either progressive or instantaneous nucleation models and which at long times indicate a combination of diffusion and kinetic control. In contrast, CTT measurements of deposition kinetics for samples reduced in I-containing electrolyte exhibited complex, potential-dependent behavior and that at long times indicates diffusion control. XPS results also indicated that the iodine adlayer on Ru reduced in I-containing electrolyte is stable upon polarization to at least −200 mV vs. Ag/AgCl. These data indicate that a protective I adlayer may be deposited on an air-exposed Ru electrode as the oxide surface is electrochemically reduced, and that this layer will inhibit reformation of an oxide during the Cu electroplating process. Therefore, electrochemical pre-treatment in I-containing electrolyte may be of practical utility under industrial conditions for Cu electroplating.     

Effect of the experimental setup in the behaviour of sol–gel coatings

Electrochemical behaviour of the sol–gel-coated AA2024-T3 samples was evaluated using electrochemical impedance spectroscopy (EIS) in a three-electrode arrangement cell using Na₂SO₄ 0.1 M solution as electrolyte. The effect of the reference electrode leakage was examined using as reference a low-leakage Ag/AgCl electrode and a platinum wire. The results show that very low-chloride concentrations in solution are able to induce heavy dissolution of intermetallic precipitates. That corrosion process masks information on the barrier properties of sol–gel coatings otherwise available through EIS measurements.     

Electroless deposition of Au around electrochemically evolved hydrogen bubbles

In this report, we use stripe-patterned substrates and TEM grids as working electrodes to demonstrate that electrochemically evolved hydrogen bubbles can serve as templates and reducing agents for electroless deposition of Au from a Na₃Au(SO₃)₂ electrolyte to form hollow particles. This new hollow nanoparticle formation mechanism, which is termed as bubble template synthesis, has the potential to become a general route to the fabrication of various metallic hollow nanoparticles. We have also found that the addition of Ni²⁺ ions in the electrolyte has an effect on the particle formation process. Electrodeposited metallic Ni enhances the hydrogen evolution and therefore the hollow particle formation. It also leads to an improved size distribution of the hollow particles.     

A SNIFTIRS study of the adsorption of ethylene carbonate at a Au(110) electrode from aqueous solutions

An in situ infrared spectroelectrochemical technique based upon the thin layer ATR optical configuration was used to examine the potential induced reorientation of ethylene carbonate (EC) at a Au(110) electrode. The behavior of EC was studied in aqueous solutions containing HClO₄, NaClO₄ and tetramethylammonium perchlorate electrolytes. Intense absorption bands due to the carbonyl and ring vibrational modes of EC were observed in the 1900-925 cm⁻¹ region. The carbonyl and ring vibrational modes are clearly influenced by the Au electrode and subsequently were frequency shifted; however, they did not show any potential dependent frequency behavior. Other bands did exhibit potential dependency. In addition, the magnitudes of some EC bands shift depending on the nature of the electrolyte cation. The spectral bands associated with the electrolyte provided evidence of ion migration in the diffuse double layer under the applied electric field.     

Hydrolysis of the 4-cyanopyridine on a Au(111) electrode studied by vibrational spectroscopies

The adsorption of 4-cyanopyridine on a Au(111) electrode is studied by cyclic voltammetry, FTIR and Sum Frequency Generation (SFG). This subject needs insight because potential-dependent irreversible reactions occur on the electrode. The present study is the continuation of a previous one which dealt with the potential-dependent orientation of 4-cyanopyridine (4-CP) on Au(111) electrodes. In this paper we are considering the hydrolysis of 4-CP into isonicotinamide occurring competitively to the reorientation of the 4-CP molecule. This results in the dissociation of the CN group into CONH₂. We show that in a perchlorate supporting test electrolyte, the adsorbed cyanopyridine adlayer is progressively hydrolyzed when the electrode potential is successively swept negatively then positively between −0.8 and +0.6 V (Ag | AgCl). The product and the mechanism of the hydrolysis reaction are identified thanks to the use of in situ FTIR. SFG spectroscopy is used in the 850–1100 cm⁻¹ range to address the question of the very slow kinetics of the reaction.     

An in situ spectroelectrochemical Raman investigation of Au electrodeposition and electrodissolution in KAu(CN)2 solution

Spectroelectrochemical behaviour of CN^– on a Au electrode in a KAu(CN)₂ bath at pH 6.3 was studied by in situ confocal Raman spectroscopy. Internal (CN stretch) and external (Au–CN) CN^–-related frequencies were investigated under potentiostatic control in a potential interval spanning cathodic and anodic ranges (–1800 to +1200 mV vs Ag/AgCl). Electrochemical behaviour was assessed by cyclic voltammetry. Stark-shifted Au–NC^– species are the dominating ones under cathodic polarization. Above the hydrogen evolution potential a Au–H stretch band can also be observed. At open circuit Au–CN^– species tend to prevail, while anodic conditions relate to the enhanced formation of Au(CN)₂ ^– and OCN^–.     

Visible light active Au:TiO2 nanocomposite photoanodes for water splitting: Sol–gel vs. sputtering

In this study, pure TiO₂ and Au:TiO₂ nanocomposite thin films are both synthesized using sol–gel and RF reactive co-sputtering methods. Physical and photoelectrochemical properties of the thin films deposited by each method are compared. The optical density spectra and scanning electron microscopy images of the Au:TiO₂ films reveal formation of gold nanoparticles in the all nanocomposite films synthesized by two methods. Moreover, the optical bandgap energy of the thin films decreases with addition of Au nanoparticles. X-ray photoelectron spectroscopy indicates that the presence of gold in metallic state and the formation of TiO₂ is stoichiometric. The photoelectrochemical properties of the TiO₂ and Au:TiO₂ thin films are characterized by using a compartment cell containing KOH solution as electrolyte. It is found that in the pure systems, TiO₂ sputtered films shows a higher photocurrent under visible light illumination while a reverse result is obtained for the Au:TiO₂ systems. In addition, photoirradiation on electrode/electrolyte (EE) and substrate/electrode (SE) interfaces for the sputtered samples reveals the EE illumination enhances the photoresponse of the layers as compared to SE case.     

Hydrodynamic voltammetric studies of the oxygen reduction at gold nanoparticles-electrodeposited gold electrodes

The electrocatalytic reduction of oxygen at Au nanoparticles-electrodeposited Au electrodes has been studied using rotating disk electrode (RDE) voltammetry in 0.5 M H₂SO₄. Upon analyzing and comparison of the limiting currents data obtained at various rotation speeds of this RDE with those obtained at the bulk Au electrode, an effective value of the number of electrons, n, involved in the electrochemical reduction of O₂ was estimated to be ca. 4 for the former electrode and ca. 3 for the bulk Au electrode at the same potential of −350 mV versus Ag/AgCl/KCl(sat.). This indicates the higher possibility of further reduction and decomposition of H₂O₂ at Au nanoparticles-electrodeposited Au electrode in this acidic medium. The reductive desorption of the self-assembled monolayer of cysteine, which was formed on the Au nanoparticles-electrodeposited Au electrode, was used to monitor the change of the specific activity of the bulk Au electrode upon the electrodeposition of the Au nanoparticles.     

Quasi in situ XPS study of electrochemical oxidation and reduction of highly oriented pyrolytic graphite in [1-ethyl-3-methylimidazolium][BF4] electrolytes

Highly oriented pyrolytic graphite (HOPG) electrodes were electrochemically oxidised and reduced in 1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄] electrolytes and studied by X-ray photoelectron spectroscopy (XPS). Sample preparation and transfer have been performed under inert nitrogen atmosphere in a preparation chamber directly attached to an ultra high vacuum system. After electrochemical treatment, both, the electrolyte and the electrode surface were investigated. While on the oxidised HOPG surface the core levels of the detected elements shift towards lower energies, on the reduced samples a shift towards higher binding energies is observed. These shifts refer to a Fermi level shift proving that graphite intercalation compounds were formed. Intercalation occurs together with co-intercalation of the ionic liquid. XPS analysis of the ionic liquids before and after electrochemical treatment reveals changes in electrolyte composition. The influence of impurities on electrochemical behaviour and XPS data is discussed.     

Electrochemistry of polyaniline: Study of the pH effect and electrochromism

Polyaniline was electrochemically synthesized from an aqueous medium with various acid electrolytes via potentiodynamic and potentiostatic techniques. The electrochemical synthesis of polyaniline was studied over various substrates, including Pt, Ti, Ni, and SnO₂ coated glass, and in various acid electrolytes. Cyclic voltammograms of electrochemically synthesized polyaniline were studied in HCl in a pH range of 1–4. Probable electrochemistry and chemical changes were deduced that occurred when polyaniline film was electrochemically oxidized and reduced between ?0.2 and 1.0 V versus a Ag/AgCl reference electrode in an acidic electrolyte at pH 1, and three corresponding oxidation and reduction peaks were described instead of two redox peaks (as observed by W. S. Huang, B. D. Humphrey, and A. G. MacDiarmid, J Chem Soc Faraday Trans 1 1986, 82, 2385). The electrochromic property was studied with changes in the chemical states of polyaniline during electrochemical oxidation and reduction. A new viscous electrolyte, aqueous AlCl₃ (pH 2), saturated with AgCl was used for the construction of an electrochromic display device. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 378–385, 2002     

Non-Faradaic catalysis: the case of CO oxidation over Ag-Pd alloy electrode in a solid oxide electrolyte cell

Studies of carbon monoxide oxidation on an Ag-25 at% Pd alloy electrode in a cell with a solid oxygen-conducting electrolyte - CO+O₂, Ag-Pd | 0.9 ZrO₂+0.1Y₂O₃ | Pt+PrO_2-x, air - were carried out. XRD, SEM and XPS techniques were used for characterisation of the Ag-Pd alloy electrode. The non-Faradaic effect of electrochemical oxygen pumping on the rate of carbon monoxide oxidation was demonstrated. The induced change in the reaction rate at cathodic polarization of the Ag-Pd alloy electrode was an order of magnitude higher than the rate of oxygen pumping from the reaction zone through the electrolyte. The observed phenomenon was qualitatively explained on the base of a chain reaction mechanism involving electrochemically generated oxygen species.     

Glucose oxidase electrodes of poly(o‐anisidine), poly(o‐toluidine), and their copolymer as biosensors: A comparative study

Thin films of poly(o‐anisidine) (POA), poly(o‐toluidine) (POT), and their copolymer poly(o‐anisidine‐co‐o‐toluidine) (POA‐co‐POT) were electropolymerized in solutions containing 0.1M monomer(s) and 1M H₂SO₄ as an electrolyte through the application of a sequential linear potential scanning rate of 50 mV/s between ?0.2 and 1.0 V versus an Ag/AgCl electrode on a platinum electrode. A simple technique was used to construct glucose sensors through the entrapment of glucose oxidase (GOD) in thin films of POA, POT, and their copolymer POA‐co‐POT, which were electrochemically deposited on a platinum plate in phosphate and acetate buffers. The maximum current response was observed for POA, POT, and POA‐co‐POT GOD electrodes at pH 5.5 and at a potential of 0.60 V (vs Ag/AgCl). The phosphate buffer yielded a fast response in comparison with the acetate buffer in amperometric measurements. The POT GOD electrode showed a fast response and was followed by POA‐co‐POT and POA GOD electrodes. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1877–1884, 2004     

Novel SEI formation of maleimide-based additives and its improvement of capability and cyclicability in lithium ion batteries

This investigation elucidates three maleimide (MI)-based aromatic molecules as additives in electrolyte that is used in lithium ion batteries. The 1.1 M LiPF₆ in ethylene carbonate (EC):propylene carbonate (PC):diethylene carbonate (DEC) (3:2:5 in volume) containing MI-based additives can prompt the formation of a solid electrolyte interface (SEI); and inhibit the entering into the irreversible state during lithium intercalation and co-intercalation. The reduction potential is 0.71-0.98 V versus Li/Li⁺ as determined by cyclic voltammetry (CV). The morphology and element analysis of the positive and negative electrode after the 100th charge-discharge cycle are examined by scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS). Moreover, the MI was used in lithium ion batteries and provided 4.9% capacity increase and 16.7% capacity retention increase when cycled at 1C/1C. The MI-based additive also ensures respectable cycle-ability of lithium ion batteries. MI is decomposed electrochemically to form a long winding narrow SEI strip on the graphite surface. This novel SEI strip not only prevents exfoliation on the graphite electrode but also stabilizes the electrolyte. The MI-based additive also ensures respectable cycle-ability of lithium ion batteries.     

Strategy for the syntheses of isolated fine silver nanoparticles and polypyrrole/silver nanocomposites on gold substrates

In this work, isolated fine silver nanoparticles and polypyrrole/silver nanocomposites with diameters of about 10 nm on gold substrates were first prepared by electrochemical methods. First, an Ag substrate was cycled in a deoxygenated aqueous solution containing 0.1 M HCl from −0.30 to +0.30 V versus Ag/AgCl at 5 mV/s with 30 scans. Subsequently the Ag working electrode was immediately replaced by an Au electrode and a cathodic overpotential of 0.2 V was applied under controlled sonication to synthesize Ag nanoparticles on the Au electrode. Then pyrrole monomers were encouragingly found to be polymerized on the deposited Ag nanoparticles. This polymerization is distinguishable from the known chemical or electrochemical one, due to the electrochemical activity of unreduced species of Ag_n⁺ clusters inside the nanoparticles. Also, this polymerization may be ascribed to the oxidizing agent of AuCl₄⁻, which is present on the Au electrode.     

In Situ Soft X‐ray Microscopy Study of Fe Interconnect Corrosion in Ionic Liquid‐Based Nano‐PEMFC Half‐Cells

This in situ soft X‐ray scanning microscopy electrochemical study of model proton exchange cathodic and anodic nano‐fuel cells is exploring the evolving structure and chemical composition of key cell components represented by Au and Fe electrodes in contact with Nafion‐ionic liquid composite electrolyte containing Pt black catalyst particles. Morphological and chemical changes of the electrodes as well as the chemical state and fate of the Fe species released into the electrolyte are monitored in short circuit and with applied cathodic or anodic polarization. The in situ X‐ray absorption images of the cathodic cell fed with 2.5 × 10^–5 mbar O₂ have revealed corrosion‐induced morphology changes in the Fe electrode, being more pronounced in the vicinity of Pt‐black particles, and deposition of the Fe species released into the electrolyte, onto the intact Au counter electrode upon cathodic polarization. The Fe electrodes of the anodic cell containing NaBH₄ in the electrolyte appear relatively more corrosion resistant. The Fe L₃ absorption spectra taken in different locations within the Fe electrode have shown lateral variations in the relative ratio between Fe²⁺ and Fe^3&4+ oxidation states, whereas the Fe species released into the RTIL electrolyte are only in the high Fe^3&4+ oxidation states.     

Evaluation of the corrosion protection performance of epoxy coatings containing Mg nanoparticle on carbon steel in 0.1 M NaCl solution by SECM and EIS techniques

The effect of corrosion protection performance of epoxy coatings containing magnesium (Mg) nanoparticles on carbon steel was analyzed using scanning electrochemical microscopy (SECM) and electrochemical impedance spectroscopy (EIS). Localized measurements such as oxygen consumption and iron dissolution were observed using SECM in 0.1 M NaCl in the epoxy-coated sample. Line profile and topographic image analysis were measured by applying ?0.70 and +0.60 V vs the Ag/AgCl/saturated KCl reference electrode as the tip potential for the cathodic and anodic reactions, respectively. The tip current at ?0.70 V for the epoxy-coated sample with Mg nanoparticles decreased rapidly, which is due to cathodic reduction in dissolved oxygen. The EIS measurements were conducted in 0.1 M NaCl after wet and dry cyclic corrosion test. The increase in the film resistance (R _f) and charge transfer resistance (R _ct) values was confirmed by the addition of Mg nanoparticles in the epoxy coating. Scanning electron microscope/energy-dispersive X-ray spectroscope analysis showed that Mg was enriched in corrosion products at a scratched area of the coated steel after corrosion testing. Focused ion beam–transmission electron microscope analysis confirmed the presence of the nanoscale oxide layer of Mg in the rust of the steel, which had a beneficial effect on the corrosion resistance of coated steel by forming protective corrosion products in the wet/dry cyclic test.     

XPS and DRS of Au/TiO2 catalysts: effect of pretreatment

TiO₂ impregnated with AuCl₃ was subjected to different pretreatments and then characterized by XPS and DRS. After drying at 298 K under vacuum, the catalyst contains highly dispersed, nonmetallic Au species; whereas drying at 393 K in an oven caused the Au to be partially reduced and agglomerate. Further treatments of the oven-dried sample at higher temperatures resulted in the disappearance of Au signals in XPS except the one after a HTR/C/LTR (high-temperature reduction/calcination/low-temperature reduction) sequence. The high-temperature reduction at 773 K shifted the plasmon resonance peak in DRS to higher wavelength, and the following C and LTR treatment did not change the peak position. This peak shifting is interpreted as a change in the electronic status of the Au. This revised version was published online in July 2006 with corrections to the Cover Date.