On the changing electrochemical behaviour of boron-doped diamond surfaces with time after cathodic pre-treatments

The electrochemical response of the Fe(CN)₆^4−/3− redox couple on boron-doped diamond (BDD) electrodes immediately after a cathodic pre-treatment and as a function of time exposed to atmospheric conditions is reported here. After this pre-treatment the electrode exhibits a changing electrochemical behaviour, i.e., a loss of the reversibility for the Fe(CN)₆^4−/3− redox couple as a function of time. Raman spectra showed that neither important bulk structural differences nor significant changes in the sp²/sp³ content are introduced into the BDD film by the cathodic pre-treatment indicating that H-terminated sites play an important role in the electrochemical response of the electrodes. Thus, the changing behaviour reflected by a progressive decrease of the electron transfer rate with time must be associated to a loss of superficial hydrogen due to oxidation by oxygen from the air, as confirmed by X-ray photoelectron spectroscopy (XPS) analysis. Moreover, it was also found that this changing electrochemical behaviour is inversely proportional to the doping level, suggesting that the boron content has a stabilizing effect on the H-terminated surface. These results point out the necessity of doing the cathodic pre-treatment just before the electrochemical experiments are carried out in order to ensure reliable and reproducible results.     

Electrochemical behavior of high-pressure synthetic boron doped diamond powder electrodes

Boron doped diamond (BDD) was synthesized under high pressure and high temperature using B-doped graphite intercalation compositions (GICs) as carbon sources. The electrochemical characteristics of high-pressure synthetic BDD powder electrodes were investigated by measuring the cyclic voltammetry curves and AC impedance spectrum. For the [Fe(CN)₆]^3−/4− redox couple, the electrode reaction process is reversible or quasi-reversible at the scan rates of 0.01-1.0 V/s. At the low scan rate the linear relation between peak current and square root of scan rate indicates that the electrode process was a diffusion-controlled mass transport process. The electrochemical behavior is similar to a planar electrode. With the increasing of the scan rate the electrode process is controlled by the mass transport plus kinetic process. AC impedance spectra exhibit the porous structure characteristic of BDD powder electrode.     

Direct electrochemistry of blue copper proteins at boron-doped diamond electrodes

Boron-doped diamond (BDD) is a promising electrode material for use in the spectro-electrochemical study of redox proteins and, in this investigation, cyclic voltammetry was used to obtain quasi-reversible electrochemical responses from two blue copper proteins, parsley plastocyanin and azurin from Pseudomonas aeruginosa. No voltammetry was observed at the virgin electrodes, but signals were observed if the electrodes were anodised, or abraded with alumina, prior to use. Plastocyanin, which has a considerable overall negative charge and a surface acidic patch which is important in forming a productive electron transfer complex with its redox partners, gave a faradaic signal at pre-treated BDD only in the presence of neomycin, a positively charged polyamine. The voltammetry of azurin, which has a small overall charge and no surface acidic patch, was obtained identically in the presence and absence of neomycin. Investigations were also carried out into the voltammetry of two site-directed mutants of azurin, M64E azurin and M44K azurin, each of which introduce a charge into the protein's surface hydrophobic patch. The oxidizing and cleaning effects of the BDD electrode pre-treatments were studied electrochemically using two inorganic probe ions, Fe(CN)₆³⁻ and Ru(NH₃)₆³⁺, and by X-ray photoelectron spectroscopy (XPS). All of the electrochemical results are discussed in relation to the electrostatic and hydrophobic contributions to the protein/diamond electrochemical interaction.     

Effects of controlled anodic treatments on electrochemical behaviour of boron doped diamond

The electrochemical behaviour of as-deposited and anodically treated samples is studied by cyclic voltammetry in the presence of redox couple (Ce⁴⁺/Ce³⁺). Two kinds of anodic pre-treatments are performed, playing on the current density and on the duration of the galvanostatic step. Mott–Schottky plots are reported, and related to the energy band diagram evolution of the electrodes after anodic processes. The electrochemical behaviour modification is correlated to the surface wettability evolution and flat band potential shift. For mild anodic pre-treatments, a conservation of the superficial conductive layer (SCL), known to exist on hydrogen-terminated boron doped diamond (BDD), is proposed, while for strong treatments, the SCL disappears.     

The impedance of fast charge transfer reactions on boron doped diamond electrodes

Reversible charge transfer on boron doped diamond (BDD) electrodes was studied using cyclic voltammetry and electrochemical impedance spectroscopy. Polycrystalline diamond films of 5 μm thickness with 200 and 3000 ppm boron content were prepared by chemical vapour deposition on niobium substrate. The samples were mounted in a Teflon holder and used as rotating disk electrodes (RDE) with rotation frequencies between 0 and 4000 rpm. The electrochemical measurements were carried out in aqueous electrolyte solutions of 0.5 M Na₂SO₄ + 5 mM K₃[Fe(CN)₆]/K₄[Fe(CN)₆] and 0.1 M KCl + 5 mM [Ru(NH₃)₆]Cl₂/[Ru(NH₃)₆]Cl₃. The electrochemical redox behaviour of the BDD electrodes was found to differ significantly from that of an active Pt electrode. The deviations are indicated by a large peak potential difference and a shift of the peak potentials in cyclic voltammograms with increasing sweep rate. At rotating electrodes lower limiting current densities are found and the impedance diagrams exhibit an additional capacitive impedance element at high frequencies. The results are described quantitatively by an impedance model which is based on partial blocking of the diamond surface.     

Effect of anodic and cathodic treatments on the charge transfer of boron doped diamond electrodes

This paper is concerned with the study of the influence of electrochemical pre-treatments on the behavior of highly boron doped diamond electrodes. Anodic and cathodic preconditioning, performed during 10 s either with 10^− 4 A/cm^− 2 (10^− 3 C cm^− 2) or 10^− 1 A/cm^− 2 (1 C cm^− 2), has been studied. Cyclic voltammetry at as-deposited, anodically and cathodically treated electrodes, in presence of 2 redox couples serving as electrochemical probes is analyzed in the light of the surface characterization given by XPS chemical analysis. Ce^4+/3+ redox couple in 0.5 M H₂SO₄ medium and Fe(CN)₆^3−/4− redox couple in 0.1 M KOH medium, have been studied before and after the different treatments. The results of Mott–Schottky plots and current voltage curves are reported and show that the electrochemical response of BDD electrodes is very dependent on the current density involved in the electrochemical preconditioning. The modification of surface bond termination – either hydrogen or oxygen – studied by XPS analyses is also strongly dependent on electrochemical pre-treatment. In particular, it is evidenced that the most important conversion of surface functionalities from hydrogen to oxygen is obtained when the anodic treatment is performed with the smallest current density. Finally, a correlation between surface terminations and charge transfer is evidenced.     

Plasma etching treatment for surface modification of boron-doped diamond electrodes

Boron-doped diamond (BDD) thin film surfaces were modified by brief plasma treatment using various source gases such as Cl₂, CF₄, Ar and CH₄, and the electrochemical properties of the surfaces were subsequently investigated. From X-ray photoelectron spectroscopy analysis, Cl and F atoms were detected on the BDD surfaces after 3 min of Cl₂ and CF₄ plasma treatments, respectively. From the results of cyclic voltammetry and electrochemical AC impedance measurements, the electron-transfer rate for Fe(CN)₆^3−/4− and Fe^2+/3+ at the BDD electrodes was found to decrease after Cl₂ and CF₄ plasma treatments. However, the electron-transfer rate for Ru(NH₃)₆^2+/3+ showed almost no change after these treatments. This may have been related to the specific interactions of surface halogen (C-Cl and C-F) moieties with the redox species because no electrical passivation was observed after the treatments. In addition, Raman spectroscopy showed that CH₄ plasma treatment of diamond surfaces formed an insulating diamond-like carbon thin layer on the surfaces. Thus, by an appropriate choice of plasma source, short-duration plasma treatments can be an effective way to functionalize diamond surfaces in various ways while maintaining a wide potential window and a low background current.     

Electrochemical behavior of carbon electrodes in organic liquid electrolytes containing tetrafluoroborate and hexafluorophosphate anionic species in different non-aqueous solvent systems

Electrochemical behavior of tetrabutylammonium salts containing tetrafluoroborate (BF₄⁻) and hexafluorophosphate (PF₆⁻) anionic species in different non-aqueous solvents had been investigated on glassy carbon (GC), boron-doped diamond (BDD) and Pt electrodes. Though both BF₄⁻ and PF₆⁻ ionic species are considered to be inert, they are found to undergo electrochemical oxidation only on GC electrode rather than BDD and Pt as found out from their anodic peaks in linear sweep and cyclic voltammograms (LSV and CV). The voltammetric peak is influenced by the sweep rate as well as by the concentration of the ionic species and the electron transfer process appears to be diffusion controlled one. The formation of an inhibitory C-F film on the electrode surface during anodic polarization either by potentiostatic or potentiodynamic techniques was clearly established by X-ray photoelectron spectroscopy (XPS) analysis and the charge transfer resistance (θ) is higher under latter conditions than the former. The inhibitory effect of this surface film towards the electron transfer reaction of Fe(CN)₆]⁴⁻/[Fe(CN)₆]³⁻ redox couple using impedance technique reveals that among the high permittivity non-aqueous solvents investigated in this work, CH₃CN shows maximum θ value and produces C-F film of optimum thickness than the others. A direct correlation was also found out from the plot of θ versus peak potential E_p and peak current density (i_p) obtained from LSV. The mechanism of film formation on GC electrode and the absence of such phenomenon on BDD were explained from the product analysis using ¹⁹F nuclear magnetic resonance (NMR) spectra resulting from the constant current electrolysis of BF₄⁻ and PF₆⁻ ionic species on both electrodes in CH₃CN medium.     

Characterization of boron-doped diamond electrodes by electrochemical impedance spectroscopy

Charge transfer on boron doped diamond (BDD) electrodes was studied by cyclic voltammetry and electrochemical impedance spectroscopy. The diamond films of 5 μm thickness and boron content between 200 ppm and 3000 ppm were prepared by the hot filament CVD technique on niobium substrate and mounted in a Teflon holder as rotating disk electrodes. The electrochemical measurements were carried out in aqueous electrolyte solutions of 0.5 M Na₂ SO ₄ + 5 mM K₃[Fe(CN)₆]/K₄[Fe(CN)₆]. Significant deviation in the redox behaviour of BDD and active Pt electrodes was indicated by a shift of the peak potentials in the cyclic voltammograms with increasing sweep rate and lower limiting diffusion current densities under rotating disk conditions. In the impedance spectra an additional capacitive element appeared at high frequencies. The potential and rotation dependence of the impedance spectra can be described quantitatively in terms of a model based on diffusion controlled charge transfer on partially blocked electrode surfaces. Direct evidence for the non-homogeneous current distribution on the diamond surface was obtained by SECM measurements.     

Tunable electrochemical properties of liquid phase deposited TiO2 films

Titanium dioxide (TiO₂) films on glassy carbon (GC) electrode surface were prepared by the liquid phase deposition (LPD) process for different deposition times. The morphological structure, interfacial property and electrocatalytic activity of as-prepared LPD TiO₂ films on GC surface were studied by field-emission scanning electron microscopy (FE-SEM), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The FE-SEM observation showed that the deposition time controlled the morphology of film on GC surface. With increasing deposition time, TiO₂ formed nanoparticles at the initial 5-h stage and compact thick films after 20 h. Due to the semiconducting properties of TiO₂, the LPD films inhibited the electron transfer process of [Fe(CN)₆]³⁻/[Fe(CN)₆]⁴⁻ on GC by increasing the redox reaction peak potential separation of CV curve and electron transfer resistance of EIS. The inhibition was increased with TiO₂ film thickness. Nevertheless, the onset reduction potential of maleic acid decreased with increasing LPD TiO₂ film thickness while the cathodic and anodic currents increased, demonstrating the useful electrocatalytic activity of LPD TiO₂ films.     

On the activation and physical degradation of boron-doped diamond surfaces brought on by cathodic pretreatments

The electrochemical activation and physical degradation of boron-doped diamond (BDD) electrodes with different boron doping levels after repeated cathodic pretreatments are reported. Galvanostatic cathodic pretreatment passing up to −14000 C cm⁻² in steps of −600 C cm⁻² using −1 A cm⁻² caused significant physical degradation of the BDD surface, with film detachment in some areas. Because of this degradation, a great increase in the electrochemically active area was observed in Tafel plots for the hydrogen evolution reaction (HER) in acid media. The minimum cathodic pretreatment needed for the electrochemical activation of the BDD electrodes without producing any observable physical degradation on the BDD surfaces was determined using electrochemical impedance spectroscopy (EIS) measurements and cyclic voltammetry: −9 C cm⁻², passed at −1 A cm⁻². This optimized cathodic pretreatment can be safely used when electrochemical experiments are carried out on BDD electrodes with doping levels in the range between 800 and 8000 ppm.     

n-Type nitrogenated nanocrystalline diamond thin-film electrodes: The effect of the nitrogenation on electrochemical properties

Nitrogenated nanocrystalline diamond thin-film electrodes with controlled conductivity are grown from microwave- or arc-plasma in CH₄-Ar-H₂-N₂ gas mixtures. Their electrochemical behavior is studied using cyclic voltammetry and electrochemical impedance spectroscopy techniques. It is concluded from Mott-Schottky plots that the studied material has n-type conductance; the donor concentration is estimated. The character of electrode behavior is controlled by the degree of nitrogenation of the material. In particular, with the increasing of nitrogen concentration in the feeding gas (0-25%) supplied to plasma-chemical reactor, the potential window in the supporting electrolyte (2.5 M H₂SO₄) becomes somewhat narrower, the reversibility of electrochemical reactions in the [Fe(CN)₆]^3−/4− redox couple becomes more pronounced. Kinetic parameters of redox reactions in this couple are determined. By and large, with the increasing of the nitrogenation the electrochemical behavior of “poor conductor” gives way to that of metal-like conductor.     

Influence of surface inhomogeneities of boron doped CVD-diamond electrodes on reversible charge transfer reactions

The electrochemical behaviour of reversible charge transfer reactions on boron doped diamond (BDD) was studied by cyclic voltammetry and electrochemical impedance spectroscopy using rotating disc electrodes under defined convection. Diamond films of 5 m thickness with doping levels of 200, 3000 and 6000 ppm were prepared by hot filament chemical vapour deposition on niobium substrate. The electrochemical measurements were carried out on BDD electrodes in deaerated 0.5 M Na₂SO₄ + 5 mM K₃[Fe(CN)₆]/K₄[Fe(CN)₆] solution at rotation frequencies 0 < f _rot < 4000 rpm. Comparative measurements were carried out on an active Pt electrode. The BDD electrodes exhibit distinct irreversibilities indicated by a larger peak potential difference in the cyclic voltammograms, lower diffusion limiting current densities and an additional impedance element at high frequencies. Mechanical polishing with carbon fleece and SiC paper strongly affects the irreversible behaviour of the BDD electrodes. The experimental results are explained by a partial blocking of the diamond surface with reversible charge transfer at active sites. The impedance spectra are analysed quantitatively using a transport impedance model for reversible reactions on partially blocked electrode surfaces.     

Synthesis and properties of polymer brushes bearing ionic liquid moieties

Poly(1-ethyl 3-(2-methacryloyloxy ethyl) imidazolium chloride) (PEMEIm-Cl) brushes were grafted onto Au surface via surface initiated atom transfer radical polymerization (ATRP). The swelling/collapsed behavior of the brushes was characterized by AFM in different electrolyte solutions. These 15 nm ultrathin polyelectrolyte brushes can be used to modulate the interfacial resistance via conformational changes triggered by external electrolytes and solvent. The interfacial resistance was characterized using electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) using [Fe(CN)₆]^3−/4− as the redox probe. The effects of electrolytes, the concentration and type of electrolytes and temperature are investigated in more detail.     

Electrochemical behavior of amorphous metal-silicon-carbon nanocomposites based on titanium or tungsten nanophase

Electrode behavior of nanocomposite films containing titanium- or tungsten-based conducting nanophase embedded in dielectric silicon-carbon matrix, deposited onto glassceramics substrate, is studied by cyclic voltammetry and electrochemical impedance spectroscopy. As the films’ resistivity decreases, their electrochemical behavior gradually changes from that of “poor conductor” to the nearly metal-like behavior. In particular, the differential capacitance increases, the charge transfer in a model redox system [Fe(CN)₆]^3−/4− accelerates, which may be explained by the increasing number of metal-containing clusters at the film/electrolyte solution interface.     

Electrochemical preconditioning of moderately boron doped diamond electrodes: Effect of annealing

This paper is concerned with the study of electrochemical preconditioning on moderately boron doped diamond electrodes. Samples were submitted to an isothermal annealing at 1100 °C in order to outgas the hydrogen introduced into the layer during the deposition process. Consequences of anodic and cathodic galvanostatic steps (1 C cm^− 2), in H₂SO₄ 0.5 M, have been studied on both as-deposited samples and annealed ones, by capacitance measurements, cyclic voltammetry in presence of Ce^4+/3+ redox system and XPS measurements. The results of Mott–Schottky plots and current voltage curves show that the electrochemical responses of BDD electrodes are strongly influence by annealing. After preconditioning, an enhancement of charge transfer is observed for as-deposited samples, while a more and more passivated behavior is recorded for annealed electrodes. On as-deposited samples a “new” superficial conductive layer linked to the creation of surface defects high above the valence band, is suggested after a specific electrochemical treatment which is not possible on annealed ones.     

The effect of CVD-diamond film thickness on the electrochemical properties of synthetic diamond thin-film electrodes

The electrochemical behavior of polycrystalline diamond films of different thickness (0.5–7 μm), grown by hot-filament CVD method, was studied by electrochemical impedance spectroscopy and cyclic voltammetry. The differential capacitance, background current, and potential window were measured in supporting electrolyte solution; the electrochemical kinetics, in [Fe(CN)₆]^3−/4− model redox system. With the increasing of the films thickness, the crystallite size increased; both the differential capacitance and background current in the indifferent electrolyte, as well as the transfer coefficients in the redox system, decreased; thus, the diamond electrode becomes as if less reversible. The effect of the films’ thickness is reduced to that of nondiamond (amorphous) carbon contribution from intercrystalline boundaries on the electrochemical behavior of the polycrystalline diamond electrodes.     

The effect of surface treatment on oxidation of oxalic acid at nanocrystalline diamond films

The surface investigation of undoped and boron doped nanocrystalline diamond (NCD/BDND) films associated to their electrochemical behavior of oxalic acid after four pre-treatments was studied. The films were produced using Hot Filament CVD technique on Si substrate with a gas mixture of CH₄/H₂/Ar. Surface pre-treatments were carried out to analyze the surface chemical changes induced by hydrogen and oxygen plasma and as well as cathodic and anodic treatments performed in 0.1 mol L^? 1 HClO₄. The films wetting analyzed by contact angle presented a strong dependence of their surface before and after each treatment was also confirmed by the electrochemical response from cyclic voltammograms. Independent of the surface pre-treatments, all the electrodes exhibited response for oxalic acid oxidation, but the electrode submitted to hydrogen plasma presented the lowest starting oxidation potential and the highest current density. Nonetheless, the BDND electrode presented higher oxidation current than that for NCD electrodes, after all pre-treatments studied. The use of square wave voltammetry with BDND electrode treated by hydrogen plasma for the analytical determination of oxalic acid is described. The detection limits of 0.75 μmol was obtained from the linear relationship between the peak currents of voltammograms as a function of the oxalic acid concentrations.     

Study on charge transfer reactions at multilayers of polyoxometalates clusters and poly(allylamine hydrochloride) (Grotthuss-018)

Multilayers of anionic phosphotungstic acid (PTA) clusters and positively charged protonated poly(allylamine hydrochloride) (PAH) were assembled by layer-by-layer self-assembled method on Au electrode modified by 3-mercaptopropionic acid (3-MPA). The effect of the charge of the surface of the multilayer assembly on the kinetics of the charge transfer reaction was studied by using the redox probes [Fe(CN)₆]^3−/4− and [Ru(NH₃)₆]^2+/3+. The cyclic voltammetry experiments showed that the peak currents and peak-to-peak potential differences changed after assembling different layers on the electrode surface indicating that the charge of the surface has a significant effect on the kinetics of the studied charge transfer reactions. These reactions were studied in more detail by electrochemical impedance spectroscopy. When [Fe(CN)₆]^3−/4− was used as the redox label, multilayers that terminated with negatively charged PTA showed a high charge transfer resistance but multilayers that terminated with positively charged PAH showed lower charge transfer resistance. With [Ru(NH₃)₆]^2+/3+ as the redox label, the charge transfer resistance at multilayers that terminated with positively charged PAH was much higher than at the multilayer terminated by the negatively charged PTA. The charge transfer resistances also increased with the addition of number of layers indicating that the entire thickness of the multilayer assembly has also an effect on the kinetics of the studied charge transfer reactions and not only the electrostatic attraction or repulsion between the surface and the redox probes. The ohmic resistance of the multilayer assembly increased non-linearly with the number of layers. Assembling a layer of PAH increased the resistance more than assembling a layer of PTA.     

Electrocatalytic oxidation of ascorbic acid by [Fe(CN)6] redox couple electrostatically trapped in cationic N,N-dimethylaniline polymer film electropolymerized on diamond electrode

Multinegatively charged metal complex, hexacyanoferrate ([Fe(CN)₆]⁴⁻), was electrostatically trapped in the cationic polymer film of N,N-dimethylaniline (PDMA) which was electrochemically deposited on the boron-doped diamond (BDD) electrode by controlled-potential electro-oxidation of the monomer. This ferrocyanide-trapped PDMA film was used to catalyze the oxidation of ascorbic acid (AA). Increase in the oxidation current response with a negative shift of the anodic peak potential was observed at the cationic PDMA film-coated BDD (PDMA|BDD) electrode, compared with that at the bare BDD electrode. A more drastic enhancement in the oxidation peak current as well as more negative shift of oxidation potential was found at the ferrocyanide-trapped PDMA film-coated BDD ([Fe(CN)₆]^3−/4−|PDMA|BDD) electrode. This [Fe(CN)₆]^3−/4−|PDMA|BDD electrode can be used as an amperometric sensor of AA. Ferrocyanide, electrostatically trapped in the polymer film shows more electrocatalytic activity than that coordinatively attached to the polymer film or dissolved in the solution phase. The electrocatalytic current depends on the surface coverage of ferricyanide, Γ_Fe, within the polymer film. Diffusion coefficient (D) of AA in the solution was estimated by rotating disk electrode voltammetry: D = (5.8 ± 0.3) × 10⁻⁶ cm² s⁻¹. The second-order rate constant for the catalytic oxidation of AA by ferricyanide was also estimated to be 9.0 × 10⁴ M⁻¹ s⁻¹. In the hydrodynamic amperometry using the [Fe(CN)₆]^3−/4−|PDMA|BDD electrode, a successive addition of 1 μM AA caused the successive increase in current response with equal amplitude and the sensitivity was calculated as 0.233 μA cm⁻² μM⁻¹.