Electrochemical characterization of nanoporous honeycomb diamond electrodes in non-aqueous electrolytes

Oxygen plasma-etched nano-honeycomb diamond thin film electrodes were examined for electrochemical capacitor applications in non-aqueous electrolytes. As-deposited and nano-honeycomb diamond electrodes in 0.5 M TEABF₄/PC both exhibited a wide potential window (approx. 7.3 V), similar to that of glassy carbon electrodes. For as-deposited diamond, the impedance behavior was found to be similar for non-aqueous and aqueous electrolytes, and the double-layer capacitance was found to be 21.8 μF cm⁻², almost the same as that obtained in aqueous electrolytes. For the honeycomb diamond electrodes, however, the impedance behavior observed in non-aqueous electrolytes was significantly different from that in aqueous electrolyte and indicated that the ac signal cannot penetrate to the bottom of the honeycomb pores in the non-aqueous electrolytes due to low conductivity, and that not all the surface may contribute to the double-layer capacitance. This result was verified by mathematical simulation.     

Interaction between myoglobin and hyaluronic acid in layer-by-layer structures—An electrochemical study

The layer-by-layer (LBL) self-assembled film construction of the biocompatible polymer hyaluronic acid (HA) and single heme redox protein, myoglobin (Mb) is described. The films were built upon gold electrode substrates, both gold quartz crystal electrodes and bulk gold (Au(bulk)) electrodes, and formation of the LBL films was gravimetrically monitored by an electrochemical quartz crystal microbalance. The electrochemical properties of the hyaluronic acid/myoglobin films ({HA/Mb}_n) were investigated after each deposition step using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The CV response presented an oxidation peak at +0.3 V vs. SCE, not characteristic of the redox protein myoglobin, and, the peak current decreased slightly with each additional bilayer. CV at Au(bulk) electrodes in pH 5.0 acetate buffer solution, containing Mb, presented the same oxidation peak as observed at {HA/Mb}_n modified electrodes, confirming the presence of the same electroactive species. The Mb oxidation peak current depends linearly on scan rate, characteristic of adsorbed thin-layer electrochemical systems, attributed to free adsorbed heme. Impedance spectra, recorded after deposition of each bilayer, were in agreement with the cyclic voltammetry observations.     

Electrochemical characteristics of boron-doped,undoped and nitrogen-doped diamond films

Boron-doped, undoped and nitrogen-doped diamond films were synthesized by microwave plasma assisted chemical vapor deposition (MP-CVD). Raman spectroscopy, XPS, EPMA and UV–Vis were used to characterize the properties of the synthesized films. Electrochemical characteristics for several redox systems on the three kinds of diamond films were examined. For Li⁺/Li (E⁰=−3.05 V) and H⁺/H₂ (E⁰=0.00 V) redox couples, the marked differences in cyclic voltammetric (CV) behaviors were observed on the nitrogen-doped diamond films, whereas for Fe(CN)³⁻/⁴⁻ (E⁰=0.36), Au/AuCl₄⁻ (E⁰=1.00) and O₂/H₂O (E⁰=1.23 V) couples, the CV behaviors on the nitrogen-doped films were similar to those on the boron-doped or undoped diamond films. The significant differences of CV behaviors could be explained by hypothesizing that the electron transfers of the redox species in the solution on diamond electrodes happened at the top of valence band together with the surface doping model suggested by F. Maier and colleagues [F. Maier, M. Riedel, B. Mantel, J. Ristein, L. Ley, Phys. Rev. Lett. 85 (2000) 3472].     

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.     

Electropolymerization of a poly(3,4-ethylenedioxythiophene) and functionalized, multi-walled, carbon nanotubes counter electrode for dye-sensitized solar cells and characterization of its performance

Composite films of poly(3,4-ethylenedioxythiophene) and functionalized, multi-walled, carbon nanotubes (PEDOT–MWCNT) were fabricated by a simple oxidative electropolymerization method. These films were formed on fluorine-doped, tin oxide, glass substrates as counter electrodes (CEs) of platinum-free, dye-sensitized solar cells (DSSCs). The surface morphology, formation mechanism and electrochemical nature of PEDOT–MWCNT films were investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), cyclic voltammetry (CV) and alternating current (AC) impedance spectroscopy. The SEM and AFM images showed that PEDOT–MWCNT films were more porous than PEDOT films. CV and AC impedance spectroscopy revealed that the PEDOT–MWCNT electrode had higher electrocatalytic activity for the I₃⁻/I⁻ redox reaction and a smaller charge transfer resistance than the PEDOT electrodes. The energy conversion efficiency of the DSSC with a PEDOT–MWCNT CE was 13.0% higher than with a PEDOT CE using the same conditions with a ruthenium sensitizer.     

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.     

Electrochemical reactivity at graphitic micro-domains on polycrystalline boron doped diamond thin-films electrodes

This paper deals with the electrochemical reactivity of boron doped diamond (BDD) electrodes. A comparative study has been carried out to show the influence of the presence of graphitic micro-domains upon the surface of these films. Those graphitic domains are sometimes present on as-grown boron doped diamond electrodes. The effect of doping a pure Csp³ diamond electrode is established by highly oriented pyrolytic graphite (HOPG) abrasion onto the diamond surface. In order to establish the effect of doping on a pure Csp³ diamond electrode, the amount of graphitic domains was increased by means of HOPG crystals grafted onto the BDD surface. Indeed that method allows the enrichment of the Csp² contribution of the electrode.The presence of graphitic domains can be correlatively associated with the presence of kinetically active redox sites. The electrochemical reactivity of boron doped diamond electrodes shows a distribution of kinetic constants on the whole surface of the electrode corresponding to different active sites. In this paper, we have studied by cyclic voltammetry and electrochemical impedance spectroscopy the kinetics parameters of the ferri/ferrocyanide redox couple in KCl electrolyte. A method is proposed to diagnose the presence of graphitic domains on diamond electrodes, and an electrochemical “pulse cleaning” procedure is proposed to remove them.     

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.     

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.     

Layer‐by‐layer self‐assembled multilayer films of single‐walled carbon nanotubes and tin disulfide nanoparticles with chitosan for the fabrication of biosensors

In this study, multilayer films containing chitosan, tin disulfide (SnS₂) nanoparticles, and single‐walled carbon nanotubes were prepared on glassy carbon electrodes with the use of a layer‐by‐layer assembly technique. The resulting films were characterized with cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), scanning electron microscopy, and ultraviolet–visible absorption spectroscopy. The results of CV and EIS indicates that the peak currents and charge‐transfer resistance all had linear responses to the number of assembled layers. The multilayer‐film‐modified electrode showed excellent electrocatalytic properties for some species, such as dopamine hydrochloride (DA), ascorbic acid (AA), and uric acid (UA). The well‐separated voltammetric signals of DA, UA, and AA could be obtained on the assembled multilayer‐film‐modified electrode, and the peak‐to‐peak potential separations were 171, 136, and 307 mV for DA–UA, DA–AA, and UA–AA on CV, respectively. These facts showed that the multilayer‐film‐modified electrode could be used as a new sensor for the simultaneous detection of DA and UA in the presence of AA in a real sample. In addition, the multilayer films were stable, selective, and reproducible. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Electrochemical evaluation of avidin-biotin interaction on self-assembled gold electrodes

The avidin-biotin interaction on 11-mercaptoundecanoic acid self-assembled gold electrodes was investigated by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The interfacial properties of the modified electrodes were evaluated in the presence of the Fe(CN)₆^3−/4− couple redox as a probe. A simple equivalent circuit model with a constant phase element was used to interpret the obtained impedance spectra. The results of cyclic voltammetry showed that the voltammetric behavior of the redox probe was influenced by the electrode surface modification. It is evident that the accumulation of treated substances and the binding of biotin to avidin on the electrode surface resulted in the increasing electron-transfer resistance and the decreasing capacitance. The changes in the electron-transfer resistance on the avidin-modified electrodes were more sensitive than that in the capacitance while detecting biotin over the 2-10 μg/mL concentration. The detection amount can be as low as 20 ng/mL based on the electron-transfer resistance that presented the change of 4.3 kΩ without the use of labels. The development of a rapid, facile, and sensitive method for the quantitation of nanogram quantities of biomolecules utilizing EIS may be achieved.     

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.     

Comparative electrochemical study of myoglobin loaded in different polyelectrolyte layer-by-layer films assembled by spin-coating

Different types of {polycation/polyanion}_n layer-by-layer (LBL) films were assembled on the surface of pyrolytic graphite (PG) electrodes by spin-coating, and then immersed in myoglobin (Mb) solutions at pH 5.0 to load Mb into the films. Compared with the traditional solution-dipping method in LBL assembly, the spin-coating approach was much more time saving but did not show substantial difference in Mb loading. The Mb-loaded LBL films demonstrated nearly reversible cyclic voltammetric (CV) responses for Mb Fe(III)/Fe(II) redox couple, and the surface concentration of electroactive Mb in the films (Γ*, mol cm⁻²) could be used to compare the loading behaviors of Mb in different films. Among the six polyelectrolyte LBL films, {HECE/PSS}_n films assembled with quaternized hydroxyethyl cellulose ethoxylate (HECE) and poly(styrenesulfonate) (PSS) demonstrated the largest Γ* value for loaded Mb and the best performance in electrocatalysis toward hydrogen peroxide. CV, UV–vis spectroscopy and electrochemical impedance spectroscopy (EIS) were used to characterize the films and explore the reason why {HECE/PSS}_n-Mb films showed better electrochemical response than the other Mb-loaded LBL films. The better understanding of the interactions involved in Mb loading may help us to find novel and more suitable protein-loaded LBL film systems in the future.     

Spectroelectrochemistry of two-layered composites of polyaniline and poly(o-aminophenol)

Electropolymerization of aniline on poly(o-aminophenol)(POAP)-coated gold and indium-doped tin oxide (ITO)-coated glass electrodes yields polyaniline(PANI)/POAP two-layer composite films, exhibiting reversible redox functions in aqueous acidic solution. The PANI deposition on the POAP-coated electrodes was monitored by cyclic voltammetry (CV) and in situ UV-vis spectroelectrochemistry. CV results show that PANI/POAP composite films exhibit better stability as compared to PANI films during potential cycling in aqueous acidic solutions. Characteristic UV-vis and Raman features of the composite films have been identified and their dependencies on the electrode potential are discussed. They were significantly different from the corresponding spectral characteristics of PANI and POAP films alone.     

Deposition and characterization of nanocrystalline diamond films on Co-cemented tungsten carbide inserts

Nanocrystalline diamond films were deposited on Co-cemented tungsten carbides using bias-enhanced hot filament CVD system with a mixture of acetone, H₂ and Ar as the reactant gas. The effect of Ar concentration on the grain size of diamond films and diamond orientation was investigated. Nanocrystalline diamond films were characterized with field emission scan electron microscopy (FE-SEM), Atomic force microscopy (AFM), Raman spectroscopy and X-ray diffraction spectroscopy (XRD). Rockwell C indentation tests were conducted to evaluate the adhesion between diamond films and the substrates. The results demonstrated that when the Ar concentration was 90%, the diamond films exhibited rounded fine grains with an average grain size of approximately 60–80 nm. The Raman spectra showed broadened carbon peaks at 1350 cm^− 1 and 1580 cm^− 1 assigned to D and G bands and an intense broad Raman band near 1140 cm^− 1 attributed to trans-polyacetylene, which confirmed the presence of the nanocrystalline diamond phase. The full width at half maximum of the <111> diamond peak (0.8°) was far broader than that of conventional diamond film (0.28°–0.3°). The Ra and RMS surface roughness of the nanocrystalline diamond film were measured to be approximately 202 nm and 280 nm with 4 mm scanning length, respectively. The Ar concentration in the reactant gases played an important role in the control of grain size and surface roughness of the diamond films. Nanocrystalline diamond-coated cemented tungsten carbides with very smooth surface have excellent characteristics, which made them a promising material for the development of high performance cutting tools and wear resistance components.     

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.     

Triply switchable bioelectrocatalysis based on poly(N-isopropylacrylamide) hydrogel films with immobilized glucose oxidase

Poly(N-isopropylacrylamide) (PNIPAM) hydrogel films containing glucose oxidase (GOD), designated as PNIPAM-GOD, were synthesized on the surface of pyrolytic graphite (PG) electrodes through radical cross-linking polymerization method. Cyclic voltammetric (CV) response of ferrocenecarboxylic acid (Fc(COOH)) at PNIPAM-GOD film electrodes was very sensitive to the environmental temperature, sulfate concentration, and addition of methanol solvent. For example, at 25 °C, Fc(COOH) exhibited a quasi-reversible CV peak pair with large peak currents in pH 7.0 aqueous solutions containing no sulfate for the films; while at 37 °C, the CV response was greatly suppressed. By switching the film electrodes in solutions between 25 and 37 °C, the CV peak currents of Fc(COOH) cycled between a quite large value and a very small one, showing the reversible thermo-sensitive switching property between the on and off states. Similarly, the reversible SO₄²⁻- and methanol-sensitive on–off behavior of the films toward the probe was also observed. This triply responsive property could be used to realize the thermo-, SO₄²⁻-, and methanol-controlled electrochemical oxidation of glucose catalyzed by GOD immobilized in the films and mediated by Fc(COOH) in solution. This “smart” interface may establish a foundation for fabricating a novel type of multi-controllable biosensors based on bioelectrocatalysis.     

Porous diamond with high electrochemical performance

Synthetic diamond materials are currently attracting attention for applications such as thin films supercapacitors or medical implantable electrodes where chemically stable materials featuring high double layer capacitance as well as low electrochemical impedance are sought. Those properties may be reached with high aspect ratio diamond provided that current collection is done efficiently through the diamond layer. In this paper, we introduce a very novel material, namely SPDia™, based on boron-doped diamond grown on a highly porous polypyrrole scaffold prepared by chemical vapour deposition. This composite was first characterised by SEM and Raman spectroscopy to cheque the diamond crystallinity and the structural evolution of the polypyrrole during the CVD process. Then cyclic voltammetry and electrochemical impedance spectroscopy were performed to assess its electrochemical reactivity. It was found to exhibit remarkable properties, that include a large double layer capacitance with values reaching up to 3 mF cm⁻² in aqueous LiClO₄ and a low electrochemical impedance, thus highly competitive with respect to other nanostructured diamond materials as recently reported.     

Electrochemical properties of nanodiamond powder electrodes

Detonation-synthesized nanocrystalline diamond is a novel carbon material. Its increased electrical conductivity, due to the features of giant specific surface area and large numbers of surface defects as well as the cluster structure, makes it possible to be used as an electrode material. Nanodiamond powder electrodes were fabricated and the electrochemistry was investigated by cyclic voltammetry and AC impedance measurement. The results show that nanodiamond powder electrode is electrochemically stable in KCl electrolytes over a wide potential range (− 1.2–2.0 V). The electrode reaction is quasi-reversible in 0.1 M KCl containing the ferricyanide–ferrocyanide redox couple. The electrode reaction rate constant k is estimated to be 2.87 × 10^− 3 cm/s. The peak current increases linearly with the rising of the concentration of [Fe(CN)₆]^3−/4−. The AC impedance spectra have been analyzed and an equivalent circuit proposed.     

The effects of nitrogenation on the electrochemical properties of nanocrystalline diamond films

The effect of the nitrogenation on the electrochemical properties of nanocrystalline diamond films produced by microwave plasma CVD in CH₄–Ar–H₂–N₂ gas mixtures was studied systematically, using cyclic voltammetry and electrochemical impedance spectroscopy measurements, for the first time. Differential capacitance, kinetic parameters of reactions in [Fe(CN)₆]^3-/4-redox system and potential window were found to be sensitive to the nitrogen concentration in the process gas. With its increase (from 0 to 25%), a transition of the NCD film behavior from “poor conductor” to metal-like character takes place. The heavily N-doped nanocrystalline diamond films have satisfactory electrochemical properties to be used as electrodes.