Cathodic and anodic pre-treated boron doped diamond with different sp content: Morphological,structural, and impedance spectroscopy characterizations

In this work, the influence of cathodic (Red) and anodic (Ox) pre-treatment on boron doped diamond (BDD) films grown with different sp²/sp³ ratios was systematically studied. The sp²/sp³ ratios were controlled by the addition of CH₄ of 1,3,5 and 7 sccm in the gas inlet during the growth process. The electrodes were treated in 0.5 mol L⁻¹ H₂SO₄ at −3 and 3 V vs Ag/AgCl, respectively, for 30 min. The electrochemical response of BDD films was investigated using electrochemical impedance spectroscopy (EIS) and Mott–Schottky Plot (MSP) measurements. Four film sample sets were produced in a hot filament chemical vapor deposition reactor. During the growth process, an additional H₂ line passing through a bubbler containing the B₂O₃ dissolved in methanol was used to carry the boron. The scanning electron microscopy morphology showed well faced films with a small decrease in their grain size as the CH₄ concentration increased. The Raman spectra depicted a pronounced sp² band, mainly for films with 5 and 7 sccm of CH₄. MSP showed a decrease in the acceptor concentration as the CH₄ increased indicating the CH₄ influence on the doping process for Red–BDD and Ox–BDD samples. Nonetheless, an apparent increase in the acceptor concentrations for both Ox–BDD samples was observed compared to that for Red–BDD samples, mainly attributed to the surface conductive layer (SCL) formation after this strong oxidation process. The EIS Nyquist plots for Red–BDD showed a capacitance increase for the films with higher sp² content (5 and 7 sccm). On the other hand, the Nyquist plots for Ox–BDD can be described as semicircles near the origin, at high frequencies, where their charge transfer resistance strongly varied with the sp² increase in such films.     

Poly(3-methylthiophene)-based porous silicon substrates as a urea-sensitive electrode

Poly(3-methylthiophene) (P3MT)-based porous silicon (PS) substrates were fabricated and characterized by cyclic voltammetry, scanning electron microscopy, and auger electron spectroscopy. After doping urease (Urs) into the polymeric matrix, sensitivity and physicochemical properties of the P3MT-based PS substrate was investigated compared to planar silicon (PLS) and bulk Pt substrates. PS substrate was formed by electrochemical anodization in an etching solution composed of HF, H₂O, and ethanol. Subsequently, Ti and Pt thin-films were sputtered on the PS substrate. Effective working electrode area (A_eff) of the Pt-deposited PS substrate was determined from a redox reaction of Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox couple in which nearly reversible cyclic voltammograms were obtained. The i_p versus v^1/2 plots showed that A_eff of the PS-based Pt thin-film electrode was 1.62 times larger than that of the PLS-based electrode.Electropolymerization of P3MT on both types of electrodes were carried out by the anodic potential scanning under the given potential range. And then, urease molecules were doped to the P3MT film by the chronoamperometry. Direct electrochemistry of a Urs/P3MT/Pt/Ti/PS electrode in an acetonitrile solution containing 0.1 mol/L NaClO₄ was introduced compared to a P3MT/Pt/Ti/PS electrode at scan rates of 10 mV s⁻¹, 50 mV s⁻¹, and 100 mV s⁻¹.Amperometric sensitivity of the Urs/P3MT/Pt/Ti/PS electrode was ca. 1.67 μA mM⁻¹ per projected unit square centimeter, and that of the Urs/P3MT/Pt/Ti/PLS electrode was ca. 1.02 μA mM⁻¹ per projected unit square centimeter in a linear range of 1-100 mM urea concentrations. 1.6 times of sensitivity increase was coincident with the results from cyclic voltammetrc analysis.Surface morphology from scanning electron microscopy (SEM) images of Pt-deposited PS electrodes before and after the coating of Urs-doped P3MT films showed that pore diameter and depth were 2 μm and 10 μm, respectively. Multilayered-film structures composed of metals and organics for both electrodes were also confirmed by auger electron spectroscopy (AES) depth profiles.     

Porous carbon-coated graphite electrodes for energy production from salinity gradient using reverse electrodialysis

Performance of graphite foil electrodes coated by porous carbon black (i.e., Vulcan) was investigated in comparison with metal electrodes for reverse electrodialysis (RED) application. The electrode slurry that was used for fabrication of the porous carbon-coated graphite foil is composed of 7.2 wt% of carbon black (Vulcan X-72), 0.8 wt% of a polymer binder (polyvinylidene fluoride, PVdF), and 92.0 wt% of a mixing solvent (dimethylacetamide, DMAc). Cyclic voltammograms of both the porous carbon (i.e., Vulcan)-coated graphite foil electrode and the graphite foil electrode without Vulcan showed good reversibility in the hexacyanoferrate(III) (i.e., Fe(CN)₆³⁻) and hexacyanoferrate(II) (i.e., Fe(CN)₆⁴⁻) redox couple and 1 M Na₂SO₄ at room temperature. However, anodic and cathodic current of the Vulcan-coated graphite foil electrode was much higher than those of the graphite foil electrode. Using a bench-scale RED stack, the current–voltage polarization curve of the Vulcan-coated graphite electrode was compared to that of metal electrodes such as iridium (Ir) and platinum (Pt). From the results, it was confirmed that resistance of four different electrodes increased with the following order: the Vulcan-coated graphite foil<the Ir-coated titanium (Ti) mesh<the Pt-coated Ti plate<the graphite foil. Moreover, the Vulcan-coated graphite foil showed 5–10% higher power density than the metal mesh electrodes. From the polarization curve of the Vulcan-coated graphite foil electrode, it was found that total resistance decreased as thickness and geometric surface area of the electrode increased.     

Influence of boron concentration on growth characteristic and electro-catalytic performance of boron-doped diamond electrodes prepared by direct current plasma chemical vapor deposition

A series of boron-doped diamond (BDD) electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) with different compositions of CH₄/H₂/B(OCH₃)₃ gas mixture. A maximum growth rate of 0.65 mg cm⁻² h⁻¹ was obtained with CH₄/H₂/B(OCH₃)₃ radio of 4/190/10 and this growth condition was also a turning point for discharge plasma stability which arose from the addition of B(OCH₃)₃ that changed electron energy distribution and influenced the plasma reaction. The surface coating structure and electro-catalytic performance of the BDD electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy, Hall test, and electrochemical measurement and electro-catalytic oxidation in phenol solution. It is suggested that the boron doping level and the thermal stress in the films are the main factors affecting the electro-catalytic characteristics of the electrodes. Low boron doping level with CH₄/H₂/B(OCH₃)₃ ratio of 4/199/1 decreased the films electrical conductivity and its electro-catalytic activity. When the carrier concentration in the films reached around 10²⁰ cm⁻³ with CH₄/H₂/B(OCH₃)₃ ratio over a range of 4/195/5-4/185/15, the thermal stress in the films was the key reason that influenced the electro-catalytic activity of the electrodes for its effect on diamond lattice expansion. Therefore, the BDD electrode with modest CH₄/H₂/B(OCH₃)₃ ratio of 4/190/10 possessed the best phenol removal efficiency.     

The influence of boron content on electroanalytical detection of nitrate using BDD electrodes

Electrochemical response of nitrate reduction was analyzed using Boron Doped Diamond (BDD) films grown with different boron levels and it was correlated with the electrode physico-chemical properties. X-ray photoelectron spectroscopy and contact angle measurements showed the evolution of oxygen content and the weattability associated to the chemical surface modification as boron content increase in such films. Raman spectroscopy showed that the broad peaks at 1220 and 500 cm⁻¹ become more evident with the boron addition. Electrochemical measurements by square wave voltammetry for nitrate reduction showed a strong dependence between the doping level of the BDD film and the nitrate detection. BDD film grown with B/C ratio of 20,000 ppm presented the best sensibility to low concentration of nitrate. This result was analyzed from the linear relationship between the peak currents as a function of the nitrate concentration. This behavior was attributed to the changes in the diamond surface chemical and the film grain size.     

Boron-Doped Diamond-Film-Based Two-Dimensional Electrode of Electrophoresis Tank

Chemically robust conductive p-type boron-doped diamond(BDD) films are an important electrode material and have been widely applied in electrochemistry.In this study,BDD films are taken as a two-dimensional(2D)electrode in a electrophoresis tank system instead of the conventional one-dimensional platinum wire electrode.The theoretical simulations by finite element numerical analysis reveal that the 2D BDD electrodes have relatively high intensity and uniformity of electric field in the tank.Experimentally,the 2D BDD electrodes with smaller size show excellent properties for the separation of DNA fragments.The advantages of the 2D BDD electrodes with chemical inertness,sustainability,high intensity and uniformity electronic field,as well as reduced small size of electrophoresis tank would open a possibility for realizing new generation,high-performance biological devices.     

Application of BDD thin film electrode for electrochemical decomposition of heterogeneous aromatic compounds

The aim of the presented study is to investigate the applicability of electrochemical oxidation of aromatic compounds containing heteroatoms, e.g. waste from production of pesticides or pharmaceutics, at a borondoped diamond (BDD) electrode. The BDD electrodes were synthesized by microwave plasma enhanced chemical vapour deposition (MW PE CVD). Investigation of the electrode surface by optical microscopy and scanning electron microscopy (SEM) confirmed that the synthesized layer was continuous and formed a densely packed grain structure with an average roughness of less than 0:5 ??m. The influence of important electrochemical parameters: current density, kind of reactor, pH or mixing operation, on the efficiency of the oxidation was investigated. The fouling of electrode??s surface caused by the deposition of organic material was observed during CV and galvanostatic experiments. At low current density the oxidation rate constant k was low, but the current efficiency was relatively high. The BDD can be used successfully to remove heterogeneous aromatic compounds existing either as molecules or cations. During 4 h of electrolysis 95% of aromatic compounds were electrochemically decomposed to mineral forms. It was observed that the influence of the initial pH on mineralization was marginal.     

Surface modification of titanium membrane by chemical vapor deposition and its electrochemical self-cleaning

Membrane separation is applied widely in many fields, while concentration polarization and membrane fouling, limiting its promotion and application greatly, are the bottlenecks in membrane application. Among which, membrane fouling is irreversible, membrane must be periodically cleaned or even replaced to restore permeability. Membrane cleaning has become one of the key issues in membrane separation areas. Considering incomparable electrochemical advantages of boron-doped diamond (BDD) film electrode over conventional electrode, a new composite membrane Ti/BDD, made by depositing CVD (chemical vapor deposition) boron-doped diamond film on titanium(Ti) membrane to modify porous titanium surface, that can be cleaned electrochemically is proposed. Feasibility of its preparation and application is discussed in this paper. Results shows that based on the unique electrochemical properties of diamond, cleaning level of this composite Ti/BDD membrane is significantly increased, making membrane life and efficiency improved prominently.     

Electrocatalytic oxidation of <Emphasis Type="SmallCaps">l</Emphasis>-tyrosine at carboxylic acid functionalized multi-walled carbon nanotubes modified carbon paste electrode

The electrocatalytic oxidation of l-tyrosine (Tyr) was investigated on a carboxylic acid functionalised multi-walled carbon nanotubes modified carbon paste electrode using cyclic voltammetry and amperometry. The surface morphology of the electrodes was studied using field emission (FE)-SEM images, and the interface properties of bare and modified electrodes were investigated by electrochemical impedance spectroscopy (EIS). The influence of the amount of modifier loading and the variation of the pH of the solution on the electrochemical parameters have been investigated. Cyclic voltammetry was carried out to study the electrochemical oxidation mechanism of Tyr, which showed an irreversible oxidation process at a potential of 637.0 mV at modified electrode. The anodic peak current linearly increased with the scan rate, suggesting that the oxidation of Tyr at modified electrode is an adsorption-controlled process. A good linear relationship between the oxidation peak current and the Tyr concentration in the range of 0.8–100.0 μM was obtained in a phosphate buffer solution at pH 7.0 with a detection limit of 14.0?±?1.36 nM (S/N?=?3). The practical utility of the sensor was demonstrated by determining Tyr in spiked cow’s milk and human blood serum. The modified electrode showed excellent reproducibility, long-term stability and antifouling effects.     

A fast and sensitive nanosensor based on MgO nanoparticle room-temperature ionic liquid carbon paste electrode for determination of methyldopa in pharmaceutical and patient human urine samples

In this study, we describe an ionic liquid–MgO nanoparticle modified carbon paste electrode (MgO/NPs/IL/CPE) was used as a simple, fast, and sensitive tool for the investigation of the electrochemical oxidation of methyldopa (MDOP) using voltammetric methods. The MgO/NPs was characterized with different methods such as TEM, SEM, and XRD. The oxidation peak potential of the MDOP at a surface of MgO/NPs/IL/CPE appeared at 450 mV that was about 100 mV lower than the oxidation peak potential at the surface of the traditional carbon paste electrode (CPE) under similar conditions. The electro-oxidation of MDOP occurred in a pH-dependent 2e^? and 2H⁺ process, and the electrode reaction followed a diffusion-controlled pathway. Under optimal conditions at pH 7.0, the anodic peak currents increased linearly with the concentration of MDOP in the range of 0.08–380 μmol L^?1 with a detection limit of 0.03 μmol L^?1 (3σ). The proposed sensor was successfully applied to the determination of MDOP in real samples such as drug and urine.     

Intercalation of lithium ions into bulk and powder highly oriented pyrolytic graphite

The electrochemical reactions of highly oriented pyrolytic graphite (HOPG) bulk and powder electrodes in 1 M LiPF₆ 1:1 EC/DMC solution were investigated and the results show that the intercalation reaction of lithium ion into HOPG electrode occurs only at the edge plane and SEI formation reaction on the basal plane is negligible in comparison with that on the edge plane. The active surface area of HOPG powder electrode could be deduced by comparing the peak area (consumed charge for SEI formation) at potential of 0.5 V on voltammograms with that of bulk HOPG edge electrode. The diffusion coefficients of lithium ion in HOPG bulk layers and in HOPG powder was for the first time measured by use of electrochemical impedance spectra and potential step chronamperameter methods. It was found that the diffusion coefficients of lithium in HOPG were in the range of 10⁻¹¹-10⁻¹² cm² s⁻¹ for the lithium-HOPG intercalation compounds at potentials from 0.2 (vs. Li/Li⁺) to 0.02 V, decreasing with the increase of lithium intercalation degree. A good agreement was obtained between the results from bulk and powder HOPG electrodes by electrochemical impedance spectra method.     

The synthesis and characterization of Ti/SnO2-Sb2O3/PbO2 electrodes: The influence of morphology caused by different electrochemical deposition time

For the electrochemical oxidative degradation of wastewater, it is crucial for electrodes to be highly catalytic active, stable in performance and inexpensive in price. This study focuses on the preparation of the Ti/SnO₂-Sb₂O₃/PbO₂ anodes by anodic deposition under galvanostatic conditions and their electrocatalytic activity affected by crystal structure and surface roughness under different electrochemical deposition time, with phenol taken as the model pollutant to evaluate the electrocatalytic activity. The electrode surface morphology is characterized by XRD and SEM-EDX. The treatment effect of phenol is reflected by electrochemical analysis like CV and LSV. An important conclusion from experiment is that electrochemical deposition time has a major impact on electrocatalytic activity with the optimal deposition time observed around 30 min. At both deposition time beyond this optimal time window, electrocatalytic activity of phenol is substantially lowered. Increasing in electrochemical deposition time leads to a more uniform and smooth electrode surface, which enjoys a more compact structure than the “cracked-mud” one but lower specific surface area and catalytic activity. On the contrary, the “cracked-mud” structure means potentially a unique porous structure, which makes morphology at 30 min a perfect one for high electrocatalytic activity.     

Studies on distribution of element contents in transient layer at interface between boron-doped diamond film electrode and tantalum substrate

The boron-doped diamond film (BDD) grown on tantalum (Ta) substrate as an electrode (BDD/Ta) was prepared by hot filament chemical vapor deposition method. The experimental results demonstrated that our BDD/Ta had high current efficiency, strong ability to degrade wastewater, good corrosion stability and long lifetime. These excellent characteristics of BDD/Ta have been explained in terms of Rutherford backscattering (RBS) experiments. RBS investigation revealed that the continuous transient layer at the interface between boron-doped diamond film and Ta-substrate was formed and the microstructure of the continuous transient layer given by the continuous distribution of all element contents at the interface was obtained. The thicknesses of boron-doped diamond film and the continuous transient layer were about equal to 8000 × 10¹⁵ atoms/cm² and 5800 × 10¹⁵ atoms/cm², respectively. The formation of the continuous transient layer at the interface can eliminate the mismatch of thermal expansion coefficients (TEC) at the interface and only lead to the slow change of TEC because of the continuous distribution of element contents of the film and substrate in the transient layer at the interface. Thus, there is no residual stress to concentrate on the interface and the stress-corrosion delamination of the film disappears. Therefore, the corrosion stability and lifetime of BDD/Ta increase and last well, that have been verified by X-ray diffraction (XRD) experiments.     

Sensitive voltammetric determination of diclofenac using room-temperature ionic liquid-modified carbon nanotubes paste electrode

An ionic liquid-modified carbon nanotubes paste electrode (IL/CNTPE) has been fabricated using hydrophilic ionic liquid (n-hexyl-3-methylimidazolium hexafluoro phosphate) as a binder. This electrode showed enhanced electrochemical response and strong analytical activity towards the direct electrochemical oxidation of diclofenac (DCF). The electron transfer coefficient, α, and charge transfer resistance (R _ct) of DCF at the modified electrode were calculated. Under optimal conditions at pH 7.0, the anodic peak currents increased linearly with the concentration of DCF in the range of 0.5–300 μmol L^?1 with a detection limit of 0.2 μmol L^?1 (3σ). The interferences of foreign substances were investigated. Differential pulse voltammetry was used to check the applicability of the proposed sensor to the determination of DCF in real samples with satisfactory results.     

Electrochemical luminescence of n-type ZnO semiconductor electrodes doped with rare earth metals under the anodic polarization

Electrochemical luminescence (ECL) at n-type ZnO semiconductor electrode was measured under anodic polarization. Scanning the potential imposed on the ZnO electrode, emission was suddenly observed around +20 V. Using the ZnO electrodes doped with rare earth metal ions as Sm³⁺, Eu³⁺, Dy³⁺, Ho³⁺ and Er³⁺, much brighter emission was obtained than the ECL of non-doped ZnO. These emission spectra are ascribed to the rare earth metal ions, respectively. This result would show that emission centers of doped ions were selectively excited by electrons that were injected from electrolyte to the electrode by avalanche breakdown under strong anodic bias on the ZnO.     

Charge storage performance of lithiated iron phosphate/activated carbon composite as symmetrical electrode for electrochemical capacitor

In this study, a symmetric electrochemical capacitor was fabricated by adopting a lithium iron phosphate (LiFePO₄)-activated carbon (AC) composite as the core electrode material in 1.0 M Na₂SO₃ and 1.0 M Li₂SO₄ aqueous electrolyte solutions. The composite electrodes were prepared via a facile mechanical mixing process. The structural properties of the nanocomposite electrodes were characterised by scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) analysis. The electrochemical performances of the prepared composite electrode were studied using cyclic voltammetry (CV), galvanostatic charge–discharge (CD) and electrochemical impedance spectroscopy (EIS). The experimental results reveal that a maximum specific capacitance of 112.41 F/g was obtained a 40 wt% LiFePO₄ loading on an AC electrode compared with that of a pure AC electrode (76.24 F/g) in 1 M Na₂SO₃. The improvement in the capacitive performance of the 40 wt% LiFePO₄–AC composite electrode is believed to be attributed to the contribution of the synergistic effect of the electric double layer capacitance (EDLC) of the AC electrode and pseudocapacitance via the intercalation/extraction of H⁺, OH⁻, Na⁺ and SO₃²⁻ and Li⁺ ions in LiFePO₄ lattices. In contrast, it appears that the incorporation of LiFePO₄ into AC electrodes does not increase the charge storage capability when Li₂SO₄ is used as the electrolyte. This behaviour can be explained by the fact that the electrolyte system containing SO₄²⁻ only exhibits EDLC in the Fe-based electrodes. Additionally, Li⁺ ions that have lower conductivity and mobility may lead to poorer charge storage capability compared to Na⁺ ions. Overall, the results reveal that the AC composite electrodes with 40 wt% LiFePO₄ loading on a Na₂SO₃ neutral electrolyte exhibit high cycling stability and reversibility and thus display great potential for electrochemical capacitor applications.     

Lithium insertion studies on boron-doped diamond as a possible anode material for lithium batteries

Boron-doped diamond (BDD) was prepared by the hot filament chemical vapor deposition method. The prepared samples were subjected to X-ray diffraction, scanning electron microscopy, and Raman spectroscopy studies. The BDD composite electrode/Li cell has been assembled, and its cycling behavior was studied. The BDD possesses large sp² sites, which effectively participate in the lithium storage process. Furthermore, nanocrystalline tin (Sn) particles were prepared by the chemical reduction method. The addition of nanotin with the BDD-active material greatly enhances the cyclability of the cell. An erratum to this article can be found at     

Effects of platinum nano electrodeposits on corrosion of carbon substrate

The electrodes for the experiments were prepared by electrodepositing Pt on a carbon substrate. In the cyclic voltammograms of the carbon electrodes with and without Pt nano electrodeposits, the total anodic current including the currents from the oxygen evolution reaction and carbon corrosion increased abruptly above a critical potential. The oxidation overpotential of the carbon electrodes with Pt nano electrodeposits was lower than that of the bare carbon electrode. This phenomenon was more prominent at 75 °C than at 25 °C. In the potentiostatic experiments, the current transients and corresponding power spectral density (PSD) increased with increasing applied potential to the electrodes. Furthermore, the current transients for the carbon electrodes with Pt nano electrodeposits were much higher than those for the bare carbon electrode. This suggests that the corrosion of the carbon substrate can be accelerated by the Pt nano electrodeposits.     

Ultrahigh supercapacitance in cobalt oxide nanorod film grown by oblique angle deposition technique

Nanorod films of cobalt oxide (Co₃O₄) have been grown by a unique oblique angle deposition (OAD) technique in an e-beam evaporator for supercapacitor electrode applications. This technique offers a non-chemical route to achieve large aspect ratio nanorods. The fabricated electrodes at OAD 80° exhibited a specific capacitance of 2875 F/g. The electrochemically active surface area was 1397 cm⁻², estimated from the non-Faradaic capacitive current region. Peak energy and power densities obtained for Co₃O₄ nanorods were 57.7 Wh/Kg and 9.5 kW/kg, respectively. The Co₃O₄ nanorod electrode showed a good endurance of 2000 charge-discharge cycles with 62% retention. The OAD approach for fabricating supercapacitor nanostructured electrodes can be exploited for the fabrication of a broad range of metal oxide materials.     

Study of oxidation process of Cr/Cu/Cr thin film electrodes

Understanding the oxidation process of Cr/Cu/Cr laminated thin film electrode is important for developing new oxidation-resistant electrodes. By studying the evolution of crystal structure, morphology and electric resistivity of Cr/Cu/Cr thin films and electrodes that were post-annealed at different temperatures, the oxidation mechanism and process of Cr/Cu/Cr electrode were proposed. Copper is first oxidized into Cu₂O at low temperatures (<310 °C), and converts to CuO phase at higher temperatures. Two pathways for oxygen diffusion were identified: diffusion from the protective Cr layer, and diffusion from the sidewall of electrode, of which the latter one leads to total oxidation of copper interlayer at high temperatures (>310 °C). As a result, the passivation of Cu metal at electrode sidewalls is crucial in reducing oxidation of Cr/Cu/Cr electrodes or designing new copper-containing oxidation-resistant electrodes.