Development and study of anodic Ti/TiO2 electrodes and their potential use as impedimetric immunosensors

Titanium dioxide films were anodically formed at various potentials up to 65 V in 1 M H₂SO₄. Oxide films were characterized by performing various techniques, including electrochemical impedance spectroscopy, scanning electron microscopy, Raman spectroscopy, ellipsometry and diffuse reflectance FT-IR spectroscopy. Low voltage anodization (up to 10 V) results to amorphous TiO₂, whereas at higher applied potentials (up to 65 V), anatase is the predominant form. Anatase films were further hydroxylated with an acidic agent and the effect of this treatment on the overall impedance of the electrodes was studied with impedance spectroscopy. The potential use of anodic (anatase) Ti/TiO₂ electrodes in the development of impedimetric immunosensors is also demonstrated by monitoring the immunoreaction of avidin/anti-avidin with different instrumental approaches based on a FRA analyzer, an LCR-meter and a home-built charge integrator (Multipulser).     

Electro-catalytic oxidation of CO on Pt catalyst supported on carbon nanotubes pretreated with oxidative acids

Characteristics of nanosized Pt electro-catalyst deposited on carbon nanotubes (CNTs) were studied with CO-stripping voltammogram and chronoamperometry measurements. The CNTs were pretreated by oxidation in HNO₃, mixed HNO₃ + H₂SO₄ and H₂SO₄ + K₂Cr₂O₇ solution, respectively, to enable surface modification. Well-homogenized Pt particles (average size: ≈3 nm) were loaded onto the pretreated CNT samples by a modified colloidal method. TEM, BET, FTIR and XRD techniques were used to characterize the physicochemical properties of the pretreated CNT samples. In the electro-oxidation of CO, all the Pt/CNT samples showed lower on-set as well as peak potentials than the conventional Pt/XC-72 electro-catalyst, indicating that the Pt/CNT samples were more resistant to CO poisoning and could be superior anode electro-catalyst for the proton exchange membrane fuel cells (PEMFCs). Moreover, we found that the pretreatment of CNTs in mixed HNO₃ + H₂SO₄ solution was very beneficial for the performance enhancement of Pt/CNT electro-catalyst; the catalyst obtained as such gave the lowest peak potential and the highest catalytic activity for the electro-oxidation of CO. Larger amount of oxygen-containing functional groups, higher percentage of mesopores, and higher graphitic crystallinity of the pretreated CNTs were considered crucial for the performance enhancement, e.g., by strengthening the interaction between Pt nanoparticles and the CNT support and enhancing the mass diffusion in the electro-chemical reaction.     

The characterisation of PbO2-coated electrodes prepared from aqueous methanesulfonic acid under controlled deposition conditions

A series of PbO₂ coatings on planar carbon substrates has been prepared by anodic deposition in aqueous methanesulfonic acid (MSA) under galvanostatic conditions. The effect of four experimental parameters, i.e., lead(II) methanesulfonate and MSA concentrations, current density, and temperature was analysed. Surface characterisation by XRD, SEM-EDX, and AFM has provided information about the structural (phase distribution, degree of crystallinity, and crystallite size), morphological (crystallite shape, degree of porosity), and tribological (surface roughness) properties of the PbO₂ coatings, respectively. Electrochemical studies based on linear and cyclic voltammetry allowed comparison between electrodes prepared in MSA and classical electrodes prepared in HNO₃. Pure α- or β-PbO₂ and α + β mixtures were obtained depending on the conditions, being temperature the most influential deposition parameter. A temperature rise caused a transition to pure β-PbO₂ and led to a higher degree of crystallinity with a progressive increase of crystallite size, always within the range of 10-30 nm, as well as to a remarkably higher roughness, from smooth (35-50 nm rms) to rough (up to 500 nm rms) surfaces. Low MSA and high lead(II) methanesulfonate concentrations were required to avoid the formation of excessively porous powdery coatings, as well as cracks, pits, and holes. Most of the coatings obtained in MSA were uniform, nanocrystalline, and moderately rough. Their electrocatalytic behaviour was comparable to that of the electrodes prepared in HNO₃, showing an O₂-overpotential of +0.66 V in 0.05 M Na₂SO₄ at pH 3.0. Such coatings can then be envisaged as suitable anodes for energy and water treatment applications. Prolonged electrolysis has shown their stability against leaching.     

A comparison of the electrocatalytic activities of ordered mesoporous carbons treated with either HNO3 or NaOH

Ordered mesoporous carbon (OMC) was treated with HNO₃ or NaOH. The two treated OMCs have many oxygen-containing functional groups. Those treated with HNO₃ have more acidic surface groups than those treated with NaOH. Nicotinamide adenine dinucleotide (NADH) and H₂O₂ were selected as marker molecules for the comparison of the electrocatalytic property of the OMCs. A comparison between the cyclic voltammograms shows that the oxidation peak potential of NADH is 0.614 V at a bare glassy carbon electrode (GCE), 0.205 V at OMC/GCE, 0.223 V at NaOH-treated OMC/GCE, and 0.0 V at HNO₃-treated OMC/GCE (vs. Ag/AgCl). The results indicate that the HNO₃-treated OMC/GCE exhibits the highest electrocatalytic activity for NADH oxidation. Thus, acidic groups rather than other oxygen-containing functional groups, play a very important role in the catalytic activity of OMC.     

Industrially scalable process to separate catalyst substrate materials from MWNTs synthesised by fluidised-bed CVD on iron/alumina catalysts

A multi-step purification process to separate metal catalysts and their support materials from mixtures of straight and spiral multi-walled carbon nanotubes (MWNTs), synthesised via fluidised-bed chemical vapour deposition (CVD) is described. The process involves: (i) refluxing as-synthesised bed materials (iron and non-porous alumina supports coated with carbon nanotubes (CNTs) and amorphous carbon) in either HNO₃, HNO₃/H₂SO₄ (v/v=1:3) or H₂SO₄ at each mixture's boiling point for 3, 6 or 12 h, (ii) filtering these samples using a two-stage (2.7 and 0.5 μm) filtration system, (iii) air drying and (iv) temperature selective, gas-phase oxidation in air to remove amorphous carbon. Both low and high purity as-synthesised bed materials (1.7 and 26.3 wt% CNTs, respectively) were used to investigate the process efficiency. Collectively these four steps were successful in removing amorphous carbon, metal catalysts and their alumina supports from the CNTs, improving the CNT purity from 1.7 wt% in the low purity as-synthesised samples to a maximum of 40.0 wt% and from 26.3 wt% in the higher purity feedstocks to 92.9 wt%. In both cases the remaining impurity was unseparated alumina, which remained bound to the CNTs even after treatment with concentrated acids for 12 h. The process has two potential advantages related to the development of large-scale CNT technologies: (i) the use of hydrofluoric acid, which is expensive and unsafe to use in large quantities has been avoided and (ii) the process is inherently scaleable and uses standard process engineering equipment suitable for large-scale CNT purification.     

Electrochemical behaviour of glassy carbon electrodes modified with aryl groups

The electrochemical modification of the glassy carbon (GC) electrode surface with biphenyl, 1-naphthyl, 2-naphthyl, 4-bromophenyl, 4-decylphenyl and 4-nitrophenyl groups was performed by the diazonium reduction method. The blocking behaviour of aryl films grafted by three different procedures was compared. Oxygen reduction was studied on these modified GC electrodes using the rotating disk electrode (RDE) method. The highest blocking efficiency for O₂ reduction was observed for 4-bromophenyl groups. The barrier properties of aryl-modified GC surfaces were also characterised using Fe(CN)₆³⁻ and dopamine redox probes. Electrochemical measurements were carried out in 0.1 M K₂SO₄ containing 1 mM K₃Fe(CN)₆ and in 0.1 M H₂SO₄ containing 1 mM dopamine using cyclic voltammetry (CV). The blocking action varied significantly depending on the surface modifier used and the solution based redox species studied.     

Evaluation of mild acid oxidation treatments for MWCNT functionalization

Acidic oxidation methods have been widely reported as an effective method to purify and functionalize the surface of carbon nanotubes (CNTs). Although effective, the strong acids typically employed and the high sonication power used to disperse the nanotubes in the solution frequently cause nanotube damage, limiting their great potential as mechanical and electrical reinforcements. This work examines the use of HNO₃, H₂SO₄ and H₂O₂ at relatively low concentrations, short treatment times and low sonication power, in an attempt to achieve experimental conditions which efficiently functionalize the surface of multiwalled CNTs minimizing nanotube damage. A low power sonochemical treatment employing 3.0 M HNO₃ for 2 h followed by 2 h of identical treatment with H₂O₂ proved to be the most effective for this aim.     

Electrochemical surface nanopatterning by selective reductive desorption from mixed metal surfaces

We report on a novel strategy to the functionalisation of electrode surfaces based on the preparation and patterning of mixed metal electrodes using metal selective electrodesorption of a sacrificial alkanethiol. Plain palladium (Pd) and plain polycrystalline gold (poly-Au) electrodes were used initially to determine metal specific potential windows within which electrodesorption of the short alkanethiol mercaptoethanol could be achieved. We found that stripping of mercaptoethanol from gold was achieved at potentials lower than −0.800 V, whilst stripping from palladium was achieved at more positive potentials i.e. around −0.650 V. Mixed metal electrodes were prepared by electroplating for short period of times palladium onto poly-Au electrodes. The resulting surfaces were characterised electrochemically in 1 M H₂SO₄ and clearly exhibited reduction peaks for both gold and palladium oxide formation. The mixed metal electrodes were coated with mercaptoethanol, which was further selectively removed from Pd by cyclic voltammetry in NaOH in the Pd-specific potential window. The presence of bare Pd domains revealed following electrodesorption was confirmed by subsequently adsorbing the electroactive alkanethiol 6-ferrocenylhexanethiol onto the freshly revealed Pd. Cyclic voltamogramms exhibited sharp redox peaks that could only be attributed to the successful immobilisation of 6-ferrocenylhexanethiol onto fresh Pd domains. Control surfaces, i.e. MCE fully coated Pd/Poly-Au electrode, exposed to 6-ferrocenylhexanethiol did not exhibit significant voltammetric features, attesting to the efficient patterning of the mixed metal electrode by employing metal specific reductive desorption of short alkanethiols. The possibility to pattern electrode surfaces in such way will find application in the field of diagnostics, and also in heterogeneous catalysis where Pd-Au alloys have received an increased interest in the recent years.     

Photoanodic response of iron oxide electrode in aqueous solution and its application to Pb removal under visible light irradiation

The iron oxide electrode was prepared from thermal oxidation of iron at 600 °C for 3 h in air atmosphere. This electrode with the structure of Fe₃O₄ and α-Fe₂O₃ showed the response of photoanodic current to the light with wavelength shorter than 600 nm. The band gap energy of this electrode was 1.99 eV. The onset potential of distinct steady photocurrent and also the flatband potential were 0.80 and 0.09 V vs. Ag/AgCl, respectively, in 0.1 M HNO₃ aqueous solution. The cell consisting of the iron oxide photoanode in HNO₃-Pb(NO₃)₂ and the graphite cathode in H₂SO₄-Ce(SO₄)₂ caused the PbO₂ deposit on the surface of the former electrode due to visible light irradiation without application of voltage. By holding the potential of this electrode at more positive value than 0.90 V, the photoanodic removal rate of Pb²⁺ in HNO₃-Pb(NO₃)₂ solution was higher than that observed when Ce⁴⁺ was used as electron acceptor.     

The characterization and bioelectrocatalytic properties of hemoglobin by direct electrochemistry of DDAB film modified electrodes

Direct electrochemistry of hemoglobin can be performed in acidic and basic aqueous solutions in the pH range 1-13, using stable, electrochemically active films deposited on a didodecyldimethylammonium bromide (DDAB) modified glassy carbon electrode. Films can also be produced on gold, platinum, and transparent semiconductor tin oxide electrodes. Hemoglobin/DDAB films exhibit one, two, and three redox couples when transferred to strong acidic, weak acidic and weak basic, and strong basic aqueous solutions, respectively. These redox couples, and their formal potentials, were found to be pH dependent. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ deposition of DDAB on gold disc electrodes and hemoglobin deposition on DDAB film modified electrodes. A hemoglobin/DDAB/GC modified electrode is electrocatalytically reduction active for oxygen and H₂O₂, and electrocatalytically oxidation active for S₂O₄²⁻ through the Fe(III)/Fe(II) redox couple. In the electrocatalytic reduction of S₄O₆²⁻, S₂O₄²⁻, and SO₃²⁻, and the dithio compounds of 2,2′-dithiosalicylic acid and 1,2-dithiolane-3-pentanoic acid, the electrocatalytic current develops from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in neutral and weakly basic aqueous solutions. Hemoglobin/DDAB/GC modified electrodes are electrocatalytically reduction active for trichloroacetic acid in strong acidic buffered aqueous solutions through the Fe(III)/Fe(II) redox couple. However, the electrocatalytic current developed from the cathodic peak of the redox couple at a potential of about −0.9 V (from the Fe(II)/Fe(I) redox couple) in weak acidic and basic aqueous solutions. The electrocatalytic properties were investigated using the rotating ring-disk electrode method.     

Development of a novel redox flow battery for electricity storage system

A novel cylindrical battery which uses carbon fibres with high specific surface area as electrodes and a porous silica glass with high chemical stability as membrane has been fabricated. The results obtained from electrolysis of 0.5 M K₃Fe(CN)₆–0.5 M KCl and of 85 mM V(IV)–1 M H₂SO₄ indicate that the cell possesses excellent electrolytic efficiency. As a redox flow battery (RFB) its performance was investigated by employing all-vanadium sulfate electrolytes. The results of the cyclic voltammetry measurements indicate that at a glassy carbon electrode the electrochemical window for 2 M H₂SO₄ solution could reach 2.0 2.4 V. Constant current charging–discharging tests indicate that the batteries could deliver a specific energy of 24 Wh L^–1 at a current density of 55 mA cm^–2. The open-circuit cell voltage, after full charging, remained constant at about 1.51 V for over 72 h, while the coulombic efficiency was over 91%, showing that there was negligible self-discharge due to active ions diffusion through the membrane during this period.     

Effect of potential cycling on structure and activity of Pt nanoparticles dispersed on different carbon supports

Platinum particles synthesized via the Bönnemann methods were dispersed on two different Vulcan XC72 carbon supports. One was used after thermal treatment at 400 °C under nitrogen atmosphere, the other after oxidation of its surface by acid leaching using diluted HNO₃ in water (1/3). Characterization of the carbon support indicated that HNO₃ treatment leads to the decrease of the BET surface and to the increase of the surface acidity of the carbon support. After dispersion of the platinum catalyst, TEM results indicated that the mean particle size was a little higher on the non-oxidized support (Pt/XC72) than that on the functionalized one (Pt/XC72_HNO3), being 2.5 and 2.0 nm, respectively. However, potential cycles from 0.05 to 1.25 V vs. RHE led to a higher increase of the particle size when catalyst is dispersed on the functionalized support, reaching after 400 potential cycles 5.5 nm against 4.0 nm with the non-functionalized one. The effect of the upper limit (1.0 and 1.25 V vs. RHE) of the potential cycles on the active surface area and on the activity towards the oxygen reduction reaction (orr) was determined for both catalysts. Results indicated that the particle growth was not the main degradation process over the whole duration of the electrochemical experiments, but that dissolution/redeposition (Otswald ripening) was also involved. The predominant role of each degradation process depends on the number of cycles, on the upper potential limit and on the carbon surface state, and could be temporally separated. However, the lower activity towards orr was recorded for the (Pt/XC72_HNO3) cycled up to 1.0 V vs. RHE.     

Catalytic activity, stability and structure of multi-walled carbon nanotubes in the wet air oxidation of phenol

Multi-walled carbon nanotubes (MWCNTs), with no supported metal, were used as catalysts in the wet air oxidation of phenol. The MWCNTs were chemically modified using HCl or HNO₃-H₂SO₄. They were characterized by BET, SEM, TEM, FT-IR and Raman spectroscopy. The functionalized MWCNTs exhibited both high activity and good stability in the wet air oxidation of phenol. At 160 °C and 2.0 MPa with an initial phenol concentration of 1000 mg/L, 100% phenol conversion and 76% total organic carbon abatement could be achieved after 120 min reaction. Upon reaction, the short chain carboxylic acids mainly maleic/fumaric, malonic, oxalic, formic and acetic acid were produced. Surface functional groups (-COOH) were shown to play a key role in the high activity of the functionalized MWCNTs. A mechanism for the CWAO of phenol was proposed.     

Test of vanadium pentoxide as anode for the electrooxidation of toluene: A theoretical approach of the electrode process

Vanadium pentoxide (V₂O₅) films were prepared by electrochemical and thermal decomposition of vanadyl sulphate on titanium dioxide covered titanium plates and glassy carbon discs. The prepared material by thermal decomposition showed high surface area and good physical stability; while the electrodeposited films, although being homogeneous, showed poor adhesion. The V₂O₅ electrodes were chemically and electrochemically stable in aqueous (1 M H₂SO₄ + 1 M NaOH, pH 3) and organic (0.1 M But₄NPF₆ + CH₃CN) solutions. In both cases, a well defined electrochemical response was observed. At the experimental conditions, the prepared materials were not active for the electrooxidation of toluene. The theoretical modeling suggests that the lack of activity is due to the weak interaction between toluene and the V₂O₅ surface.     

Adsorption of ochratoxin A (OTA) anodic oxidation product on glassy carbon electrodes in highly acidic reaction media: Its thermodynamic and kinetics characterization

We study the thermodynamics and kinetics of the adsorption of a redox couple having quinone nature on glassy carbon electrodes. This couple is produced by the anodic oxidation of mycotoxin ochratoxin A in 10% acetonitrile + 90% 1 M HClO₄ aqueous solution. The quasi-reversible redox couple was studied by both cyclic (CV) and square wave (SWV) voltammetric techniques. The Frumkin adsorption isotherm best described the specific interaction of the redox couple with carbon electrodes. By fitting the experimental data, we obtained values of −28.4 kJ mol⁻¹ and 0.70 ± 0.02 for the Gibbs free energy of adsorption and the interaction parameter, respectively. SWV fully characterized the thermodynamics and kinetics of the adsorbed redox couple, using a combination of the “quasi-reversible maximum” and the “splitting of SW peaks” methods. Average values of 0.609 ± 0.003 V and 0.45 ± 0.06 were obtained for the formal potential and the anodic transfer coefficient, respectively. Moreover, a formal rate constant of 10.7 s⁻¹ was obtained. SWV was also employed to generate calibration curves. The lowest concentration of mycotoxin was 1.24 × 10⁻⁸ M (5 ppb), measured indirectly with a signal to noise ratio of 3:1.     

Synthesis and characterization of carbon-coated Li3V2(PO4)3 cathode materials with different carbon sources

The carbon-coated monoclinic Li₃V₂(PO₄)₃ (LVP) cathode materials were synthesized by a solid-state reaction process under the same conditions using citric acid, glucose, PVDF and starch, respectively, as both reduction agents and carbon coating sources. The carbon coating can enhance the conductivity of the composite materials and hinder the growth of Li₃V₂(PO₄)₃ particles. Their structures and physicochemical properties were investigated using X-ray diffraction (XRD), thermogravimetric (TG), scanning electron microscopy (SEM) and electrochemical methods. In the voltage region of 3.0-4.3 V, the electrochemical cycling of these LVP/C electrodes all presents good rate capability and excellent cycle stability. It is found that the citric acid-derived LVP owns the largest reversible capacity of 118 mAh g⁻¹ with no capacity fading during 100 cycles at the rate of 0.2C, and the PVDF-derived LVP possesses a capacity of 95 mAh g⁻¹ even at the rate of 5C. While in the voltage region of 3.0-4.8 V, all samples exhibit a slightly poorer cycle performance with the capacity retention of about 86% after 50 cycles at the rate of 0.2C. The reasons for electrochemical performance of the carbon coated Li₃V₂(PO₄)₃ composites are also discussed. The solid-state reaction is feasible for the preparation of the carbon coated Li₃V₂(PO₄)₃ composites which can offer favorable properties for commercial applications.     

Electrochemical reactivity of aqueous SO2 on glassy carbon electrodes in acidic media

The electrochemical reactivity of dissolved SO₂ on glassy carbon (GC) electrodes was studied in sulfuric and perchloric acid solutions. The surface changes accompanying voltammetric scans were analysed with the aid of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The influence of the GC pretreatment (polished versus electrochemically activated) on the oxidation of SO₂ was examined. It was found that GC samples electrochemically treated so to develop a reduced graphite oxide film on the surface were more active for SO₂ oxidation. The reduction of SO₂ was observed to take place at potentials below 0.0 V to yield soluble sulfide species. This species was reoxidized on positive scans to form a sulfur deposit, consisting of an underlying layer of chemisorbed sulfur (161.9-162.3 eV) and an on-top layer of bulk elemental sulfur with S₈-like structure (163.6-163.8 eV). Surface sulfur did not impart electrocatalytic activity for the oxidation of SO₂.     

Nanosized α-LiFeO2 as electrochemical supercapacitor electrode in neutral sulfate electrolytes

In this work we have explored the electrochemical properties of two lithiated iron oxide powders for supercapacitor purposes. These samples mainly consisted of α-LiFeO₂ in nanosized or micrometric form. Electrolyte was an aqueous 0.5 M Li₂SO₄ solution and voltage range studied was between 0 and −0.7 V vs. a Ag/AgCl reference electrode. As expected, electrochemical performance was dependent on the particle size. When electrolyte was deaerated a stable capacitance of ≈50 F g⁻¹ is provided by the nanosized sample for several hundred cycles. Other sulfate based salts (Na₂SO₄, K₂SO₄, Cs₂SO₄) were investigated as electrolytes but only Li₂SO₄ leads to a stable capacitance upon cycling, probably due to lithium intercalation. An hybrid cell consisting of this sample and MnO₂ as negative and positive electrodes, respectively, delivered 0.3 F cm⁻² (10 F g⁻¹). Although these values are lower than reported for other aqueous hybrid cell, α-LiFeO₂/MnO₂ asymmetric capacitor is interesting from both, an economic and an environmental point of view.     

Hot corrosion behaviors of gas tunnel type plasma sprayed La2Zr2O7 thermal barrier coatings

Gas tunnel type plasma sprayed free-standing La₂Zr₂O₇ coating specimens with a thickness of 300-400 μm were prepared under optimized operating conditions and were subjected to hot corrosion test in the presence of corrosive impurities such as V₂O₅, Na₂SO₄, and Na₂SO₄ + V₂O₅ mixtures (60:40 wt%) at two different temperatures for duration of 5 h, i.e. 1000 and 1350 K for V₂O₅ and Na₂SO₄ + V₂O₅ mixtures, 1200 and 1350 K for Na₂SO₄. For temperatures at 1350 K, the reaction mechanism of V₂O₅ and the mixture of Na₂SO₄ + V₂O₅ are similar and LaVO₄ is formed as the corrosive product, which leads to massive phase transformation from pyrochlore to tetragonal and monoclinic phases. Microstructural observations from planar reaction zone (PRZ) and melt infiltrated reaction zone (MIRZ) reveals that the present La₂Zr₂O₇ coating exhibits good hot corrosion resistance in V₂O₅ environment and moderate for the mixture of Na₂SO₄ + V₂O₅, but is worst in Na₂SO₄ environment.     

Enhancement of H2 and CH4 adsorptivities of single wall carbon nanotubes produced by mixed acid treatment

Single wall carbon nanotubes (SWCNTs) were treated with a HNO₃/H₂SO₄ mixed solution to increase the number of narrow micropores. The mixed acid treatment increased the micropore volume from 0.13 to 0.35 mL g⁻¹ as measured by N₂ adsorption at 77 K. The micropore volume evaluated with CO₂ adsorption at 273 K increased from 0.06 to 0.27 mL g⁻¹. This remarkable micropore volume increase was ascribed to the formation of a highly packed and ordered SWCNT assembly with the acid treatment, which was confirmed by field emission scanning electron microscopy. The adsorption amount of supercritical H₂ at 77 K under 5 MPa pressure increased twofold as a result of the acid treatment, while the supercritical CH₄ adsorption amount at 303 K and 5 MPa pressure increased by 40%. These remarkable increases were caused by increased amount of narrow micropores as a result of the acid treatment.