Development of a new biosensor for mediatorless voltammetric determination of hydrogen peroxide and its application in milk samples

A new biosensor for the voltammetric detection of hydrogen peroxide was developed based on immobilization of catalase on a clinoptilolite modified carbon paste electrode using bovine serum albumin and glutaraldehyde. The biosensor response was evaluated according to electrode composition, reaction time, solution pH and temperature. The voltammetric signals were linearly in proportion to H₂O₂ concentration in the range 5.0 × 10⁻⁶–1.0 × 10⁻³ M with a correlation coefficient of 0.9975. The detection limit is 8.0 × 10⁻⁷ M and the relative standard deviation for 4.0 × 10⁻⁴ M hydrogen peroxide was 1.83% (n = 6). The biosensor exhibited high sensitivity, and it was determined that it could be used for more than 2 months. In addition, the biosensor was successfully applied for the determination of hydrogen peroxide in milk samples.     

Oxygen electroreduction on Ag(1 1 1): The pH effect

The rotating ring disk method (RRDE) is applied to investigate the pH effect on oxygen reduction reaction (ORR) on Ag(1 1 1) single crystal surface in 0.1 M KOH and 0.1 M HClO₄. In 0.1 M KOH, the ORR proceeds through 4e⁻ reaction pathway with a very small (0.5-2.5%) peroxide formation in the entire potential range. In 0.1 M HClO₄ the onset potential for the ORR is shifted for ca. 400 mV toward the higher overpotentials compared to the 0.1 M KOH solution. At the low overpotentials, in 0.1 M HClO₄ the ORR proceeds entirely as a 2e⁻ process, i.e, 100% H₂O₂ formation. At higher overpotentials, the initial mixed a 2e⁻ and 4e⁻ reduction is followed by the potential region where the ORR proceeds entirely as a 4e⁻ process, with H₂O formation as a final product. The pH dependent shift in the onset of the ORR as well as the reaction pathway has been explained based on both: a thermodynamic analysis of pH independent rate determining step, and on the pH dependent change in availability of surface active sites and adsorption energies of molecular oxygen and reaction intermediates.     

Electrochemical behavior of non-precious dental alloys in bleaching agents

Corrosion behavior of dental alloys in artificial saliva containing different concentrations of hydrogen peroxide, carbamide peroxide and fluoride ions was studied using electrochemical technique. The alloys have been arranged according to its corrosion resistance in the hydrogen peroxide and carbamide peroxide as follows: wiron99 > wirolloy > wironit. Alloys suffer less corrosion rates in presence of carbamide peroxide than hydrogen peroxide. The effect of CH₆N₂O₃ on the corrosion is less than the effect of H₂O₂ and this is due to the presence of centers rich by electrons such as nitrogen and oxygen in CH₆N₂O₃. Nitrogen and oxygen adsorbed on the alloy surface forming protective layer isolate it relatively from the corrosive medium. The order of increasing resistivity of the alloys in fluoride solution is as follows: wironit > wiron99 > wirolloy. SEM for the three alloys in artificial saliva containing 0.015 M F⁻ shows that wironit has less corrosion compared to the two other alloys and this agrees with the results obtained from potentiodynamic polarization curves and Nyquist impedance diagrams.     

Scale-up of the perforated bipole trickle-bed electrochemical reactor for the generation of alkaline peroxide

This paper reports work on the scale-up of a perforated bipole trickle-bed electrochemical reactor for the electro-synthesis of alkaline peroxide. The reactor uses a relatively simple cell configuration in which a single electrolyte flows with oxygen gas in a flow-by graphite felt cathode, sandwiched between a microporous polyolefin diaphragm and a nickel mesh/perforated Grafoil anode/bipole. Both one and two-cell reactors are scaled-up from cathode dimensions 120 mm high by 25 mm wide and 3.2 mm thick (reactor-A) to 630 mm high by 40 mm wide and 3.2 mm thick (reactor-B). The scale-up is achieved by the use of constrictions that prevent segregation of the 2-phase flow in the larger cell, combined with switching from a polypropylene to a polyethylene diaphragm with improved transport properties and raising the electrolyte feed concentration from 1 to 2 M NaOH.For the one-cell reactor-B with a polypropylene diaphragm, operating on a feed of 1 M NaOH and oxygen at 900 kPa(abs)/20 °C, the peroxide current efficiency at a superficial current density of 5 kA m⁻² increases from 27% (un-constricted cathode) to 57% with a constricted cathode. The corresponding current efficiencies at 3–5 kAm⁻² for reactor-A and the constricted reactor-B are respectively 69–64% and 66–57%. Under similar conditions at 3–5 kA m⁻² the one-cell constricted reactor-B with a polyethylene diaphragm gives current efficiencies of 88–64%, and changing to an electrolyte of 2 M NaOH raises this range to 90–80%. At 3–5 kA m⁻² the equivalent two-cell (bipolar) constricted reactor-B shows current efficiencies of 82–74% and at 5 kA m⁻² obtains 0.6 M peroxide in 2 M NaOH with specific energy 6.5 kWh per kg H₂O₂.     

Oxidation of herbicides by in situ synthesized hydrogen peroxide and fenton’s reagent in an electrochemical flow reactor: study of the degradation of 2,4-dichlorophenoxyacetic acid

This paper reports an investigation of H₂O₂ electrogeneration in a flow electrochemical reactor with RVC cathode, and the optimization of the O₂ reduction rate relative to cell potential. A study of the simultaneous oxidation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by the in situ electrogenerated H₂O₂ is also reported. Experiments were performed in 0.3 M K₂SO₄ at pH 10 and 2.5. Maximum hydrogen peroxide generation rate was reached at −1.6 V versus Pt for both acidic and alkaline solutions. Then, 100 mg L⁻¹ of 2,4-D was added to the solution. 2,4-D, its aromatic intermediates such as chlorophenols, chlororesorcinol and chlorinated quinone, as well as TOC were removed at different rates depending on pH, the use of UV radiation and addition of Fe(II). The acidic medium favored the hydroxylation reaction, and first order apparent rate constants for TOC removal ranged from 10⁻⁵ to 10⁻⁴ s⁻¹. In the presence of UV and iron, more than 90% of TOC was removed. This value indicates that some of the intermediates derived from 2,4-D decomposition remained in solution, mainly as more biodegradable light aliphatic compounds.     

Gold nanoparticles mediate the assembly of manganese dioxide nanoparticles for H2O2 amperometric sensing

Aggregates of gold nanoparticles (AuNPs) that mediate the assembly of manganese dioxide nanoparticles (nano-MnO₂) for hydrogen peroxide (H₂O₂) amperometric sensing have been developed. The aggregates were prepared by directly mixing citric-capped AuNPs and poly(allylamine hydrochloride) (PAH)-capped nano-MnO₂ using an electrostatic self-assembly strategy. The prepared sensor exhibited excellent electrochemical behaviors and a wide linear range from 7.80 × 10⁻⁷ to 8.36 × 10⁻⁴ M with a detection limit of 4.68 × 10⁻⁸ M (S/N = 3) because of the synergistic influence of excellent catalytic ability of MnO₂ and good electrical conductivity of AuNPs. In addition, its applicability to practical samples for measuring H₂O₂ in toothpastes has obtained a satisfactory result. Due to the ease of preparation and excellent properties of the sensor, indicating the MnO₂-AuNP material may be a potential H₂O₂ sensor.     

The Impact of Traces of Hydrogen Peroxide and Phosphate on the Ozone Decomposition Rate in “Pure Water”

To obtain an idea of the magnitudes of the ozone loss rates r_O3 in practical applications of ozone, an overall determination of the ozone decay profiles and rate constants was carried out in four different systems. These systems resemble different conditions for industrial application of ozone and the peroxone process, such as in the field of micro electronics, drinking water purification, disinfection, etc. Therefore, the behavior of ozone was monitored in the pH range from 4.5 to 9.0, in pure water and phosphate buffered systems in absence and presence of small amounts of hydrogen peroxide (10^?7 M to 10^?5 M H₂O₂). First the reproducibility of the ozone decay profiles was checked and from the various kinetic formalism tests, the reaction order 1.5 for the ozone decay rate has been selected. As expected, hydrogen peroxide increases the decay rates. In pure systems, added concentrations of 10^?7M H₂O₂ already cause a remarkable acceleration of the ozone decay in the acidic and neutral pH range compared to the pure systems. However for alkaline pH conditions almost no effect of the low hydrogen peroxide concentrations was noticed. Contradictory to literature data, in the absence of hydrogen peroxide, ozone displays faster decays in the buffered systems of low ionic strength of 0.02 compared to pure water. This acceleration is more pronounced for acidic pH conditions. Low concentrations of phosphate may indeed accelerate the ozone decay in the presence of organic matter. Adding H₂O₂ concentrations below 10^?5M to phosphate buffered solutions has a negligible effect on the ozone decay rate compared with pure water systems, except for pH 7. It appears that phosphate masks the effect of hydrogen peroxide below 10^?5 M as tested here. Thus the application of AOP's by adding low concentrations of hydrogen peroxide is not well feasible in the presence of phosphate buffers in pure water systems.     

Electro-Oxidation of Carbonate in Aqueous Solution on a Platinum Rotating Ring Disk Electrode

The kinetics of electro-oxidation of carbonate aqueous solution on a platinum electrode were examined by a rotating ring (platinum) – disk (platinum) electrode in aqueous sodium carbonate/bicarbonate solutions (25 °C, pH = 10.75) with the peroxide stabilizing additives sodium silicate, magnesium sulphate and sodium DTPA such as are used in brightening mechanical wood pulp. A theoretical model based on the experimental data is proposed to describe this electro-oxidation process. The model shows consistency between the experimental results and the expectation from the proposed reaction sequence. The first-order rate constants at 25 °C, pH = 10.75 in 1.13 M (Na₂CO₃ + NaHCO₃) for carbonate electro-oxidation to percarbonate (a.k.a. peroxidicarbonate C₂O₆^2-), percarbonate hydrolysis to hydrogen peroxide and hydrogen peroxide electro-oxidation to oxygen are estimated from the experimental data, respectively, as (1.43±0.1) × 10⁻¹¹cm s⁻¹ (extrapolated to the equilibrium electrode potential which is estimated as ca. 0.21 (vs SCE)), (1.1 ± 0.2) × 10⁻² s⁻¹ and (5.6±0.5) × 10⁻⁸cm s⁻¹ (extrapolated to the equilibrium electrode potential of −0.019 V (vs SCE)).     

Preparation of tungsten oxide nanoporous thin film at carbon ceramic electrode for electrocatalytic applications

The electrodeposition of nanoporous tungsten oxide (WO₃) on the surface of carbon ceramic electrode (CCE) was described. The morphology of the WO₃ modified electrode was characterized by scanning electron microscopy and X-ray diffraction. The modified electrode was utilized as an electrochemical hydrogen peroxide sensor in a low potential with a high sensitivity and selectivity. The role of supporting matrix on the sensitivity of modified electrode was studied. The detection limit of 0.26 μM (S/N = 3) and the sensitivity of 16.8 A M⁻¹ cm⁻² were compared with some other metal oxides hydrogen peroxide sensors. The modified electrode has exhibited good reproducibility, long-term stability and negligible interference of some inorganic and biological compounds.     

Influence of surfactants on the electroreduction of oxygen to hydrogen peroxide in acid and alkaline electrolytes

The effect of surfactants on the electroreduction of O₂ to H₂O₂ was investigated by cyclic voltammetry and batch electrolysis on vitreous carbon electrodes. The electrolytes were either 0.1 M Na₂CO₃ or 0.1 M H₂SO₄ at 295 K, under 0.1 MPa O₂. Electrode kinetics and mass transport parameters showed the influence of surfactants on the O₂ electroreduction mechanism. The cationic surfactant (Aliquat 336^®, tricaprylmethylammonium chloride), at mM levels, increased the standard rate constant of O₂ electroreduction to H₂O₂ 15 times in Na₂CO₃ and 1900 times in H₂SO₄, to 1.8 × 10^–6 m s^–1 and 9.9 × 10^–10 m s^–1, respectively. This effect on the reaction rate might be due to an increase of the surface pH, induced by the Aliquat 336^® surface film. The nonionic (Triton X-100) and anionic (sodium dodecyl sulfate) surfactants retarded the O₂ electroreduction, presumably by forming surface structures, which blocked the access of O₂ to the electrode. Ten hour batch electrosynthesis experiments performed at 300 A m^–2 superficial current density, 0.1 MPa O₂, 300 K, on reticulated vitreous carbon (30 ppi), showed that compared to the values obtained in the absence of surfactant, mM concentrations of Aliquat 336^® increased the current efficiency for peroxide from 12% to 61% (0.31 M H₂O₂) in 0.1 M Na₂CO₃ and from 14% to 55% (0.26 M H₂O₂) in 0.1 M H₂SO₄, respectively.     

Kinetic correlation between degradation and dechlorination of perchloroethylene in the Fenton reaction

In the Fenton reaction, degradation and dechlorination are directly affected by the concentrations of hydrogen peroxide and Fe³⁺. Although there is considerable research on the biodegradation of chlorinated compounds combined with the Fenton reaction, the kinetics of degradation and dechlorination of the reaction, with various concentrations of hydrogen peroxide and Fe³⁺, have been rarely investigated. Therefore, we investigated the degradation and dechlorination of PCE with various concentrations of hydrogen peroxide and Fe³⁺. The initial concentration of PCE (10 μM) decreased from a value of 8.9 μM (with 0.1 mM of hydrogen peroxide and 5 mM of Fe³⁺) to 1.1 μM (with 10 mM of hydrogen peroxide and 5 mM of Fe³⁺); the respective values for chloride ions produced were 0.9 and 21.6 μM. Also, the initial 10 μM of PCE decreased from 8.9 (with 0.1 mM of Fe³⁺ and 5 mM of hydrogen peroxide) to 2.2 μM (with 10mM of Fe³⁺ and 5 mM of hydrogen peroxide); the respective chloride ions produced were 0.7 and 14.5 μM. The logarithmic correlations between the degradation and dechlorination coefficients were 0.7682 and 0.7834 for concentrations of hydrogen peroxide and Fe³⁺, respectively. Both coefficients were used, from all possible cases, to derive six models which displayed both the ratio of degradation and dechlorination and the hydrogen peroxide and Fe³⁺ concentrations. The dechlorination of PCE could then be predicted with the model obtained by the coefficient with the concentration of hydrogen peroxide and Fe³⁺. The models could be applied to various Fenton reactions for optimization of degradation or dechlorination, such as biodegradation of PCE which is scarcely degraded by aerobic bacteria.     

Sol-gel derived carbon ceramic electrode for the investigation of the electrochemical behavior and electrocatalytic activity of neodymium hexacyanoferrate

The electrochemical properties of an electroactive rare earth metal hexacyanoferrate, neodymium hexacyanoferrate (NdHCF) were studied by mechanically attaching NdHCF samples to the surface of carbon ceramic electrodes (CCEs) derived from sol-gel technique. The resulting modified electrodes exhibit well-defined redox responses with the formal potential of 0.241 V (versus SCE) at a scan rate of 20 mV s⁻¹ in 0.5 M KCl solution. The voltammetric characteristics of the NdHCF-modified CCEs in the presence of different alkali metal cations (Li⁺, Na⁺, K⁺, Rb⁺ and Cs⁺) were investigated by voltammetry. The NdHCF-modified CCEs presented a good electrocatalytic activity towards the reduction of hydrogen peroxide (H₂O₂), and was used for amperometric detection of H₂O₂. In addition, the NdHCF-CCEs exhibited a distinct advantage of simple preparation, surface renewal, good stability and reproducibility.     

Paired electrosynthesis of epoxides and dibromides from olefinic compounds

A VO(acac)₂/[VO(acac)₂OOH]⁻ redox mediator was used for the cathodic oxidation of olefinic compounds to the corresponding epoxides. The oxidation process consists of a multi-step such as (a) cathodic reduction of dioxygen to hydrogen peroxide, (b) chemical oxidation of VO(acac)₂ to [VO(acac)₂OOH]⁻ with the resulting hydrogen peroxide, (c) the chemical epoxidation of olefins with [VO(acac)₂OOH]⁻, and (d) the regeneration of VO(acac)₂. On the other hand, the olefinic compounds are indirectly oxidized (brominated) with a Br⁻/Br⁺ mediator to give the corresponding 1,2-dibromides. Pairing this indirect anodic oxidation (bromination) with the above indirect cathodic epoxidation, an efficient paired electrosynthetic system could be developed for preparation of epoxides and 1,2-dibromides.     

Electrosynthesis of hydrogen peroxide in acidic solutions by mediated oxygen reduction in a three-phase (aqueous/organic/gaseous) system Part I: Emulsion structure, electrode kinetics and batch electrolysis

The mediated electrosynthesis of H₂O₂ in acidic solutions (pH 0.9–3.0) was investigated in a three-phase, aqueous/organic/gaseous system using 2-ethyl-9,10-anthraquinone (EtAQ) as mediator (redox catalyst). The main hydrogen peroxide producing route is the in situ mediating cycle: EtAQ electroreduction–homogeneous oxidation of anthrahydroquinone (EtAQH₂). The organic phase was composed of tributylphosphate solvent (TBP) with 0.2 M tetrabutylammonium perchlorate (TBAP) supporting electrolyte, 0.06 M tricaprylmethylammonium chloride (A336) surface active agent, and 0.1–0.2 M EtAQ mediator. Part I of this two part work deals with the physico-chemical characteristics of the emulsion electrolyte (e.g., ionic conductivity, emulsion type, H₂O₂ partition between the aqueous and organic phases), and kinetic aspects (both electrode and homogenous) of the mediation cycle. Furthermore, batch electrosynthesis experiments are presented employing reticulated vitreous carbon cathodes (specific surface area 1800 m² m^–3) operated at superficial current densities of 500–800 A m^–2. During 10 h batch electrolysis involving the emulsion mediated system with O₂ purge at 0.1 MPa pressure, H₂O₂ concentrations in the range 0.53–0.61 M were obtained in 0.1 M H₂SO₄ (pH 0.9) and 2 M Na₂SO₄(acidified to pH3). The corresponding apparent current efficiencies were from 46 to 68%. Part II of the present work describes investigations using flow-by fixed-bed electrochemical cells with co-current upward three-phase flow.     

Electrocatalysis by design: Effect of the loading level of Au nanoparticles-MnOx nanoparticles binary catalysts on the electrochemical reduction of molecular oxygen

This study concerns the efficient electrochemical reduction of molecular oxygen (O₂), in O₂-saturated 0.1 M KOH solution, to OH⁻ through a four-electron reduction pathway by a novel binary catalyst that is comprised of two kinds of catalysts, i.e., Au nanoparticles (nano-Au) and manganese oxide nanoparticles (nano-MnOx) electrodeposited onto a relatively inert substrate, e.g., glassy carbon (GC) electrode. The nano-Au catalyst is efficiently used for the electro-reduction of O₂ to hydrogen peroxide through a two-electron reduction pathway at a reasonably low overpotential. While the latter (i.e., nano-MnOx) is effectively used for the subsequent catalytic decomposition of the electrogenerated hydrogen peroxide to water and molecular oxygen. The dependence of the electrocatalytic activity of the proposed binary catalysts towards the oxygen reduction on the loading level of both species has been investigated in this paper. This is done aiming at the preparation of a binary catalyst composed of the optimum amounts of both species which supports an apparent four-electron reduction of O₂ at sufficiently low overpotential in replacement of the costly Pt-based electrocatalysts.     

Kinetics of hydrogen peroxide oxidation of alkyl dimethyl amines

We measured the absolute rate constants for the hydrogen peroxide oxidation of two different octyl dimethyl amines in isopropanol/water mixtures at 23°C. The amines were 1-octyl dimethyl amine (1) and 2-ethylhexyl dimethyl amine (2); their structures were analogous to those most often encountered in commercial alkyl dimethyl amine oxide production. The observed first-order rate constants for the disappearance of amine across a range of H₂O₂ concentrations (0.5–8 M) indicated that the overall rate was first-order in amine and 3/2-order in H₂O₂. Calculations showed k ₁=0.16 M⁻¹h⁻¹, k ₂=0.046 M⁻¹h⁻¹, and k ₁/k ₂=3.5. The rates appeared to decrease with increasing steric hindrance around the nitrogen atom. We also investigated the effect of water on the reaction rates. When [H₂O]<∼4.5 M in isopropanol, the rates increased with increasing [H₂O]; for [H₂O]>∼4.5 M, the rates were insensitive to [H₂O].     

Simultaneous electrosynthesis of alkaline hydrogen peroxide and sodium chlorate

Simultaneous electrosynthesis of alkaline hydrogen peroxide and sodium chlorate in the same cell was investigated. The alkaline hydrogen peroxide was obtained by the electroreduction of oxygen in NaOH on a fixed carbon bed while the chlorate was obtained by the reaction of anodic electrogenerated hypochlorite and hypochlorous acid in an external reactor. An anion membrane, protected on the anode side with an asbestos diaphragm, was used as the separator between the two chambers of the cell. The trickle bed electrode of dimensions 0.23 m high ×0.0362 m wide × 0.003 m thick was used on the cathode side. The anolyte chamber of the cell, 0.23 m high × 0.0362 m, wide × 0.003 m thick was operated at a fixed anolyte flow of 2.0 × 10^–6 m³ s^–1 while the oxygen loadings in the trickle bed was kept constant at 0.102 kg m^–2 s^–1. Other operating conditions include inlet and outlet temperatures of 27–33°C (anode side), 20–29°C (cathode side), cell voltages of 3.0–4.2 V (at current density of 1.2–2.4 kAm^–2) and a fixed temperature of 70°C in the anolyte tank.The effects of superficial current density, NaOH concentration (0.5–2.0 M) and catholyte liquid loadings (0.92–4.6 kg m^–2 s^–1) on the chlorate and peroxide current efficiencies were measured. The effect of peroxy to hydroxyl mole ratio on the chlorate current efficiency was also determined.Depending on the conditions, alkaline peroxide solution and sodium chlorate were cogenerated at peroxide current efficiency between 20.0 and 86.0%; chlorate current efficiency between 51.0 and 80.6% and peroxide concentration ranging from 0.069 to 0.80 M. The cogeneration of the two chemicals was carried out at both concentrated (2.4–2.8 M) and dilute (0–0.5 M) chlorate solutions. A relative improvement on the current efficiencies at concentrated chlorate was observed. A chloride balance indicated a less than 0.4% chloride loss to the catholyte. The results are interpreted in terms of the electrochemistry, chemical kinetics and the hydrodynamics of the cell.Nomenclature C _i concentration of speciesi (mol m^–3) - F Faraday constant (96 500 C mol^–1) - I current (A) - Q catholyte flow rate (m³s^–1) - total time of cell operation (s) - _i current efficiency of speciesi (%)     

Hydrothermal synthesis of well-stable silver nanoparticles and their application for enzymeless hydrogen peroxide detection

We reported on a facile hydrothermal synthesis of well-stable silver nanopartiles (AgNPs) from an aqueous solution of AgNO₃ and poly[(2-ethyldimethylammonioethyl methacrylate ethyl sulfate)-co-(1-vinylpyrrolidone)] (PQ11), a kind of cationic polyelectrolyte, at 100 °C without the extra introduction of other reducing agents and protective agents. Transmission electron microscopy (TEM) observation reveals that the AgNPs thus formed mainly consist of small nanoparticles about 5 nm in diameter. It is found that such dispersion can form stable AgNPs-embedded films on bare electrode surfaces and these nanoparticles exhibit remarkable catalytic performance for hydrogen peroxide (H₂O₂) detection. The sensor has a fast amperometric response time of less than 2 s. The linear range is estimated to be from 1 × 10⁻⁴ M to 0.18 M (r = 0.998) and the detection limit is estimated to be 3.39 × 10⁻⁵ M at a signal-to-noise ratio of 3, respectively.     

Electrochemically multi-anodized TiO2 nanotube arrays for enhancing hydrogen generation by photoelectrocatalytic water splitting

An enhanced hydrogen production by photoelectrocatalytic water splitting was obtained using extremely highly ordered nanotubular TiO₂ arrays in this work. Highly ordered TiO₂ nanotube arrays with a regular top porous morphology were grown by a facile and green three-step electrochemical anodization. The well ordered hexagonal concaves were uniformly distributed on titanium substrate by the first anodization, served as a template for further growth of TiO₂ nanotubes. As a result, the TiO₂ nanotube arrays constructed through the third anodization showed appreciably more regular architecture than that of the sample by conventional single anodization under the same conditions. The enhanced photoelectrochemical activity was demonstrated through the hydrogen generation by photoelectrocatalytic water splitting, with an exact H₂ evolution rate up to 420 μmol h⁻¹ cm⁻² (10 mL h⁻¹ cm⁻²) in 2 M Na₂CO₃ + 0.5 M ethylene glycol. The photocurrent density of the third-step anodic TiO₂ nanotubes is about 24 mA cm⁻² in 0.5 M KOH, which is 2.2 times higher than that of the normal TiO₂ nanotubes (∼11 mA cm⁻²) by a single electrochemical anodization.     

An Effective Amperometric Biosensor Based on Gold Nanoelectrode Arrays

A sensitive amperometric biosensor based on gold nanoelectrode array (NEA) was investigated. The gold nanoelectrode array was fabricated by template-assisted electrodeposition on general electrodes, which shows an ordered well-defined 3D structure of nanowires. The sensitivity of the gold NEA to hydrogen peroxide is 37 times higher than that of the conventional electrode. The linear range of the platinum NEA toward H₂O₂ is from 1 × 10⁻⁶ to 1 × 10⁻² M, covering four orders of magnitudes with detection limit of 1 × 10⁻⁷ M and a single noise ratio (S/N) of four. The enzyme electrode exhibits an excellent response performance to glucose with linear range from 1 × 10⁻⁵ to 1 × 10⁻² M and a fast response time within 8 s. The Michaelis–Menten constant km and the maximum current density i _max of the enzyme electrode were 4.97 mM and 84.60 μA cm⁻², respectively. This special nanoelectrode may find potential application in other biosensors based on amperometric signals.