The non-linear fitting method to analyze the measured M-S plots of bipolar passive films

Mott-Schottky (M-S) analysis is an effective approach to investigate the electronic property of passive films of metals, and it is well suitable for the passive film with single space charge capacitance. But there is no proper method to analyze the C_sc⁻² vs. V_m plots of passive films with several space charge capacitances in series connection, such as bipolar passive films. In this paper, the relationship between the space charge capacitance of the bipolar passive film and the applied potential was deduced and the features of corresponding plots were given out simultaneously. Accordingly, a non-linear fitting method was presented to analyze the C_sc⁻² vs. V_m plots of bipolar passive films. Then the method was used to study the semiconductor characteristics of bipolar passive films formed on the surface of Nickel base alloy after being corroded in the environments with high temperatures and high partial pressures of H₂S/CO₂. The fitting results indicate that the non-linear fitting of M-S plots can well help to understand the anti-corrosion mechanism of bipolar passive films.     

Effects of solution temperature on electronic properties of passive film formed on Fe in pH 8.5 borate buffer solution

Effects of solution temperature on the electronic properties of passive film formed on Fe in pH 8.5 borate buffer solution were investigated to clarify why the passive current density of Fe increases with solution temperature. The Mott-Schottky analysis and photocurrent measurement were employed to determine the electronic properties of the film. The Mott-Schottky analysis and photocurrent measurement revealed that as solution temperature increased, the concentration of oxygen vacancy in the passive film increased accompanying with an increase in the concentration of Fe²⁺ ion in the γ-Fe₂O₃ passive film due to a charge neutrality reaction in the film. Further, the increase in passive current density of Fe with solution temperature was found due primarily to the increase in the concentration of oxygen vacancy in the passive film, which is well explained by the point defect model (PDM).     

Electrochemical detection of in situ DNA damage with layer-by-layer films containing DNA and glucose oxidase and protection effect of catalase layers against DNA damage

Natural double-stranded DNA and the enzyme glucose oxidase (GOD) were assembled into layer-by-layer films on electrode surface. In the presence of glucose and Fe²⁺ in incubation solutions, GOD in the films could catalyze the reaction of glucose and O₂, and the produced H₂O₂ would further react with Fe²⁺, generating hydroxyl radical (OH) as in the Fenton reaction, which could severely damage DNA in the films. The electrocatalytic oxidation of DNA guanines by (bpy = 2,2′-bipyridine) produced by electrooxidation of at the electrodes was used to detect DNA damage induced by the in situ Fenton reaction. The additional catalase (Cat) layers assembled into the films could effectively protect the DNA from damage by decomposing the H₂O₂ produced in situ, and only when the Cat layers were located in close proximity to the GOD layers, the protection of DNA in the inner layers was most effective. The present work provides an in vitro model system to mimic the real bioprocess in DNA damage and protection through a simple electrochemical approach combined with layer-by-layer assembly.     

Electrochemical corrosion behavior of nanocrystallized bulk 304 stainless steel

By employing Mott-Schottky analysis in conjunction with the point defect model (PDM), we compared donor density and donor diffusion coefficients in the passive films formed on the surface of nanocrystallized bulk 304 stainless steel (NB304ss) and cast 304 stainless steel (304ss) in 0.05 mol/L H₂SO₄ + 0.25 mol/L Na₂SO₄ solution. The donor density at the metal/film interface of the NB304ss was lower than that at the metal film interface of the cast 304ss. Based on the Mott-Schottky analysis, an exponential relationship between donor density and formation potentials of the passive films on the NB304ss and the cast 304ss was built up. The results showed that the donor diffusion coefficients in the passive film formed on the surface of NB304ss was lower than that in the cast 304ss. The lower donor density and the lower diffusion coefficient restrained the electrochemical reaction in the passive film and improved the stability of the passive film. That is the reason why the passive film formed on the NB304ss was more protective.     

Development of electrochemical oxidase biosensors based on carbon nanotube-modified carbon film electrodes for glucose and ethanol

Functionalised multi-walled carbon nanotubes (MWCNTs) were cast on glassy carbon (GC) and carbon film electrodes (CFE), and were characterised electrochemically and applied in a glucose-oxidase-based biosensor. MWCNT-modified carbon film electrodes were then used to develop an alcohol oxidase (AlcOx) biosensor, in which AlcOx-BSA was cross-linked with glutaraldehyde and attached by drop-coating. The experimental conditions, applied potential and pH, for ethanol monitoring were optimised, and ethanol was determined amperometrically at −0.3 V vs. SCE at pH 7.5. Electrocatalytic effects of MWCNT were observed with respect to unmodified carbon film electrodes. The sensitivity obtained was 20 times higher at carbon film/MWCNT-based biosensors than without MWCNT.     

Dual oxygen and Ir oxide regeneration of glucose oxidase in nanostructured thin film glucose sensors

A nanoparticulate iridium oxide (IrOx) thin film has been developed as a redox-active matrix material for an advanced generation glucose biosensor, in which IrOx serves as the non-physiological mediator, replacing oxygen in the enzymatic re-oxidation of glucose oxidase (GOx). Ethanolic solutions of Nafion and an Ir sol were mixed with an aqueous GOx solution and then deposited on a Au support. The Ir nanoparticles were then oxidized electrochemically to IrOx and the resulting films (IrOx-GOx-Nafion) were tested for their glucose response in both oxygen- and argon-saturated solutions, with the oxygen content in both solutions monitored by a Pt electrode. The sensors that are regenerated largely by O₂ are characterized by a Michaelis-Menten K^′m value of ∼30 mM or more and i_max values of at least 20 μA cm⁻². Under fully deareated conditions, the sensors lose only ∼50% of their response to glucose, clearly indicating that a dual oxygen-regeneration and IrOx mediation mechanism is operative for the biosensor under these conditions. Under optimized conditions, involving a controlled GOx:Ir ratio, only the Ir oxide sites in the film serve to mediate GOx regeneration, giving K^′m (10-15 mM) and i_max values that are independent of the O₂ content of the solution.     

Direct electrochemistry of glucose oxidase assembled on graphene and application to glucose detection

The direct electrochemistry of glucose oxidase (GOx) integrated with graphene was investigated. The voltammetric results indicated that GOx assembled on graphene retained its native structure and bioactivity, exhibited a surface-confined process, and underwent effective direct electron transfer (DET) reaction with an apparent rate constant (k_s) of 2.68 s⁻¹. This work also developed a novel approach for glucose detection based on the electrocatalytic reduction of oxygen at the GOx-graphene/GC electrode. The assembled GOx could electrocatalyze the reduction of dissolved oxygen. Upon the addition of glucose, the reduction current decreased, which could be used for glucose detection with a high sensitivity (ca. 110 ± 3 μA mM⁻¹ cm⁻²), a wide linear range (0.1-10 mM), and a low detection limit (10 ± 2 μM). The developed approach can efficiently exclude the interference of commonly coexisting electroactive species due to the use of a low detection potential (−470 mV, versus SCE). Therefore, this study has not only successfully achieved DET reaction of GOx assembled on graphene, but also established a novel approach for glucose detection and provided a general route for fabricating graphene-based biosensing platform via assembling enzymes/proteins on graphene surface.     

Effects of 1-butyl-3-methylimidazolium tetrafluoroborate on the oxidation of glucose catalyzed by glucose oxidase

The effects of room temperature ionic liquids (ILs) on the conformation and electrocatalytic activity of enzymes were studied using glucose oxidase (GOx) and 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF₄) as models. UV-vis and circular dichroic (CD) spectra indicated that [bmim]BF₄ did not affect the conformation of the enzyme, and the secondary structure of GOx in [bmim]BF₄-PBS mixtures (the content of the IL is from 0 to 20 vol%) was essentially the same as that of the native one. The Raman spectra showed that no interaction existed between glucose and [bmim]BF₄. The oxidation of glucose catalyzed by GOx was investigated under a substrate-saturated condition in [bmim]BF₄-PBS mixtures using ferroceneacetic acid (FcA) as a mediator. The voltammetric results showed that electrocatalytic current (i_cat) decreased with the increase of the content of [bmim]BF₄ in the mixtures. The reason causing the decrease of i_cat was analyzed. The reduction in the diffusion rate of FcA due to the increase of the viscosity after the addition of the IL was a key factor of causing the decrease of i_cat. The results presented here will be useful for the designing of the related biosensor used in ILs-containing system.     

The structure and electronic properties of passive and prepassive films of iron in borate buffer

The films that form on pure iron during potentiodynamic anodic polarization in aqueous borate buffer were investigated by surface enhanced Raman spectroscopy (SERS), and by electrochemical impedance spectroscopy and Mott-Schottky analysis at selected potentials. According to SERS, the passive film is a bilayer film with an outer layer of an as yet undetermined Fe(III)oxide/hydroxide, identified by a strong Raman peak at 560 cm⁻¹. The inner layer was a spinel compound. The capacitances of passive iron were frequency dependent and a constant phase element (CPE) best described the frequency dispersion. Current increases in cathodic polarization scans confirmed the accuracy of flatband potentials calculated from Mott-Schottky tests at two different film formation potentials. Both films were found to be n-type and flatband potentials of −846 and −95 mV vs. SHE and carrier densities of 1.6 × 10²² and 8.3 × 10²⁰/cm³ were found for films grown at −500 and +1000 mV, respectively. The cathodic polarization curve of passivated iron exhibited a complex shape that was explained by the electronic properties of iron's passive and prepassive films. The reductive dissolution of the films abruptly began when the potential was lowered below their flatband potentials. It is suggested that the cathodic polarization behavior contributes to iron's susceptibility to localized corrosion.     

Chemical composition and electronic structure of the passive layer formed on stainless steels in a glucose-oxidase solution

This article deals with the interaction between the passive layer formed on UNS S30403 and S31254 stainless steels and an enzymatic solution containing glucose oxidase (GOx) and its substrate d-glucose. This enzymatic solution is often used to reproduce in laboratory the ennoblement occuring in non-sterile aerated aqueous environments because of the biofilm settlement on the surface of the metallic material. GOx catalyses the oxidation of d-glucose to gluconic acid by reducing oxygen to hydrogen peroxide and produces an organic acid. Thanks to photocurrent measurements, XPS analysis and Mott-Schottky diagrams, it is here shown that such an environment generates modifications in the chemical composition and electronic structure of the passive layer: it induces a relative enrichment of the n-type semi-conducting phase containing chromium (chromine Cr₂O₃) and an increase of the donors density in the space charge region.     

Layer by layer assembly of glucose oxidase and thiourea onto glassy carbon electrode: Fabrication of glucose biosensor

For the first time a novel, simple and facile approach is described to construct highly stable glucose oxidase (GOx) multilayer onto glassy carbon (GC) electrode using thiourea (TU) as a covalent attachment cross-linker. The layer by layer (LBL) attachment process was confirmed by cyclic voltammetry, electrochemical impedance spectroscopy and Fourier transform infrared reflection spectroscopy (FT-IR-RS) techniques. Immobilized GOx shows excellent electrocatalytic activity toward glucose oxidation using ferrocenemethanol as artificial electron transfer mediator and biosensor response was directly correlated to the number of bilayers. The surface coverage of active GOx per bilayer, heterogeneous electron transfer rate constant (k_s) and Michaelis–Menten constant (K_M), of immobilized GOx were 1.50 × 10⁻¹² mol cm⁻², 9.2 ± 0.5 s⁻¹ and 3.42(±0.2) mM, respectively. The biosensor constructed with four-bilayers of TU/GOx showed good stability, high reproducibility, long life-time, fast amperometric response (5 s) with the high sensitivity of 5.73 μA mM⁻¹ cm⁻² and low detection limit of 6 μM at concentration range up to 5.5 mM.     

Electrochemical corrosion behavior of nickel coating with high density nano-scale twins (NT) in solution with Cl

In this work, a nickel coating with high density nano-scale twins (NT) was synthesized on Q235 steel by using pulsed electrodeposition technique. The effects of NT structure on pitting corrosion resistance and semi-conducting properties of passive films formed on pure Ni in borate buffer solution with chloride ions were investigated by the potentiodynamic polarization measurements and capacitance measurements. The results indicated that the passive films formed on NT coatings showed higher pitting corrosion resistance and a bi-layer semi-conducting structure distribution, comparing with those formed on industrial electrodeposited (IE) nickel. The passive films are p-type semi-conductors at low potentials, but they show an n-type semi-conductor behavior at high potentials. It demonstrated that NT structure decreased vacancy diffusion velocity and slowed down the growth of passive films consequently. This led to the enhancement of pitting resistance for NT nickel.     

A hybrid photocatalytic and enzymatic process using glucose oxidase immobilized on TiO2/polyurethane for removal of a dye

A rectangular recycling photo-bioreactor using glucose oxidase (GOx) immobilized on TiO₂/polyurethane (PU) was developed as a novel coupling of photodegradation and enzymatic process. This method was tested for removal of Acid Orange 7 (AO7), as a model pollutant. High efficiency of decolorization (>99%) was achieved after 22 min using the GOx/TiO₂/PU photo-biocatalyst. Roles of various processes including photodegradation (TiO₂/PU), enzymatic process (GOx/PU) and a coupling of photocatalytic–enzymatic (GOx/TiO₂/PU) process were investigated in the presence and absence of UV light. All the experiments were performed in a circulation photoreactor equipped with a 6 W UV lamp with rate of 5 mL/min.     

Direct electron transfer and electrocatalysis of glucose oxidase immobilized on glassy carbon electrode modified with Nafion and mesoporous carbon FDU-15

In this paper, it was found that glucose oxidase (GOD) has been stably immobilized on glassy carbon electrode modified with mesoporous carbon FDU-15 (MC-FDU-15) and Nafion by simple technique. The sorption behavior of GOD immobilized on MC-FDU-15 matrix was characterized by transmission electron microscopy (TEM), ultraviolet-visible (UV-vis), FTIR, respectively, which demonstrated that MC-FDU-15 could facilitate the electron exchange between the active center of GOD and electrode. The direct electrochemistry and electrocatalysis behavior of GOD on the modified electrode were characterized by cyclic voltammogram (CV) which indicated that GOD immobilized on Nafion and MC-FDU-15 matrices display direct, reversible and surface-controlled redox reaction with an enhanced electron transfer rate constant of 4.095 s⁻¹ in 0.1 M phosphate buffer solution (PBS) (pH 7.12). Furthermore, it was also discovered that, in the presence of O₂, GOD immobilized on Nafion and MC-FDU-15 matrices could produce a linear response to glucose. Thus, Nafion/GOD-MC-FDU-15/GC electrode is hopeful to be used in glucose biosensor. In addition, GOD immobilized on MC-FDU-15 and Nafion matrices possesses an excellent bioelectrocatalytic activity for the reduction of O₂. So, the Nafion/GOD-MC-FDU-15/GC electrode can be utilized as the cathode in biofuel cell.     

Electrochemical impedance spectroscopy study of the passive films of alloy 22 in low pH nitrate and chloride environments

Utilizing electrochemical impedance spectroscopy (EIS), we characterize the passive film properties of alloy 22 during immersion in low pH nitrate and chloride solutions. In pure HCl, the passive film grows thinner with increasing acid concentration. In contrast, in HNO₃, the passive film corrosion protection properties are enhanced, which leads to low corrosion rates, even at pH < −0.5. The combined influence of both HCl and HNO₃ in contact simultaneously with the alloy 22 surface shows multiple phases in the passive film properties depending on the pH. EIS results show that the passive film changes either thickness and/or composition as the system is driven chemically through different corrosion states, including: active, passive, active/passive and transpassive.     

Correlation between repassivation kinetics and corrosion rate over a passive surface in flowing slurry

The effect of hydrodynamics of flowing slurry on anodic dissolution rate of passive metals was quantitatively evaluated using a theoretical model recently developed by the authors. The enhanced anodic dissolution over a passive metal in flowing slurry is dominated by the passive film breakdown caused by the impingement of solid particles and the decay of local current density over the impacted area due to repassivation. In the present study, the anodic current densities of 304 stainless steel and carbon steels were measured in flowing slurries under potentiostatic control condition. The difference in the repassivation modes indicates different repassivation mechanisms that depend on electrode material and corrosive medium. The parameters of repassivation kinetics experimentally determined enable estimation of the average anodic current density on the electrode surface in flowing slurry using the theoretical model. The theoretical predictions are in good agreement with the experimental data.     

Influence of yttrium as a minority alloying element on the corrosion behavior in Fe-based bulk metallic glasses

The role of yttrium in corrosion behavior in an HCl solution was studied systematically by comparing bulk FeCrMoCB metallic glasses with and without yttrium. The corrosion resistance was very sensitive to minor yttrium addition. The material exhibits a detrimental effect on corrosion resistance at 0.5 at.% yttrium addition while a beneficial effect at more yttrium additions. Such effects are argued to be associated with variations of the semiconductor properties of passive film (i.e. defects concentration and band structure of passive film), induced by minority yttrium alloying element doping. It was shown that there exhibits a bi-layer structure of passive film on Fe-based metallic glasses. The outer layer with high valence cations is responsible for the dissolution behavior of the passive film, whereas the inner layer with doped oxides connects with the semiconductor properties. This result presents us an important hint that the corrosion resistance of metallic glasses can be improved by elaborately tailoring the defect structure of passive film via proper additions of minor alloying elements.     

pH-controllable bioelectrocatalysis of glucose by glucose oxidase loaded in weak polyelectrolyte layer-by-layer films with ferrocene derivative as mediator

Oppositely charged poly(allylamine hydrochloride) (PAH) and hyaluronic acid (HA) were assembled into {PAH/HA}_n layer-by-layer (LBL) films on pyrolytic graphite (PG) electrodes. Glucose oxidase (GOD) in solution was then loaded into the films, designated as {PAH/HA}_n-GOD. When the {PAH/HA}_n-GOD film electrodes were placed in pH 5.0 buffers containing ferrocenedicarboxylic acid (Fc(COOH)₂) and glucose, a well-defined and large cyclic voltammetric (CV) oxidation wave of glucose catalyzed by GOD immobilized in the films and mediated by Fc(COOH)₂ in solution was observed. However, when the films were placed in pH 9.0 buffers containing the same amount of Fc(COOH)₂ and glucose, the electrocatalytic response was quite small. The bioelectrocatalysis for the film system was at the “on” state at pH 5.0 and at the “off” state at pH 9.0. This pH-sensitive “on-off” behavior was reversible and could be repeated for several times. The possible mechanism of the pH-switchable bioelectrocatalysis was explored and discussed, and should be mainly attributed to the different electrostatic interaction between Fc(COOH)₂ and the films at different pH. This work provides a novel model to realize pH-controllable bioelectrocatalysis based on the enzyme-loaded LBL assembly films, and may guide us to develop the tunable electrochemical biosensors based on electrocatalysis with immobilized enzymes.     

Amperometric glucose biosensor based on immobilization of glucose oxidase in electropolymerized o-aminophenol film at Prussian blue-modified platinum electrode

An amperometric glucose biosensor is developed, based on immobilization of glucose oxidase (GO_X) in an electrochemically polymerized, non-conducting poly(o-aminophenol) (POAP) film at Prussian blue (PB)-modified platinum (Pt) microelectrode. Effects of polymerization cycle number for POAP and PB, applied potential used in the determination, pH value of the detection solution and electroactive compounds on the amperometric response of the sensor were investigated and discussed. The electroactive property and rough surface of PB film result in the improvement of the detection limit and the increase of the maximum response current and sensitivity. The biosensor based on Pt/PB/POAP/GO_X electrode has two times lower detection limit, five times larger maximum current and nine times higher sensitivity than those of the biosensor based on Pt/POAP/GO_X electrode. Additionally, the biosensor shows fast response time, large response current, and good anti-interferent ability for l-ascorbic acid, uric acid and acetaminophen. Excellent reproducibility and stability of biosensor are also observed.     

DNA-templated synthesis of PtAu bimetallic nanoparticle/graphene nanocomposites and their application in glucose biosensor

In this paper, single-stranded DNA (ss-DNA) is demonstrated to functionalize graphene (GR) and to further guide the growth of PtAu bimetallic nanoparticles (PtAuNPs) on GR with high densities and dispersion. The obtained nanocomposites (PtAuNPs/ss-DNA/GR) were characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDS), and electrochemical techniques. Then, an enzyme nanoassembly was prepared by self-assembling glucose oxidase (GOD) on PtAuNP/ss-DNA/GR nanocomposites (GOD/PtAuNPs/ss-DNA/GR). The nanocomposites provided a suitable microenvironment for GOD to retain its biological activity. The direct and reversible electron transfer process between the active site of GOD and the modified electrode was realized without any extra electron mediator. Thus, the prepared GOD/PtAuNP/ss-DNA/GR electrode was proposed as a biosensor for the quantification of glucose. The effects of pH, applied potential, and temperature on the performance of the biosensor were discussed in detail and were optimized. Under optimal conditions, the biosensor showed a linearity with glucose concentration in the range of 1.0 to 1,800 μM with a detection limit of 0.3 μM (S/N = 3). The results demonstrate that the developed approach provides a promising strategy to improve the sensitivity and enzyme activity of electrochemical biosensors.