Surface poisoning during electrocatalytic monosaccharide oxidation reactions at gold electrodes in alkaline medium

In the present study, the surface poisoning of electrocatalytic monosaccharide oxidation reactions at gold electrodes were investigated. In the cyclic voltammetric studies, the electrocatalytic oxidation of aldohexose and aldopentose type monosaccharides, aminosugars, acetyl-glucosamine and glucronamide were observed at gold plate electrodes in alkaline medium. However, in controlled-potential electrolytic studies ranging −0.3 to −0.2 V in reaction solutions, current flows during electrolyses decreased quickly with time, except when glucosamine was used as a substrate.Results from surface enhanced infrared adsorption (SEIRA) spectroscopic measurements at an evaporated gold electrode for the electrocatalytic oxidation of glucose in 0.1 mol dm⁻³ NaOH at −0.3 V and Gaussian simulated spectra indicated that the gluconic acid as a 2-electron oxidation product and/or its analogs adsorbed onto the gold surface. Electrochemical quartz crystal microbalance (EQCM) measurement results, along with surface adsorption results from surface poisoning at the gold electrode during electrolytic reactions, suggested that gluconic acid and/or its analogs adsorbed vertically onto electrode surfaces in a full monolayer packing-like conformation. In the case of the electro oxidation of glucosamine in 0.1 mol dm⁻³ NaOH at −0.2 V, the obtained SEIRA spectra and EQCM results, clearly indicated that the glucosaminic acid as a 2-oxidation glucosamine product did not strongly bind onto the gold electrode surface.     

Morphology dependent electrocatalytic activity of Au nanoparticles

The electrocatalytic activity of spherical shape Au particles chemically grown on a sol–gel derived 3D silicate network modified conducting surface has been studied using ascorbate as a model. The nanostructured Au particles show morphology dependent electrocatalytic activity towards ascorbate. Unusual voltammetric behavior for ascorbate has been observed. Unlike the polycrystalline Au electrode, the nanostructured electrode shows two well defined voltammetric peaks for ascorbate at 0 and 0.3 V in neutral and alkaline pHs. These voltammetric peaks are assigned for the oxidation of ascorbate to dehydroascorbate (DHA) and the further oxidation of 2,3-diketogluonic acid (DKG), the hydrolyzed product of DHA. The voltammetric peak corresponding to the oxidation of DKG is very sensitive to the supporting electrolyte anions and solution pH. Voltammetric behavior of DHA has been investigated to support the oxidation pathway of ascorbate on the nanostructured electrode. Surface morphology of the particle controls the electrocatalytic activity.     

Electrochemical properties of ordered mesoporous carbon and its electroanalytical application for selective determination of dopamine

The electrochemical properties of one novel carbon material, ordered mesoporous carbons (OMC), synthesized by templating SBA-15 mesoporous silica materials and the electrocatalytic behaviors of OMC modified electrode towards the oxidation of dopamine (DA) and ascorbic acid (AA) were studied. Cyclic voltammetry was used to evaluate the electrochemical behaviors of OMC in 5 mM K₃Fe(CN)₆/0.1 M KCl solution. OMC showed a faster electron transfer rate, as compared with glass carbon (GC) electrode. The higher electron transfer kinetics can be attributed to the existence of a large amount of edge plane defect sites in the OMC materials, which was verified by Raman spectroscopy. The cyclic voltammetric studies also showed the presence of oxygen-containing functional groups on the surface of OMC. Furthermore, the OMC modified electrode showed high electrocatalytic activities toward the oxidation of DA and AA, and resolved their voltammetric responses into two well-defined peaks with peak separation of ca. 0.210 V. The OMC modified electrode could be effectively used for the selective electrochemical determination of DA in the presence of AA.     

Electrodeposition of monodispersed metal nanoparticles in a nafion film: Towards highly active nanocatalysts

We have explored a new and facile method for the fabrication of metal nanoparticles on the electrode surface. The approach for fabricating metal nanoparticles was carried out by two steps consisting of ion-exchange in nafion film coated on the electrode and subsequent reduction of metal ions to metallic nanoparticles by electrochemical method. The results of characterization by TEM show that metal nanoparticles were nearly monodispersed in the whole nafion film. The average diameters of Cu, Co and Ni nanoparticles were statistically measured to be 5.1 nm ± 0.2 nm, 4.6 nm ± 0.2 nm and 4.7 nm ± 0.2 nm, respectively. The amount of metal nanoparticles can be readily controlled by the amount of nafion coated on the electrode. By performing the H₂O₂ reduction at the obtained Cu nanoparticles, the high electrocatalytic activity of metal nanoparticles fabricated has been confirmed.     

Amperometric biosensing of glutamate using carbon nanotube based electrode

Amperometric biosensing of glutamate using nanobiocomposite derived from multiwall carbon nanotube (CNT), biopolymer chitosan (CHIT), redox mediator meldola’s blue (MDB) and glutamate dehydrogenase (GlDH) is described. The CNT composite electrode shows a reversible voltammetric response for the redox reaction of MDB at −0.15 V; the composite electrode efficiently mediates the oxidation of NADH at −0.07 V, which is 630 mV less positive than that on an unmodified glassy carbon (GC) electrode. The CNTs in the composite electrode facilitates the mediated electron transfer for the oxidation of NADH. The CNT composite electrode is highly sensitive (5.9 ± 1.52 nA/μM) towards NADH and it could detect as low as 0.5 μM of NADH in neutral pH. The CNT composite electrode is highly stable and does not undergo deactivation by the oxidation products. The electrode does not suffer from the interference due to other anionic electroactive compounds such as ascorbate (AA) and urate (UA). Separate voltammetric peaks have been observed for NADH, AA and UA, allowing the individual or simultaneous determination of these bioanalytes. The glutamate biosensor was developed by combining the electrocatalytic activity of the composite film and GlDH. The enzymatically generated NADH was electrocatalytically detected using the biocomposite electrode. Glutamate has been successfully detected at −0.1 V without any interference. The biosensor is highly sensitive, stable and shows linear response. The sensitivity and the limit of detection of the biosensor was 0.71 ± 0.08 nA/μM and 2 μM, respectively.     

Simultaneous determination of ascorbic acid,epinephrine, and uric acid by differential pulse voltammetry using poly(p-xylenolsulfonephthalein) modified glassy carbon electrode

A novel poly(p-xylenolsulfonephthalein) modified glassy carbon electrode was prepared for the simultaneous determination of ascorbic acid (AA), epinephrine (EP) and uric acid (UA). Cyclic voltammetric, chronoamperometric, and differential pulse voltammetric methods were used to investigate the modified electrode for the electrocatalytic oxidation of EP, AA, and UA in aqueous solutions. The separation of the oxidation peak potentials for AA–EP and EP–UA was about 200 and 130 mV, respectively. The calibration curves obtained for AA, EP, and UA were in the ranges of 10–1343, 2–390, and 0.1–560 μmol L⁻¹, respectively. The detection limits (S/N = 3) were 4, 0.1, and 0.08 μmol L⁻¹ for AA, EP and UA, respectively. The diffusion coefficient and the catalytic rate constant for the oxidation of EP at the modified electrode were calculated as 1.40(±0.10) × 10⁻⁴ cm² s⁻¹ and 1.06 × 10³ mol⁻¹ L s⁻¹, respectively. The present method was applied to the determination of EP in pharmaceutical and urine samples, AA in commercially available vitamin C tablet, and EP plus UA in urine samples.     

Promotion of PtIr and Pt catalytic activity towards ammonia electrooxidation through the modification of Zn

Zn is introduced into Pt and PtIr electrodes by applying potential cycles to their corresponding polycrystalline microdisc electrodes in a ZnCl₂-containing ionic liquid bath. Scanning-electron microscopy and energy-dispersive X-ray microanalysis studies show that nanostructured PtIrZn and PtZn layers created on the microdisc electrodes contain approximately 5 wt% Zn. Cyclic voltammetric studies reveal that PtZn and PtIrZn are significantly more active towards electrochemical ammonia oxidation in alkaline media than virgin Pt and PtIr electrodes. The PtIrZn electrode demonstrates a low onset potential of 0.30 V vs RHE and a high exchange current density of 4.3 × 10^− 8 A cm^− 2, which is favorably comparable to state-of-the-art electrocatalyts for the same reaction. The catalytic activity promotion by the Zn modification may be related to the inhibition of the hydrogen electrochemistry. PtIrZn appears therefore to be a very promising anode catalyst for direct ammonia fuel cells and ammonia electrolysis.     

Determination of formal potential of NADH/NAD+ redox couple and catalytic oxidation of NADH using poly(phenosafranin)-modified carbon electrodes

The electrochemical regeneration of NADH/NAD⁺ redox couple has been studied using poly(phenosafranin) (PPS)-modified carbon electrodes to evaluate the formal potential and catalytic rate constant for the oxidation of NADH. The PPS-modified electrodes were prepared by electropolymerization of phenosafranin onto different carbon substrates (glassy carbon (GC) and basal-plane pyrolytic graphite (BPPG)) in different electrolytic solutions. The formal potential was estimated to be ? 0.365 ± 0.002 V vs. SHE at pH 7.0. As for the bare carbon electrodes, the oxidation of NADH at the BPPG electrode was found to be enhanced compared with the GC electrode. For the PPS-modified electrodes, it was found that the electrocatalysis of PPS-modified electrodes for the oxidation of NADH largely depends on the carbon substrate and electrolyte solution employed for their preparation, i.e., the PPS-modified BPPG electrode prepared in 0.2 M NaClO₄/acetonitrile solution exhibits an excellent and persistent electrocatalytic property toward NADH oxidation in phosphate buffer solution (pH 7.0) with a diminution of the overpotential of about 740 and 670 mV compared with those at the bare GC electrode and the PPS-modified GC electrode prepared in 0.2 M H₂SO₄ solution, respectively. A quantitative analysis of the electrocatalytic reaction based on rotating disk voltammetry gave the electrocatalytic reaction rate constants of the order of 10³–10⁴ M^?1 s^? 1 depending on the preparation conditions of the PPS-modified electrodes.     

Silver particle-decorated carbon paste electrode based on ionic liquid for improved determination of nitrite

A simple silver particle-modified carbon paste electrode is proposed for the determination of low concentration levels of nitrite ions. The electrode consists of a carbon powder decorated with silver sub-micrometre particles (AgPs) and a hydrophobic ionic liquid trihexyltetradecylphosphonium chloride as a binder. It has been shown that AgPs exhibit a strong electrocatalytic effect on the nitrite oxidation. For optimal electroanalytical performance the electrode was conditioned via silver oxidation/reduction cycle. The electrode revealed a linear square-wave voltammetric response in a wide examined concentration range of 0.05 to 1.0 mmol L^− 1, limit of detection (LOD) of 3 μmol L^− 1 and excellent repeatability with RSD of 0.3%.     

Electrooxidation of insulin at silicon carbide nanoparticles modified glassy carbon electrode

For the first time silicon carbide nanoparticles (SiC) was used for electrode modification and electrocatalytic oxidation of insulin. In comparison to bare glassy carbon (GC) electrode, the oxidation of insulin at GC electrode modified with SiC nanoparticles occurred at reduced overpotentials. The modified electrode was applied for insulin detection using cyclic voltammetry, differential pulse voltammetry (DPV) and flow injection analysis (FIA). Flow injection amperometric determination of insulin at this modified electrode yielded a calibration curve with the following characteristics; linear dynamic range up to 600 pM, sensitivity of 710 pA pM^?1 cm^?2 and detection limit of 3.3 pM. In addition interference effect of the electroactive existing species (uric acid, glucose, lactic acid, l-cysteine and cholesterol) was diminished and for ascorbic acid eliminated by covering the surface of modified electrode with nafion film. This electrode shows many advantages as an insulin sensor such as simple preparation method without using any specific electron transfer mediator or specific reagent, high sensitivity, excellent catalytic activity, short response time, long term stability and remarkable antifouling property toward insulin and its oxidation product. Sensitivity, detection limit and antifouling properties of this insulin sensor are better than all of the reports in the literature for insulin detection at physiological pH solutions.     

Activity of Pt anode catalyst modified by underpotential deposited Pb in a direct formic acid fuel cell

We characterized the electrocatalytic activity of platinum electrode modified by underpotential deposited lead (PtPb_upd) for a formic acid (HCOOH) oxidation and investigated the influence on the power performance of direct formic acid fuel cells (DFAFC). Based on the electrochemical analysis using cyclic voltammetry and chronoamperometry, PtPb_upd electrode modified by underpotential deposition (UPD) exhibited significantly enhanced catalytic activity for HCOOH oxidation below anodic overpotential of 0.4 V (vs. SCE). Multi-layered PtPb_upd electrode structure of Pt/Pb_upd/Pt resulted in more stable and enhanced performance using 50% reduced loading of anode catalyst. The performance of multi-layered PtPb_upd anode is about 120 mW/cm² at 0.4 V and it also showed a sustainable cell activity of 0.52 V at an application of constant current loading of 110 mA/cm².     

Poly-xanthurenic acid as an efficient mediator for the electrocatalytic oxidation of NADH

This paper describes, for the first time, the development of a simple and highly sensitive chemical sensor based on a new electroactive material, electrogenerated in situ from xanthurenic acid on an electrode modified with MWCNT. The modified electrode shows efficient electrocatalytic oxidation activity towards NADH at an applied potential of 0.1 V vs. Ag/AgCl. The kinetic constant, k_kin, for the electrocatalytic oxidation of NADH, evaluated by chronoamperometry and voltammetry using RDE, provided values close to 10⁵ mol^?1 L s^?1.     

Choline biosensors based on a bi-electrocatalytic property of MnO2 nanoparticles modified electrodes to H2O2

An interesting mode of reactivity of MnO₂ nanoparticles modified electrode in the presence of H₂O₂ is reported. The MnO₂ nanoparticles modified electrodes show a bi-direction electrocatalytic ability toward the reduction/oxidation of H₂O₂. Based on this property, a choline biosensor was fabricated via a direct and facile electrochemical deposition of a biocomposite that was made of chitosan hydrogel, choline oxidase (ChOx) and MnO₂ nanoparticles onto a glassy carbon (GC) electrode. The biocomposite is homogeneous and easily prepared and provides a shelter for the enzyme to retain its bioactivity. The results of square wave voltammetry showed that the electrocatalytic reduction currents increased linearly with the increase of choline chloride concentration in the range of 1.0 × 10⁻⁵ –2.1 × 10⁻³ M and no obvious interference from ascorbic acid and uric acid was observed. Good reproducibility and stability were obtained. A possible reaction mechanism was proposed.     

Electrochemical synthesis of a ferrocenecarboxylic acid–C60 composite and its electrocatalysis to hydrogen peroxide

A new ferrocenecarboxylic acid–C₆₀ composite (Fc–C₆₀) has been synthesized by controlled potential electrolysis. A composite modified glassy carbon electrode has been prepared based on its good electrochemical activity. The modified electrode in 0.1 M NaClO₄ solution shows a reversible oxidation wave at E_1/2 = 0.32 V (vs. SCE) attributed to the oxidation of the ferrocene entity and a quasi-reversible reduction wave of C₆₀ entity at E_1/2 = ?0.54 V (vs. SCE). Electrocatalytic studies show that Fc–C₆₀ at the modified electrode can mediate the reduction of hydrogen peroxide (H₂O₂), and a broad linear range from 1.2 μM to 21.9 mM for H₂O₂ were obtained with a determination limit of 2.5 × 10^?7 M by amperometry.     

Porous cuprous oxide microcubes for non-enzymatic amperometric hydrogen peroxide and glucose sensing

Using porous cuprous oxide (Cu₂O) microcubes, a simple non-enzymatic amperometric sensor for the detection of H₂O₂ and glucose has been fabricated. Cyclic voltammetry (CV) revealed that porous Cu₂O microcubes exhibited a direct electrocatalytic activity for the reduction of H₂O₂ in phosphate buffer solution and the oxidation of glucose in an alkaline medium. The non-enzymatic amperometric sensor used in the detection of H₂O₂ with detection limit of 1.5 × 10^?6 M over wide linear detection ranges up to 1.5 mM and with a high sensitivity of 50.6 μA/mM. This non-enzymatic voltammetric sensor was further utilized in detection of glucose with a detection limit of 8.0 × 10^?7 M, a linear detection range up to 500 μM and with a sensitivity of ?70.8 μA/mM.     

Functional multiwalled carbon nanotube nanocomposite with iron picket-fence porphyrin and its electrocatalytic behavior

A kind of nanocomposite with good dispersion in water was prepared through noncovalent adsorption of iron picket-fence porphyrin (FeTMAPP), iron-5,10,15,20-tetrakis[αααα-2-trismethylammoniomethyl-phenyl]porphyrin, on multiwalled carbon nanotubes (MWNTs). UV–visible spectroscopic and electrochemical methods were used to characterize the nanocomposite. A gold nanoparticles/nanocomposite self-assembled monolayer was formed on gold electrode and showed highly synergetic behavior towards the electrocatalytic reduction of O₂ with a decrease of overpotential of 200 mV. FeTMAPP acted as the catalytic active center, and MWNTs increased the amount of FeTMAPP adsorbed and accelerated the electron transfer between FeTMAPP and electrode. The resulting biosensor exhibited good response to oxygen with a linear range from 0.52 to 180 μM and a detection limit of 0.38 μM, without the interference of ascorbic acid and uric acid, which showed an application potential of the proposed nanocomposite and monolayer in detection of dissolved oxygen and oxidase substrates.     

Microfluidic cell with a TiO2-modified gold electrode irradiated by an UV-LED for in situ photocatalytic decomposition of organic matter and its potentiality for voltammetric analysis of metal ions

A novel microreactor for TiO₂-assisted photocatalysis in a microfluidic electrochemical cell was designed and constructed by a technology that can be reproduced in any chemical laboratory. The cell is obtained by a two-step thermal transfer of laser printed masks onto gold CD-Rs, a subtractive one to define the electrodes, and an additive one to define the channels. The TiO₂ nanoparticles are physically embedded in a gold matrix by electrodeposition from a solution of ions of this metal also containing colloidal suspension of anatase. This modification is conducted in the assembled microfluidic cell, with minimum material and time consumption. A 100 mW UV-LED (365 nm) is focused on the modified electrode and irradiation of the sample in the thin layer microreactor is conducted under stopped flow condition. The Cu–EDTA complex served as model system to demonstrate the in situ photocatalytic digestion of organic matter followed by the voltammetric determination of the metal ion in aqueous solution. The voltammetric wave of 1.0 × 10⁻³ mol L⁻¹ Cu(II) in acetate buffer (pH 4.7) at the gold electrode is suppressed by EDTA in the −0.3 to 0.8 vs. Ag/AgCl region. Irradiation of the bare electrode at 365 nm does not recover the wave, while irradiation of the TiO₂-modified gold electrode causes the recovery of the copper wave, proving the photocatalytic destruction of the chelating agent. Diffusion transport to/from the modified electrode rapidly enrolls the whole volume of sample in the thin-layer above the electrode (about 19 nL), so that in less than four minutes the recorded voltammogram become indistinguishable from that of a copper ion solution without EDTA. This novel in situ sample pre-treatment approach is very promising, deserving further research aiming its integration in micro-TAS.     

Ultrasonic-electrodeposition of gold–platinum alloy nanoparticles on multi-walled carbon nanotubes – ionic liquid composite film and their electrocatalysis towards the oxidation of nitrite

We report here for the first time on the electrochemical co-deposition of gold–platinum (AuPt) nanoparticles on multi-walled carbon nanotubes (MWNT) – ionic liquid (i.e. trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide, [P_6,6,6,14][NTf₂]) composite surface in ultrasonic field. The obtained AuPt nanoparticles were characterized by scanning electron microscope, X-ray diffraction and X-ray photoelectron spectroscopy. It was found that they were well-dispersed on the composite surface, with particle size about 10 nm. Furthermore, they exhibited alloy features. Electrochemical impedance spectroscopy and voltammetric experiments showed that the resulted AuPt-MWNT-[P_6,6,6,14][NTf₂] modified electrode possessed rather small electron transfer resistance and good catalytic activity towards nitrite oxidation. Under the optimized conditions, the oxidation current of nitrite was linear to its concentration in the range of 5–200 nM and the detection limit was down to 1.0 nM (S/N = 3).     

Voltammetric behavior of selenocystine at modified gold substrates

The voltammetric response of seleno-l-cystine has been studied at gold substrates under physiological conditions. The reactivity of diselenides is utilized to generate a modified electrode surface, which in turn allows for electroanalysis of solution-based selenium species. Stable and reproducible voltammetry is observed for selenocystine reduction at pH 7 on selenium-modified gold substrates (E_mid = − 486 mV vs. Ag/AgCl) and is consistent with a diffusionally controlled process. Modification of the gold surface is readily achieved via electrochemical cycling in the presence of a diselenide source at conventional scan rates. These studies afford voltammetric characterization of the selenocystine/selenocysteine redox couple under physiologically relevant conditions and highlight the potential utility of selenium-modified substrates for electroanalysis of chalcogen-containing species.     

Switchable electrode functionalized with an azobenzene-containing copolymer thin film using the Langmuir–Schaefer technique for a “smart” uric acid/air fuel cell

A new photoswitchable electrode triggered by a brief light signal was fabricated by depositing an azobenzene-containing copolymer on an indium tin oxide substrate decorated with gold nanoparticles. The polymer formed a compact, complete thin film on the electrode surface using the Langmuir–Schaefer technique and offered reversible and stable switching performance. The conductivity and hydrophilicity of the electrode changed under UV/visible light due to the photoisomerization of the azobenzene moieties in the polymer film, influencing electron transfer and mass transport at the electrode. The electrochemical characterization demonstrated that the electrode exhibited reversibly switchable electrochemical behavior. In its active state, the as-prepared electrode possessed efficient electrocatalytic capability towards uric acid oxidation with a maximum anodic current density of 0.97 mA·cm^− 2. The uric acid/air fuel cell assembled from the photo-triggered anode and a Pt/C-modified cathode operated with an open circuit voltage of 0.12 V and a maximum power density of 41.33 μW·cm^− 2. The cell exhibited reversible switching performance (four cycles) and high stability: after one month the power output was 94.2% of the original maximum value.