Electrosynthesis of hydrogen peroxide from oxygen in a gas-diffusion electrode in solutions of mineralized exometabolites

The electrosynthesis of H₂O₂ in aqueous solutions (pH 1–9) of mineralized liquid and solid bio-wastes (exometabolites) for their processing in closed life-support systems was studied. It was shown that H₂O₂ can be obtained in these solutions by electrochemical reduction of oxygen in carbon black gas diffuse electrodes to concentrations of over 2 M with current efficiency 80%. The composition of the solution was found to affect the accumulation of H₂O₂ during the synthesis. The solutions can be concentrated further to 19 M H₂O₂. The results showed that the electrolytic method is promising for preparing H₂O₂ for closed life-support systems.     

Electrochemical reduction of oxygen in gas-diffusion electrodes based on expanded natural graphite

Electroreduction of oxygen in gas-diffusion hydrophobized porous electrodes containing 8–10 wt % fluoroplastic, made of expanded natural graphite and acetylene black, in acidic (pH 0.6) and alkaline electrolytes was studied.     

Effects of the composition of acid solutions and the presence of organic acids on oxygen electroreduction to hydrogen peroxide in a carbon black gas-diffusion electrode

This paper reports on the effects of the K₂SO₄, H₂SO₄, NaCl, HCl, and tetrabutylammonium bromide concentrations (0.01–0.0002 M) and the presence of formic, acetic, and butyric acids in the electrolyte on the kinetic characteristics of oxygen reduction to H₂O₂ in a carbon black gas-diffusion electrode (GDE) and on the H₂O₂ accumulation kinetics in electrolyte at current densities of 30–100 mA/cm². The introduction of K₂SO₄ and tetrabutylammonium bromide in the electrolyte led to an increase in the transfer coefficient α and a decrease in the coefficients in the Tafel equation. The concentration and the current efficiency of H₂O₂ decreased with the salt to acid concentration ratio. The organic acids reduced the current efficiency of H₂O₂ and increased the electrode polarization. Peracids with a current efficiency of up to 0.27% and concentration of up to 7.5 mM were obtained. Solutions of H₂O₂ with concentrations of 0.6–3.3 M and current efficiencies of 17–75% were obtained at current densities of 30–100 mA/cm² in electrolytes with salt and inorganic acid concentrations of 0.9–40 g/l and in the presence of organic acids.     

Effect of the composition of gas-diffusion carbon black electrodes on electrosynthesis of hydrogen peroxide from atmospheric oxygen

Electroreduction of oxygen to H₂O₂ on gas-diffusion air electrodes made of A 437-E acetylene black and its mixture with P 702 and P 268-E furnace blacks with various particle sizes and wettabilities by an alkaline aqueous electrolyte with 8 and 20 wt % polytetrafluoroethylene was studied.     

Effect of trialkylammonium salts and current density on the electrosynthesis of hydrogen peroxide from oxygen in a gas-diffusion electrode in acid solutions

The influence exerted by the nature of cation of a supporting electrolyte and by the current density on the electroreduction of oxygen to hydrogen peroxide in acid K₂SO₄ solutions (pH 0.9–1.4) in gas-diffusion hydrophobized carbon black electrodes with varied electrolyte porosity was studied.     

Electrochemical reduction of oxygen at a porous flow-through electrode

The electrochemical reduction of oxygen at a porous flow-through electrode is described with emphasis on the effects of concentration, flow speed and surface area. On a packed bed copper electrode in sulfuric acid, it was found that oxygen undergoes a two electron reduction process giving rise to H₂O₂.     

Electrocatalytic hydrogen peroxide formation on mesoporous non-metal nitrogen-doped carbon catalyst

Direct electrochemical formation of hydrogen peroxide(H2O2) from pure O2 and H2on cheap metal-free earth abundant catalysts has emerged as the highest atom-efficient and environmentally friendly reaction pathway and is therefore of great interest from an academic and industrial point of view. Very recently,novel metal-free mesoporous nitrogen-doped carbon catalysts have attracted large attention due to the unique reactivity and selectivity for the electrochemical hydrogen peroxide formation [1–3]. In this work,we provide deeper insights into the electrocatalytic activity, selectivity and durability of novel metal-free mesoporous nitrogen-doped carbon catalyst for the peroxide formation with a particular emphasis on the influence of experimental reaction parameters such as p H value and electrode potential for three different electrolytes. We used two independent approaches for the investigation of electrochemical hydrogen peroxide formation, namely rotating ring-disk electrode(RRDE) technique and photometric UV–VIS technique. Our electrochemical and photometric results clearly revealed a considerable peroxide formation activity as well as high catalyst durability for the metal-free nitrogen-doped carbon catalyst material in both acidic as well as neutral medium at the same electrode potential under ambient temperature and pressure. In addition, the obtained electrochemical reactivity and selectivity indicate that the mechanisms for the electrochemical formation and decomposition of peroxide are strongly dependent on the p H value and electrode potential.     

A hydrogen peroxide biosensor based on multiwalled carbon nanotubes-polyvinyl butyral film modified electrode

A novel approach to construct a amperometric biosensor for determination of H₂O₂ is described. Horseradish peroxidase (HRP) as a base enzyme was immobilized into the mixture of multiwalled carbon nanotubes (MWNTs) and polyvinyl butyral (PVB). Taking the classical hydroquinone as mediator, cyclic voltammetry and amperometric measurements were used to study and optimize the performance of the resulting H₂O₂ biosensor. The effect of the concentration of MWNTs, HRP, hydroquinone, solution pH, and the working potential of amperometry on the electrochemical biosensor was systematically studied. The results showed that the fabricated biosensor demonstrated significant electrocatalytic activity for the reduction of hydrogen peroxide with wide linear range from 0.000832 to 0.6 mM, and low detection limit 0.000167 mM (S/N = 3) with fast response time less than 8 s. The apparent Michaelis–Menten constant was determined to be 0.049 mM. Additionally, the biosensor exhibited high sensitivity, rapid response and good long-term stability.     

Highly sensitive hydrogen peroxide sensor based on a glassy carbon electrode modified with platinum nanoparticles on carbon nanofiber heterostructures

We are presenting a sensor for hydrogen peroxide (H₂O₂) that is based on the use of a heterostructure composed of Pt nanoparticles (NPs) and carbon nanofibers (CNFs). High-density Pt NPs were homogeneously loaded onto a three-dimensional nanostructured CNF matrix and then deposited in a glassy carbon electrode (GCE). The resulting sensor synergizes the advantages of the conducting CNFs and the nanoparticle catalyst. The porous structure of the CNFs also favor the high-density immobilization of the NPs and the diffusion of water-soluble molecules, and thus assists the rapid catalytic oxidation of H₂O₂. If operated at a working voltage of −0.2 V (vs. Ag/AgCl), the modified GCE exhibits a linear response to H₂O₂ in the 5 μM to 15 mM concentration range (total analytical range: 5 μM to 100 mM), with a detection limit of 1.7 μM (at a signal-to-noise ratio of 3). The modified GCE is not interfered by species such as uric acid and glucose. Its good stability, high selectivity and good reproducibility make this electrode a valuable tool for inexpensive amperometric sensing of H₂O₂.

The Pt NPs/CNF heterostructure-based H₂O₂ sensor synergizes the advantages of both the conducting carbon nanofibers and the nanoparticle catalyst. The 3D structure of the nanofibers favor high density immobilization of the nanoparticles and penetration by water-soluble molecules, which assists the catalyic oxidation of H₂O₂. The sensor shows outstanding performance in terms of detection range, detection limit, response time, stability and selectivity.

     

Amperometric hydrogen peroxide biosensor based on a glassy carbon electrode modified with polythionine and gold nanoparticles

We report on a novel hydrogen peroxide biosensor that was fabricated by the layer-by-layer deposition method. Thionine was first deposited on a glassy carbon electrode by two-step electropolymerization to form a positively charged surface. The negatively charged gold nanoparticles and positively charged horseradish peroxidase were then immobilized onto the electrode via electrostatic adsorption. The sequential deposition process was characterized using electrochemical impedance spectroscopy by monitoring the impedance change of the electrode surface during the construction process. The electrochemical behaviour of the modified electrode and its response to hydrogen peroxide were studied by cyclic voltammetry. The effects of the experimental variables on the amperometric determination of H₂O₂ such as solution pH and applied potential were investigated for optimum analytical performance. Under the optimized conditions, the biosensor exhibited linear response to H₂O₂ in the concentration ranges from 0.20 to 1.6?mM and 1.6 to 4.0?mM, with a detection limit of 0.067?mM (at an S/N of 3). In addition, the stability and reproducibility of this biosensor was also evaluated and gave satisfactory results.

A hydrogen peroxide biosensor with high stability based on gelatin-multiwalled carbon nanotubes modified glassy carbon electrode

A biosensor with high stability was prepared to determine hydrogen peroxide (H₂O₂). This hydrogen peroxide biosensor was obtained by modifying glassy carbon electrode (GCE) with a composite film composed of gelatin-multiwalled carbon nanotubes. Catalase (Cat) was covalently immobilized into gelatin-multiwalled carbon nanotubes modified GCE through the well-known glutaraldehyde (GAD) chemistry in order to enhance the stability of electrodes. The enzyme sensor can achieve direct electrochemical response of hydrogen peroxide. The cyclic voltammograms at different scan rates, electrochemical impedance spectroscopy (EIS), and scanning electron microscope (SEM) tests indicate that the enzyme sensor performs positively on increasing permeability, reducing the electron transfer resistance, and improving the electrode performance. The linear response of standard curve for H₂O₂ is in the range of 0.2 to 5.0 mM with a correlation coefficient of 0.9972, and the detection limit of 0.001 mM. A high operational and storage stability is demonstrated for the biosensor. The peak potential at room temperature in two consecutive weeks stays almost consistent, and the enzyme activity is kept stable even after 30 days in further study.     

Nonenzymatic hydrogen peroxide sensor based on a glassy carbon electrode modified with electrospun PdO-NiO composite nanofibers

A glassy carbon electrode was modified with PdO-NiO composite nanofibers (PdO-NiO-NFs) and applied to the electrocatalytic reduction of hydrogen peroxide (H₂O₂). The PdO-NiO-NFs were synthesized by electrospinning and subsequent thermal treatment, and then characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. Factors such as the composition and fraction of nanofibers, and of the applied potential were also studied. The sensor exhibits high sensitivity for H₂O₂ (583.43 μA?·?mM^?1?·?cm^?2), a wide linear range (from 5.0 μM to 19 mM), a low detection limit (2.94 μM at an SNR of 3), good long term stability, and is resistant to fouling.

An oxygen reduction sensor based on a novel type of porous carbon composite membrane electrode

The development of a simple, efficient and sensitive sensor for dissolved oxygen is proposed using a novel type of porous carbon composite membrane/glassy carbon electrode based on the low-cost common filter paper by a simple method. The resulting device exhibited excellent electrocatalytic activities toward the oxygen reduction reaction. Scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and electrochemical measurements demonstrated that the porous morphology and uniformly dispersed Fe₃C nanoparticles of the PCCM play an important role in the oxygen reduction reaction. A linear response range from 2μmol/L up to 110 μmol/L and a detection limit of 1.4 μmol/L was obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation, was 3.0%. The successful fabrication of PCCM/GC electrode may promote the development of new porous carbon oxygen reduction reaction material for the oxygen reduction sensor.     

Electrochemical sensors based on binuclear cobalt phthalocyanine/surfactant/ordered mesoporous carbon composite electrode

A new ordered mesoporous carbon (OMC) composite modified electrode was fabricated for the first time. Binuclear cobalt phthalocyaninehexasulfonate sodium salt (bi-CoPc) can be adsorbed onto didodecyldimethylammonium bromide (DDAB)/OMC film by ion exchange. UV-vis spectroscopy, scanning electron microscopy (SEM) and electrochemical methods were used to characterize the composite film. The cyclic voltammograms demonstrate that the charge transfer of bi-CoPc is promoted by the presence of OMC. Further study indicated that bi-CoPc/DDAB/OMC film is the excellent electrocatalyst for the electrochemical reduction of oxygen in a neutral aqueous solution and hemoglobin (Hb) at lower concentrations. Additionally, as an amperometric 2-mercaptoethanol (2-ME) sensor, this modified electrode shows a wider linear range (2.5 × 10⁻⁶ to 1.4 × 10⁻⁴ M), high sensitivity (16.5 μA mM⁻¹) and low detection limit of 0.6 μM (S/N = 3). All these confirm the fact that the new composite film may have wide potential applications in biofuel cells, biological and environmental sensors.     

Determination of hydrogen peroxide based on calcined layered double hydroxide-modified glassy carbon electrode in flavored beverages

In this paper, we developed an amperometric hydrogen peroxide (H₂O₂) sensor based on cobalt-containing calcined layered double hydroxide (Co CLDH). The electrocatalytic activity of the Co CLDH towards the determination of H₂O₂ showed a fast response and high sensitivity. Moreover, the sensor exhibited good reproducibility and long-term stability. The superior electrocatalytic response to H₂O₂ is mainly attributed to the large surface area, minimized diffusion resistance, and enhanced electron transfer of the synthesized Co CLDH. This method with good analytical performance, low cost, and straightforward preparation made this novel electrode material promising for the determination of trace H₂O₂ in beverages with high accuracy, demonstrating its potential for practical application.