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1.
This work demonstrates that iron-enriched natural zeolitic volcanic tuff (Paglisa deposit, Cluj county, Transilvania, Romania) resulting from a previous use as adsorbent in wastewater treatment can be recycled into effective electrode modifier applied to the electrocatalytic detection of hydrogen peroxide. After physico-chemical characterization of tuff samples using various techniques such as chemical analysis, X-ray diffraction, scanning electron microscopy, infrared spectroscopy, BET analysis and X-ray photoelectron spectroscopy, the electrochemical response of the iron-enriched zeolites was studied on the basis of solid carbon paste electrodes modified with these samples. The results indicate that iron centers in the zeolite are electroactive and that they act as electrocatalysts in the voltammetric and amperometric detection of H2O2. Best performance was achieved in phosphate buffer at pH 7, showing a sensitivity of 0.57 mA M−1 cm−2, a detection limit down to 60 μM, and a linear domain up to 100 mM H2O2.  相似文献   

2.
A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with single wall carbon nanotubes (SWCNTs) and phenazine derivative of Mn-complex. With immersing the GC/CNTs modified electrode into Mn-complex solution for a short period of time 20–100 s, a stable thin layer of the complex was immobilized onto electrode surface. Modified electrode showed a well defined redox couples at wide pH range (1–12). The surface coverages and heterogeneous electron transfer rate constants (ks) of immobilized Mn-complex were approximately 1.58 × 10−10 mole cm−2 and 48.84 s−1. The modified electrode showed excellent electrocatalytic activity toward H2O2 reduction. Detection limit, sensitivity, linear concentration range and kcat for H2O2 were, 0.2 μM and 692 nA μM−1 cm−2, 1 μM to 1.5 mM and 7.96(±0.2) × 103 M−1 s−1, respectively. Compared to other modified electrodes, this electrode has many advantageous such as remarkable catalytic activity, good reproducibility, simple preparation procedure and long term stability.  相似文献   

3.
Graphene was prepared successfully by introducing -SO3 to separate the individual sheets. TEM, EDS and Raman spectroscopy were utilized to characterize the morphology and composition of graphene oxide and graphene. To construct the H2O2 biosensor, graphene and horseradish peroxidase (HRP) were co-immobilized into biocompatible polymer chitosan (CS), then a glassy carbon electrode (GCE) was modified by the biocomposite, followed by electrodeposition of Au nanoparticles on the surface to fabricate Au/graphene/HRP/CS/GCE. Cyclic voltammetry demonstrated that the direct electron transfer of HRP was realized, and the biosensor had an excellent performance in terms of electrocatalytic reduction towards H2O2. The biosensor showed high sensitivity and fast response upon the addition of H2O2, under the conditions of pH 6.5, potential −0.3 V. The time to reach the stable-state current was less than 3 s, and the linear range to H2O2 was from 5 × 10−6 M to 5.13 × 10−3 M with a detection limit of 1.7 × 10−6 M (S/N = 3). Moreover, the biosensor exhibited good reproducibility and long-term stability.  相似文献   

4.
D. Fu 《Electrochimica acta》2010,55(11):3787-18529
The electrochemical reduction and oxidation kinetics of hydrogen peroxide on γ-FeOOH films chemically deposited on indium tin oxide substrates were studied over the pH range of 9.2-12.6 and the H2O2 concentration range of 10−4 to 10−2 mol dm−3. The Tafel slopes for H2O2 reduction and oxidation obtained from polarization measurements are 106 ± 4 and 93 ± 15 mV dec−1, respectively, independent of pH and the concentration of H2O2. Both the reduction and oxidation of H2O2 on γ-FeOOH have a first-order dependence on the concentration of molecular H2O2. However, for the pH dependence, the reduction has an inverse first-order dependence, whereas the oxidation has a first-order dependence, on the concentration of OH. For both cases the electroactive species is the molecular H2O2, not its base form, HO2. Based on these observations, reaction kinetic mechanisms are proposed which involve adsorbed radical intermediates; HOOH and HO for the reduction, and HO2H+, HO2, and O2 for the oxidation. These intermediates are assumed to be in linear adsorption equilibria with OH and H+ in the bulk aqueous phase, respectively, giving the observed pH dependences. The rate-determining step is the reduction or oxidation of the adsorbed H2O2 to the corresponding intermediates, a reaction step which involves the use of FeIII/FeII sites in the γ-FeOOH surface as an electron donor-acceptor relay. The rate constant for the H2O2 decomposition on γ-FeOOH determined from the oxidation and reduction of Tafel lines is very low, indicating that the γ-FeOOH surface is a very poor catalyst for H2O2 decomposition.  相似文献   

5.
A novel nanocomposite was synthesized using a cathodic, low-potential, electrochemical reduction of H2O2 to homogeneously deposit cobalt oxide/hydroxide (denoted as CoOx·nH2O) nanostructures onto vertically well-aligned multi-walled carbon nanotube arrays (MWCNTs), while the MWCNTs were prepared by catalytic chemical vapor deposition (CVD) on a tantalum (Ta) substrate. The CoOx·nH2O–MWCNTs nanocomposite exhibits much higher electrocatalytic activity towards glucose (Glc) after modification with CoOx·nH2O than before. This non-enzymatic Glc sensor has a high sensitivity (162.8 μA mM−1 cm−2), fast response time (<4 s) and low detection limit (2.0 μM at signal/noise ratio = 3), and a linear dynamic range up to 4.5 mM. The sensor output is stable over 30 days and unaffected by common interferents that co-exist with Glc in analytical samples; it is also resistant to chloride poisoning. These features make the CoOx·nH2O–MWCNTs nanocomposite a promising electrode material for non-enzymatic Glc sensing in routine analysis.  相似文献   

6.
We have developed a polyaniline/carboxy-functionalized multiwalled carbon nanotube (PAn/MWCNTCOOH) nanocomposite by blending the emeraldine base form of polyaniline (PAn) and carboxy-functionalized multiwalled carbon nanotubes (MWCNT) in dried dimethyl sulfoxide (DMSO) at room temperature. The conductivity of the resulting PAn/MWCNTCOOH was 3.6 × 10−3 S cm−1, mainly as a result of the protonation of the PAn with the carboxyl group and the radical cations of the MWCNT fragments. Horseradish peroxidase (HRP) was immobilized within the PAn/MWCNTCOOH nanocomposite modified Au (PAn/MWCNTCOOH/Au) electrode to form HRP/PAn/MWCNTCOOH/Au for use as a hydrogen peroxide (H2O2) sensor. The adsorption between the negatively charged PAn/MWCNTCOOH nanocomposite and the positively charged HRP resulted in a very good sensitivity to H2O2 and an increased electrochemically catalytical current during cyclic voltammetry. The HRP/PAn/MWCNTCOOH/Au electrode exhibited a broad linear response range for H2O2 concentrations (86 μM–10 mM). This sensor exhibited good sensitivity (194.9 μA mM−1 cm−2), a fast response time (2.9 s), and good reproducibility and stability at an applied potential of −0.35 V. The construction of the enzymatic sensor demonstrated the potential application of PAn/MWCNTCOOH nanocomposites for the detection of H2O2 with high performance and excellent stability.  相似文献   

7.
In this work, Ni(OH)2 nanoplates grown on the Cu substrate were synthesized and characterized by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Then a novel Cu-Ni(OH)2 modified glass carbon electrode (Cu-Ni(OH)2/GCE) was fabricated and evaluated by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and typical amperometric response (i-t) method. Exhilaratingly, the Cu-Ni(OH)2/GCE shows significant electrocatalytic activity toward the reduction of H2O2. At an applied potential of −0.1 V, the sensor produces an ultrahigh sensitivity of 408.1 μA mM−1 with a low detection limit of 1.5 μM (S/N = 3). The response time of the proposed electrode was less than 5 s. What's more, the proposed sensor displays excellent selectivity, good stability, and satisfying repeatability.  相似文献   

8.
A monolayer of Keggin-type heteropolyanion [SiNi(H2O)W11O39]6− was fabricated by electrodepositing [SiNi(H2O)W11O39]6− on cysteamine modified gold electrode. The monolayer of [SiNi(H2O)W11O39]6− modified gold electrode was characterized by atomic force microscopy (AFM) and electrochemical method. AFM results showed the [SiNi(H2O)W11O39]6− uniformly deposited on the electrode surface and formed a porous monolayer. Cyclic voltammetry exhibited one oxidation peak and two reduction peaks in 1.0 M H2SO4 in the potential range of −0.2 to 0.7 V. The constructed electrode could exist in a large pH (0-7.6) range and showed good catalytic activity towards the reduction of bromate anion (BrO3) and nitrite (NO2), and oxidation of ascorbic acid (AA) in acidic solution. The well catalytic active of the electrode was ascribed to the porous structure of the [SiNi(H2O)W11O39]6 monolayer.  相似文献   

9.
Au nanoparticles (AuNPs) are good quenchers once they closely contact with luminophore. Here we reported a simple approach to obtain enhanced electrogenerated chemiluminescence (ECL) behavior based on Au/CdS nanocomposite films by adjusting the amount of AuNPs in the nanocomposite. The maximum enhancement factor of about 4 was obtained at an indium tin oxide (ITO) electrode in the presence of co-reactant H2O2. The mechanism of this enhancement was discussed in detail. The strong ECL emission from Au/CdS nanocomposites film was exploited to determine H2O2. The resulting ECL biosensors showed a linear response to the concentration of H2O2 ranging from 1.0 × 10−8 to 6.6 × 10−4 mol L−1 with a detection limit of 5 nmol L−1 (S/N = 3) and good stability and reproducibility.  相似文献   

10.
E. Jin  Lili Cui 《Electrochimica acta》2010,55(24):7230-7234
In this work, graphene/prussian blue (PB) composite nanosheets with good dispersibility in aqueous solutions have been synthesized by mixing ferric-(III) chloride and potassium ferricyanide in the presence of graphene under ambient conditions. Transmission electron microscopy (TEM) shows that the average size of the as-synthesized PB nanoparticles on the surface of graphene nanosheets is about 20 nm. Fourier-transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) patterns have been used to characterize the chemical composition of the obtained graphene/PB composite nanosheets. The graphene/PB composite nanosheets exhibit good electrocatalytic behavior to detection of H2O2 at an applied potential of −0.05 V. The sensor shows a good linear dependence on H2O2 concentration in the range of 0.02-0.2 mM with a sensitivity of 196.6 μA mM−1 cm−2. The detection limit is 1.9 μM at the signal-to-noise ratio of 3. Furthermore, the graphene/PB modified electrode exhibits freedom of interference from other co-existing electroactive species. This work provides a new kind of composite modified electrode for amperometric biosensors.  相似文献   

11.
[PFeW11O39]4− (PFeW11) supported on the surface of 3-aminopropyl(triethoxy)silane modified silica gel was synthesized and used as a bulk modifier to fabricate a renewable three-dimensional chemically modified electrode. The electrochemical behavior of the modified electrode was investigated. Cyclic voltammetry studies showed that the PFeW11 on the electrode surface sustained the same electrochemical properties as that of the PFeW11 in solution. The preparation of chemically modified electrode is simple and quiet reproducible using inexpensive material. The modified electrode had high electrocatalytic activity toward H2O2 reduction and it was successfully applied as an electrochemical detector to monitor H2O2 in flow injection analysis (FIA). The electrocatalytic peak current was found to be linear with the H2O2 concentration in the range 10-200 μmol L−1 with a correlation coefficient of 0.998 and a detection limit (3σ) of 7.4 μmol L−1 H2O2. The electrode has the remarkable advantage of surface renewal owing to bulk modification, as well as simple preparation, good mechanical and chemical stability and reproducibility.  相似文献   

12.
Electrochemical behavior of oxo-bridged dinuclear ruthenium(III) complex ([(bpy)2(H2O)RuIII-O-RuIII(H2O)(bpy)2]4+) has been studied in aqueous solution (KCl 0.5 mol L−1) by both cyclic and rotating disk electrode (RDE) voltammetry in order to identify and elucidate the reaction mechanism. Modified electrode containing the oxo-bridged ruthenium complex incorporated into a cation-exchange polymeric film deposited onto platinum electrode surface was studied. Cyclic voltammetry at the modified electrode in KCl solution showed a single-electron reduction/oxidation of the couple RuIII-O-RuIII/RuIII-O-RuIV. The modified electrode exhibited electrocatalytic property toward hydrogen peroxide oxidation in KCl solution with a decrease of the overpotential of 340 mV compared with the platinum electrode. The Tafel plot analyses have been used to elucidate the kinetics and mechanism of the hydrogen peroxide oxidation. The first at low overpotential region there is no significant change in the Tafel slope (∼0.130 V dec−1) with varying peroxide concentration. The second region at higher overpotential the slope values (0.91–0.47 V dec−1) were depended on the peroxide concentration. The apparent reaction order for H2O2 varies from 0.16 to 0.50 in function of the applied potential. The apparent reaction order (at constant potential) with respect to H+ concentration of 10−5 to 10−1 mol L−1 was 0.25. A plot of the anodic current vs. the H2O2 concentration for chronoamperometry (potential fixed = +0.61 V) at the modified electrode was linear in the 1.0 × 10−5 to 2.5 × 10−4 mol L−1 concentration range.  相似文献   

13.
The direct electrochemistry of hemoglobin (Hb) has been achieved by immobilizing Hb on mesoporous Al2O3 (meso-Al2O3) film modified glassy carbon (GC) electrode. Meso-Al2O3 shows significant promotion to the direct electron-transfer of Hb, thus it exhibits a pair of well defined and quasi-reversible peaks with a formal potential of −0.345 V (vs. SCE). The electron-transfer rate constant (ks) is estimated to be 3.17 s−1. The immobilized Hb retains its biological activity well and shows high catalytic activity to the reduction of hydrogen peroxide (H2O2) and nitrite (NO2). Under the optimized experimental conditions, the catalytic currents are linear to the concentrations of H2O2 and NO2 in the ranges of 0.195-20.5 μM and 0.2-10 mM, respectively. The corresponding detection limits are 1.95 × 10−8 M and 3 × 10−5 M (S/N = 3). The resulting protein electrode has high thermal stability and good reproducibility due to the protection effect of meso-Al2O3. Ultraviolet visible (UV-vis) absorption spectra and reflection-absorption infrared (RAIR) spectra display that Hb keeps almost natural structure in the meso-Al2O3 film. The N2 adsorption-desorption experiments show that the pore size of meso-Al2O3 is about 14.4 nm, suiting for the encapsulation of Hb (average size: 5.5 nm) well. Therefore, meso-Al2O3 is an alternative matrix for protein immobilization and biosensor preparation.  相似文献   

14.
Huajun Qiu 《Electrochimica acta》2010,55(20):6081-6087
A 3-dimentional (3D) micro-nano hierarchical porous Cu film was fabricated by surface rebuilding of smooth Cu substrates in a blank solution of 1 M NaOH with square wave potential perturbation. The potential step from 0.4 to −2.5 V (vs. SCE) and a frequency of 50 Hz were chosen for the fabrication. The pore formation and Cu nanostructure evolution were characterized by scanning electron microscopy. The fabrication process involved fast Cu electrochemical oxidation-reduction and suitable rate of H2 releasing. During the repeated Cu oxidation-reduction, the Cu atoms were removable, forming dendrite-like structures. At the same time, the formed H2 bubbles acted as a dynamic template to shape the formation of micropores. The effect of H2 bubble as a template on the size of the formed micropores was demonstrated by adding a small amount of surfactant (cetyltrimethylammonium bromide, CTAB) into the basic solution to adjust the size of the bubbles. The as-prepared 3D porous Cu showed high electrocatalytic activity toward the reduction of NO3 and H2O2. The present in situ preparation method was green, convenient and required neither Cu(II) species and additives in solution nor post-treatment for template removal.  相似文献   

15.
Bromine (Br)-adatom (Br(ads)) was in situ fabricated onto polycrystalline gold (Au (poly)) electrode in Br-containing alkaline media. The surface coverage of Br(ads) (ΓBr) varied only in the submonolayer coverage within the investigated potential window under potentiodynamic condition because of the coadsorption of hydroxyl ion (OH) in alkaline media. The in situ fabricated Br(ads)-submonolayer-coated Au (poly) electrode was successfully used for the electrochemical oxidation of hydrogen peroxide (H2O2). About five times higher oxidation current was achieved at the modified electrode as compared with the bare electrode. The enhancement of the electrode activity towards the electrochemical oxidation of H2O2 was explained based on the enhanced electrostatic attraction between the anionic HO2 molecules and Br(ads)-adlayer-induced positively polarized Au (poly) electrode surface.  相似文献   

16.
T. Uma 《Electrochimica acta》2007,52(24):6895-6900
The scope of the present work was to investigate and evaluate the electrochemical activity of H2/O2 fuel cells based on the influence of a heteropolyacid glass membrane with a Pt/C electrode at low temperature. A new trend of sol-gel derived PMA (H3PMo12O40) heteropolyacid-containing glass membranes inherent of a high proton conductivity and mechanical stability, was heat treated at 600 °C and implemented to H2/O2 fuel cell activities through electrochemical characterization. Significant research has been focused on the development of H2/O2 fuel cells using optimization of heteropolyacid glasses as electrolytes with Pt/C electrodes at 30 °C. A maximum power density of 23.9 mW/cm2 was attained for operation with hydrogen and oxygen, respectively, at 30 °C and 30% humidity with the PMA glass membranes (4-92-4 mol%). Impedance spectroscopy measurements were performed on a total ohmic cell resistance of a membrane-electrode-assembly (MEA) at the end of the experiment.  相似文献   

17.
Electrochemical reduction of oxygen (O2) in air electrode with manganese oxides (MnOx) as electrocatalysts was studied with MnOx/Nafion-modified gold (Au) electrodes using cyclic voltammetry, potential-controlled amperometry and rotating ring-disk electrode (RRDE) voltammetry in alkaline aqueous solution. At Nafion-modified (MnOx free) Au electrode, O2 reduction undergoes two successive two-electron processes with HO2 as intermediate. The presence of MnOx, including Mn2O3, Mn3O4, Mn5O8 and MnOOH, on Nafion-modified Au electrodes obviously increases the first reduction peak current of O2 to hydrogen peroxide (HO2 in this case) and decreases the second one of HO2 to OH, while does not shift the reduction potential. MnOx was found to show catalytic activity for the disproportionation reaction of HO2 to O2 and OH and thus, the O2 reduction in air electrode was considered to include an initial two-electron reduction of O2 to HO2 followed by a disproportionation reaction of HO2 into O2 and OH catalyzed by MnOx. The excellent activity of MnOx for the follow-up disproportionation reaction substantially results in an overall four-electron reduction of O2 at MnOx/Nafion-modified Au electrodes in the first reduction step, depending on potential scan rate and the kind of MnOx. The present work provides a scientific significance of the mechanism of O2 reduction in air electrode using MnOx as electrocatalysts to effect a four-electron reduction of O2 to OH.  相似文献   

18.
Numerous transition metal–carbon composite catalysts (M = V, Zn, Ni, Sn, Ce, Ba, Fe, Cu) have been synthesized and tested for electroreduction of O2 to H2O2, The activity and selectivity of all synthesized catalysts for electrosynthesis of H2O2 were determined by the rotating ring-disk electrode method in acidic and neutral electrolytes. The Co-based catalysts in general showed the highest activity towards H2O2 formation. Experiments with different loading contents of Co showed that the activation overpotential losses of oxygen reduction to H2O2 reduces as loading increases to about 4 wt% Co. Addition of Co beyond this level did not seem to impact the overpotential losses. The cobalt-based catalysts, were spray-coated onto 120 μm thick Toray® graphite substrates, and were studied in bulk electrolysis cells for up to 100 h at potentiostatic conditions (0.25 V vs. RHE) in pH 0, 3, and 7 electrolytes. At (25 °C and 1 bar) with a catalysts loading of about and using dissolved O2 in 0.5 M H2SO4, typical H2O2 electrosynthesis rates of about were reached with current efficiencies of about 85 ± 5% at 0.25 V (vs. RHE).  相似文献   

19.
Graphite electrodes chemically modified with Prussian Blue (G/PB) were obtained by spreading, on the electrode surface, appropriate volumes of 100 mM K3[Fe(CN)6] and 100 mM FeCl3 solutions, both containing 10 mM HCl. In order to improve the electrochemical response stability, the potential of G/PB electrodes was cycled (in the domain where PB exhibits electrochemical activity) in 0.1 M KCl solution (G/PB-K), as well as in 2 mM RhCl3 solution, containing 0.05 M KCl (G/PB-Rh). Compared with G/PB-K, the G/PB-Rh modified electrodes showed: (i) higher relative stability of the PB electrochemical response; (ii) better analytical parameters for H2O2 amperometric detection; (iii) slightly lower rate constant corresponding to the second order electrocatalytic reaction for H2O2 amperometric detection; (iv) an electrocatalytic activity not affected by the H2O2 concentration.  相似文献   

20.
Cobalt ferrite nanoparticles (CoxFe3−xO4) and chitosan (CS) film were used to immobilize/adsorb hemoglobin (Hb) to create a protein electrode to study the direct electron transfer between the redox centers of the proteins and the electrode. X-ray diffraction (XRD) and transmission electron microscopy (TEM) revealed that the CoxFe3−xO4 particles were nanoscale in size and formed an ordered layered structure. The native structure of the immobilized Hb was preserved as indicated by Fourier-transform infrared (FTIR) and UV–visible (UV–vis) spectroscopy. The Hb-CoxFe3−xO4–CS modified electrode showed a pair of well-defined and quasi-reversible cyclic voltammetric peaks at −0.373 V (vs. SCE) and exhibited appreciable electrocatalytic activity for the reduction of H2O2. The catalysis currents increased linearly with H2O2 concentration in a wide range of 5.0 × 10−8 to 1.0 × 10−3 mol L−1 with a detection limit of 1.0 × 10−8 mol L−1 (S/N = 3) and had long-term stability. Finally, the proposed method was applied to investigate the coexistence of hydrogen peroxide with the interfering substances. Experimental results showed that the ascorbic acid, glucose, l-cysteine, uric acid, and dopamine at corresponding concentrations did not influence the detection of H2O2.  相似文献   

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