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1.
FeTAPc-single walled carbon nanotube (SWCNT) dendrimers are employed as glassy carbon electrode modifiers for the electrocatalytic oxidations of amitrole and diuron. The catalytic rate constants were 4.55 × 103 M−1 s−1 and 1.79 × 104 M−1 s−1 for amitrole and diuron, respectively using chronoamperometric studies. The diffusion constants were found to be 1.52 × 10−4 cm2 s−1 and 1.91 × 10−4 cm2 s−1 for diuron and amitrole, respectively. The linear concentration range for both were from 5.0 × 10−5 to 1.0 × 10−4 M and sensitivities of 0.6603 μA/μM and 0.6641 μA/μM for amitrole and diuron, with corresponding limits of detection of 2.15 × 10−7 and 2.6 × 10−7 M using the 3δ notation, respectively.  相似文献   

2.
Three different films, poly(acrylonitrile-co-methylacrylate)/single wall carbon nanotubes (PAN-MA/SWCNT), poly(acrylonitrile-co-methylacrylate)/carbon black (PAN-MA/CB) and pure functionalized SWCNT, are analyzed. The diffuse reflectance and transmittance of the films from 2 μm to 18 μm are characterized with an integrating-sphere Fourier transform spectrophotometer system. The SWCNT film shows high reflectance and low emissivity. Surface roughness characterization by laser scanning confocal microscopy confirms that the low emissivity is not due to a highly polished surface and is therefore more likely due to the metallic behavior of the SWCNTs. Characterization using infra red thermography highlighted the thermal protective behavior of the SWCNT film; the maximum temperature obtained from a 5.2 kW/m2 heat flux exposure was 50 °C lower than that for the two (SWCNT, CB) PAN-MA based films.  相似文献   

3.
This paper provides first evidence of the impact of solution pH on the heterogeneous electron transfer rate constants of self-assembled films of single-walled carbon nanotubes (SWCNT) and SWCNT integrated to cobalt(II)tetra-aminophthalocyanine (SWCNT-CoTAPc) by sequential self-assembly. Using cyclic voltammetry and electrochemical impedance spectroscopy, we proved that both SAMs exhibit notable differences in their response to different buffered solution pH, with and without the presence of redox probe, [Fe(CN)6]4−/[Fe(CN)6]3−. Surface pKa value for the Au-Cys-SWCNT-CoTAPc was estimated as ca. 7.8, compared to that of the Au-Cys-SWCNT of about 5.5. Interestingly, both redox-active SAMs gave similar analytical response for epinephrine, giving well-resolved square wave voltammograms, with linear concentration range up to 130 μM, sensitivity of ca. 9.4 × 10−3 AM−1, and limit of detection ca. 6 μM. This analytical result implies that there is no detectable advantage of one of the SAMs over the other in the electrocatalytic detection of this neurotransmitter.  相似文献   

4.
The construction by sequential self-assembly process of reproducible, highly stable and pH-responsive redox-active nanostructured arrays of single-walled carbon nanotubes (SWCNTs) integrated with octa(hydroxyethylthio)phthalocyaninatoiron(II) (FeOHETPc) via ester bonds on a gold surface (Au-Cys-SWCNT-FeOHETPc) is investigated and discussed. The successful construction of this electrode is confirmed using atomic force microscopy and X-ray photoelectron spectroscopy as well as from the distinct cyclic voltammetric and electrochemical impedance spectroscopic profiles. The Au-Cys-SWCNT-FeOHETPc electrode exhibited strong dependence on the reaction of the head groups and the pH of the working electrolytes, the surface pKa is estimated as 7.3. The high electron transfer capability of the Au-Cys-SWCNT-FeOHETPc electrode over other electrodes (Au-Cys-SWCNT or the Au-Cys-FeOHETPc or the Au-FeOHETPc) suggests that SWCNT greatly improves the electronic communication between FeOHETPc and the bare gold electrode. The electron transfer rate constant (kapp) of Au-Cys-SWCNT-FeOHETPc in pH 4.8 conditions (∼1.7 × 10−2 cm−2 s−1) over that of the electrode obtained from SWCNT integrated with tetraaminophthalocyninatocobalt(II) (Au-Cys-SWCNT-CoTAPc) (5.1 × 10−3 cm−2 s−1) is attributed to the possible effect of the central metal on the phthalocyanine core and substituents on the peripheral positions of the phthalocyanine rings. We also prove that aligned SWCNT arrays exhibit much faster electron transfer kinetics to redox-active species in solutions compared to the randomly dispersed (drop-dried) SWCNTs.  相似文献   

5.
This paper describes detailed comparative electrochemical and electrocatalytic behaviours of basal plane pyrolytic graphite electrodes (BPPGEs) modified with single-wall carbon nanotube (BPPGE-SWCNT) and SWCNTs functionalised with cobalt(II) tetra-aminophthalocyanine by physical (BPPGE-SWCNT-CoTAPc(mix)), chemical (BPPGE-SWCNT-CoTAPc(cov)) and electrochemical adsorption (BPPGE-SWCNT-CoTAPc(ads)) processes. SWCNT improves both solution and surface electrochemistry of CoTAPc. Electrochemical kinetics of the SWCNT-CoTAPc modified BPPGE yielded different ks values, indicative of different rate-determining steps for the cathodic and anodic reactions. Electrochemical impedance spectroscopy (EIS) analyses in the presence of [Fe(CN)6]3−/4− as a redox probe revealed that the SWCNT and SWCNT-CoTAPc(mix) films have comparable data in terms of solution resistance (Rs), electron transfer resistance (Ret), Warburg impedance (Zw) and electron-transfer rate constant (kapp). Also, these surface-confined films showed comparable electrocatalytic responses towards the detection of V-type nerve agent sulfhydryl hydrolysis products, dimethylaminoethanethiol (DMAET) and diethylaminoethanethiol (DEAET). Using the BPPGE-SWCNT-CoTAPc(mix), the estimated catalytic rate constants and diffusion coefficients were higher for DEAET than for the DMAET. Also, the detection limits of approximately 8.0 and 3.0 μM for DMAET and DEAET were obtained with sensitivities of 5.0 and 6.0 × 10−2 A M−1 for DMAET and DEAET, respectively. BPPGE-SWCNT-CoTAPc showed better potential discrimination for detection of these sulfhydryl analytes than the BPPGE-SWCNT, the latter exhibited enhanced catalytic response for the sulfhydryls than the former.  相似文献   

6.
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   

7.
8.
In this study, multi-wall carbon nanotubes (MWCTs) is evaluated as a transducer, stabilizer and immobilization matrix for the construction of amperometric sensor based on iron-porphyrin. 5,10,15,20-Tetraphenyl-21H,23H-porphine iron(III) chloride (Fe(III)P) adsorbed on MWCNTs immobilized on the surface of glassy carbon electrode. Cyclic voltammograms of the Fe(III)P-incorporated-MWCNTs indicate a pair of well-defined and nearly reversible redox couple with surface confined characteristics at wide pH range (2-12). The surface coverage (Γ) and charge transfer rate constant (ks) of Fe(III)P immobilized on MWCNTs were 7.68 × 10−9 mol cm−2 and 1.8 s−1, respectively, indicating high loading ability of MWCNTs for Fe(III)P and great facilitation of the electron transfer between Fe(III)P and carbon nanotubes immobilized on the electrode surface. Modified electrodes exhibit excellent electrocatalytic activity toward reduction of ClO3, IO3 and BrO3 in acidic solutions. The catalytic rate constants for catalytic reduction of bromate, chlorate and iodate were 6.8 × 103, 7.4 × 103 and 4.8 × 102 M−1 s−1, respectively. The hydrodynamic amperometry of rotating-modified electrode at constant potential versus reference electrode was used for detection of bromate, chlorate and iodate. The detection limit, linear calibration range and sensitivity for chlorate, bromate and iodate detections were 0.5 μM, 2 μM to 1 mM, 8.4 nA/μM, 0.6 μM, 2 μM to 0.15 mM, 11 nA/μM, and 2.5 μM, 10 μM to 4 mM and 1.5 nA/μM, respectively. Excellent electrochemical reversibility of the redox couple, good reproducibility, high stability, low detection limit, long life time, fast amperometric response time, wide linear concentration range, technical simplicity and possibility of rapid preparation are great advantages of this sensor. The obtained results show promising practical application of the Fe(III)P-MWCNTs-modified electrode as an amperometric sensor for chlorate, iodate and bromate detections.  相似文献   

9.
A novel amperometric sensor was fabricated based on the immobilization of hemin onto the poly (amidoamine)/multi-walled carbon nanotube (PAMAM/MWCNT) nanocomposite film modified glassy carbon electrode (GCE). Electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and ultraviolet visible (UV-vis) adsorption spectroscopy were used to investigate the possible state and electrochemical activity of the immobilized hemin. In the Hemin/PAMAM/MWCNT nanocomposite film, MWCNT layer possessed excellent inherent conductivity to enhance the electron transfer rate, while the layer of PAMAM greatly enlarged the surface average concentration of hemin (Γ) on the modified electrode. Therefore, the nanocomposite film showed enhanced electrocatalytical activity towards the oxidation of l-tyrosine. The kinetic parameters of the modified electrode were investigated. In pH 7.0 phosphate buffer solution (PBS), the sensor exhibits a wide linear range from 0.1 μM to 28.8 μM l-tyrosine with a detection limit of 0.01 μM and a high sensitivity of 0.31 μA μM−1 cm−2. In addition, the response time of the l-tyrosine sensor is less than 5 s. The excellent performance of the sensor is largely attributed to the electro-generated high reactive oxoiron (IV) porphyrin (O = FeIV-P) which effectively catalyzed the oxidation of l-tyrosine. A mechanism was herein proposed for the catalytic oxidation of l-tyrosine by oxoiron (IV) porphyrin complexes.  相似文献   

10.
A series of CuO-doped activated carbons (CDACs) were prepared by chemical deposition. The electrochemical behavior of CDACs was investigated in electrochemical capacitors based on ionic liquid 1-ethyl-3-methylimidazolium thiocyanate ([EMIm]SCN) as electrolyte. The results indicated that a diffusion-controlling, reversible redox reaction of CuO particles happened in ionic liquid and porous carbon. When the amount of CuO-doped activated carbon with a specific surface area of 2460 m2 g−1 reached 2%, the single electrode average specific capacitance can reach the maximal value of 210 F g−1, about 20% higher than the one used pure activated carbon as electrode material.  相似文献   

11.
The attachment of biotin to nanotube modified electrodes by formation of π-stacking interactions using a biotinylated pyrene derivative is reported. The specific anchoring of biological macromolecules via avidin bridges was investigated using biotinylated glucose oxidase (GOX-B) as model enzyme. Further studies focus the possibility of the electropolymerization of pyrene derivatives. Four types of biotin-SWCNT modified electrodes were investigated: (1) deposits of biotin-pyrene functionalized nanotubes (B-SWCNTs); (2) deposits of regular nanotubes, functionalized by incubation in a biotin-pyrene solution; (3) the latter configuration and subsequent electropolymerization of the adsorbed biotin-pyrene; and (4) deposits of regular nanotubes subsequently modified by electropolymerization of a pyrene-biotin monomer (2 mM). The nanotubes deposits were characterized by SEM imaging and the electropolymerization of the pyrene derivatives were investigated using cyclic voltammetry. These types of biotin-SWCNT modified electrodes were tested due to their capacity to immobilize biotinylated biomolecules (GOX-B) via avidin bridges and their performances in glucose detection were examined using amperometry. The best configuration (3) was obtained with SWCNT coatings modified by specific adsorption and electropolymerization of biotin-pyrene. A maximum current density of 584 μA cm−2 could be realized with a sensitivity of 37 mA M−1 cm−2 for a linear range between 5 μM and 13 mM.  相似文献   

12.
The electrochemical decoration of edge plane pyrolytic graphite electrode (EPPGE) with cobalt and cobalt oxide nanoparticles integrated with and without single-walled carbon nanotubes (SWCNTs) is described. Successful modification of the electrodes was confirmed by field emission scanning electron microscopy (FESEM), AFM and EDX techniques. The electron transfer behaviour of the modified electrodes was investigated in [Fe(CN)6]3−/4− redox probe using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) and discussed. The study showed that cobalt nanoparticles modified electrodes exhibit faster electron transfer behaviour than their oxides. The catalytic rate constant (K) obtained at the EPPGE-SWCNT-Co for nitrite at pH 7.4 and 3.0 are approximately the same (∼3 × 104 cm3 mol−1 s−1) while the limits of detection (LoD = 3.3δ/m) are in the μM order. From the adsorption stripping voltammetry, the electrochemical adsorption equilibrium constant β was estimated as (13.0 ± 0.1) × 103 M−1 at pH 7.4 and (56.7 ± 0.1) × 103 M−1 at pH 3.0 while the free energy change (ΔG°) due to the adsorption was estimated as −6.36 and −10.00 kJ mol−1 for nitrite at pH 7.4 and 3.0, respectively.  相似文献   

13.
Hydrolytic lignin (HL) was adsorbed from an aqueous/organic solution on bare and iodine-modified gold electrode. Subsequent electrooxidation of the lignin adsorbate generated redox-active quinone-based groups in the biopolymer structure, exhibiting high reversibility during potential cycling and fast electron transfer kinetics. The presence of the chemisorbed iodine layer on the supporting gold electrode had a pronounced effect on the electrochemical properties of the final modified electrode in terms of double-layer capacitance (Cdl) and the observed surface coverage (Γobs). The high electrochemical activity in connection with low Cdl made it possible to apply the Au|I(ads)|HL electrode as a fast-responding and sensitive electrochemical sensor for NADH. When tested in the amperometric mode at a constant potential of +0.4 V vs. Ag/AgCl, the modified electrode showed a linear current-concentration response over the range of 5-120 μM with a sensitivity of 2.39 nA μM−1 cm−2 and a detection limit of 1.0 μM (S/N = 3). Kinetic studies using the rotating disk electrode revealed that the mediated oxidation of NADH on the Au|I(ads)|HL electrode was limited by the second order reaction of the analyte molecules with o-quinone moieties with a rate constant of ca. 4.7 × 102 M−1 s−1 (CNADH → 0). The modified electrode showed high resistivity against fouling and retained ca. 65% activity after storage in phosphate buffer (pH 7.4) at room temperature for 1 week.  相似文献   

14.
A boron-doped carbon nanotube (BCNT)-modified glassy carbon (GC) electrode was constructed for the detection of l-cysteine (L-CySH). The electrochemical behavior of BCNTs in response to l-cysteine oxidation was investigated. The response current of L-CySH oxidation at the BCNT/GC electrode was obviously higher than that at the bare GC electrode or the CNT/GC electrode. This finding may be ascribed to the excellent electrochemical properties of the BCNT/GC electrode. Moreover, on the basis of this finding, a determination of L-CySH at the BCNT/GC electrode was carried out. The effects of pH, scan rate and interferents on the response of L-CySH oxidation were investigated. Under the optimum experimental conditions, the detection response for L-CySH on the BCNT/GC electrode was fast (within 7 s). It was found to be linear from 7.8 × 10−7 to 2 × 10−4 M (r = 0.998), with a high sensitivity of 25.3 ± 1.2 nA mM−1 and a low detection limit of 0.26 ± 0.01 μM. The BCNT/GC electrode exhibited high stability and good resistance against interference by other oxidizable amino acids (tryptophan and tyrosine).  相似文献   

15.
Electropolymerization of a new phenothiazine derivative (bis-phenothiazin-3-yl methane; BPhM) on glassy carbon (GC) electrode generates a conducting film of poly-BPhM, in stable contact with the electrode surface. The heterogeneous electron-transfer process corresponding to the modified electrode is characterized by a high rate constant (50.4 s−1, pH 7). The GC/poly-BPhM electrode shows excellent electrocatalytic activity toward NADH oxidation. The rate constant for catalytic NADH oxidation, estimated from rotating disk electrode (RDE) measurements and extrapolated to zero concentration of NADH, was found to be 9.4 × 104 M−1 s−1 (pH 7). The amperometric detection of NADH, at +200 mV vs. SCE, is described by the following electroanalytical parameters: a sensitivity of 1.82 mA M−1, a detection limit of 2 μM and a linear domain up to 0.1 mM NADH.  相似文献   

16.
A new amperometric glucose biosensor has been developed based on platinum (Pt) nanoparticles/polymerized ionic liquid-carbon nanotubes (CNTs) nanocomposites (PtNPs/PIL-CNTs). The CNTs was functionalized with polymerized ionic liquid (PIL) through directly polymerization of the ionic liquid, 1-vinyl-3-ethylimidazolium tetrafluoroborate ([VEIM]BF4), on carbon nanotubes and then used as the support for the highly dispersed Pt nanoparticles. The electrochemical performance of the PtNPs/PIL-CNTs modified glassy carbon (PtNPs/PIL-CNTs/GC) electrode has been investigated by typical electrochemical methods. The PtNPs/PIL-CNTs/GC electrode shows high electrocatalytic activity towards the oxidation of hydrogen peroxide. Taking glucose oxidase (GOD) as the model, the resulting amperometric glucose biosensor shows good analytical characteristics, such as a high sensitivity (28.28 μA mM−1 cm−2), wide linear range (up to 12 mM) and low detection limit (10 μM).  相似文献   

17.
Fast and simple quantitative determination in dispersed systems (layered double hydroxides - LDHs - suspensions in aqueous solutions) was performed by a procedure that couples flow injection and amperometric detection (FI-AM). LDH dispersions are injected in a continuous flow (1 mL min−1) of 0.05 mol L−1 KNO3 solution and [Cu(H2O)6]2+, used as a probe, is detected at a glassy carbon electrode housed in a flat electrochemical cell. The current intensity, recorded at the selected working potential (−0.25 V vs Ag/AgCl/NaCl (3 mol L−1)), presents a linear relationship with [Cu(H2O)6]2+ concentration and the procedure offers high sensitivity (slope = 0.036 μA/(μmol L−1)), a low detection limit (=0.7 μmol L−1) and a wide quantification range (4-200 μmol L−1).The method was applied to [Cu(H2O)6]2+ determination in two particular LDH-aqueous solution dispersed systems: (1) [Cu(H2O)6]2+ scavenging by etilendiammintetraacetic acid (EDTA) modified Zn-Al-LDHs, and (2) [Cu(H2O)6]2+ release from a copper doped Mg-Al-LDHs. The results obtained are comparable to those reported in previous works using different quantification techniques. FI-AM determination is applied without sample pretreatment (solid-supernatant separation) providing a high sampling rate (above 120 samples h−1) that allows a better comprehension of the processes, particularly at the initial stages.  相似文献   

18.
Platinum nanoparticles incorporated ZnO hybrid nanospheres (PtZONS) have been synthesized via electrodeposition which is easy to control over the size distribution range. The Pt nanoparticles in ZnO nanospheres have been identified with high-resolution transmission electron microscopy (HRTEM) and energy dispersive spectroscopy (EDS). Methanol sensing capabilities of the nanospheres have been investigated through electrochemical measurements. The electrochemical measurements prove that these nanospheres demonstrate the abilities to electrocatalyze the oxidation of methanol and substantially raise the response current. The sensitivity of the Nafion/PtZONS/glassy carbon modified electrode to methanol is 235.47 μA M−1 cm−2, which is much higher than that of a pure ZnO and Pt nanospheres modified electrodes. Furthermore, it has been revealed that the electrode exhibits a good anti-interference and long-term stability. Our investigation demonstrates that the Pt-ZnO nanospheres can be employed for various applications.  相似文献   

19.
The sol-gel technique was used to fabricate nickel powder carbon composite electrode (CCE). The nickel powder successfully used to deposit NiOx thin film on conductive carbon ceramic electrode for large surface area catalytic application. Repetitive cycling in potential range −0.2 to 1.0 V was used to form of a thin nickel oxide film on the surface carbon composite electrode. The thin film exhibits an excellent electro-catalytic activity for oxidation of SO32−, S2O42−, S2O32−, S4O62− and S2− in alkaline pH range 10-14. Optimum pH values for detection of all sulfur derivatives is 13 and catalytic rate constants are in range 2.4 × 103-8.9 × 103 M−1 s−1. The hydrodynamic amperometry at rotating modified CCE at constant potential versus reference electrode was used for detection of sulfur derivatives. Under optimized conditions the calibration plots are linear in the concentration range 10 μM-15 mM and detection limit 1.2-34 μM and 0.53-7.58 nA/μM (sensitivity) for electrode surface area 0.0314 cm2. The nickel powder doped modified carbon ceramic electrode shows good reproducibility, a short response time (2.0 s), remarkable long term stability, less expense, simplicity of preparation, good chemical and mechanical stability, and especially good surface renewability by simple mechanical polishing and repetitive potential cycling. This sensor can be used into the design of a simple and cheap chromatographic amperometry detector for analysis of sulfur derivatives.  相似文献   

20.
A bismuth-film electrode for use in cathodic electrochemical detection was employed in order to quantify sulfadiazine in pharmaceutical formulations. The bismuth film was deposited ex situ onto a glassy carbon substrate. Analysis of two sulfa drugs was carried out by differential-pulse voltammetry in 0.05 mol L−1 Britton-Robinson pH 4.5 solution. Sulfadiazine reduction was observed at −0.74 V vs. Ag/AgCl in one well-resolved irreversible reduction peak. The analytical curve with two slopes was obtained in the concentration range of 3.2-97.0 μmol L−1. The detection limit was 2.1 μmol L−1 for concentrations of 3.2-20.0 μmol L−1 (r = 0.9949) and 12.2 μmol L−1 for concentrations between 20.0 and 97.0 μmol L−1 (r = 0.9951). Recovery studies carried out with both sulfadiazine samples gave values from 93.6 to 109.3%. The accuracy of the results supplied by the bismuth-film electrode was compared to those obtained by the standard amperometric titration method. The relative error between them was lower than 2.0%.  相似文献   

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