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1.
The electrochemical redox properties of a surface‐confined thin solid film of nanostructured cobalt(II) tetracarboxyphthalocyanine integrated with multiwalled carbon nanotube (nanoCoTCPc/MWCNT) have been investigated. This novel nanoCoTCPc/MWCNT material was characterized using SEM, TEM, zeta analysis and electrochemical methods. The nanoCoTCPc/MWCNT nanohybrid material exhibited an extra‐ordinarily high conductivity (15 mS cm?1), which is more than an order of magnitude greater than that of the MWCNT‐SO3H (527 µS cm?1) and three orders of a magnitude greater than the nanoCoTCPc (4.33 µS cm?1). The heterogeneous electron transfer rate constant decreases as follows: nanoCoTCPc/MWCNT (kapp≈19.73×10?3 cm s?1)>MWCNT‐SO3H (kapp≈11.63×10?3 cm s?1)>nanoCoTCPc (kapp≈1.09×10?3 cm s?1). The energy‐storage capability was typical of pseudocapacitive behaviour; at a current density of 10 µA cm?2, the pseudocapacitance decreases as nanoCoTCPc/MWCNT (3.71×10?4 F cm?2)>nanoCoTCPc (2.57×10?4 F cm?2)>MWCNT‐SO3H (2.28×10?4 F cm?2). The new nanoCoTCPc/MWCNT nanohybrid material promises to serve as a potential material for the fabrication of thin film electrocatalysts or energy‐storage devices.  相似文献   

2.
A novel bioelectrocatalytic system was prepared by immobilizing alcohol oxidase (AOx) onto multiwalled carbon nanotubes (MWCNT) modified with 4‐(pyrrole‐1‐yl) benzoic acid (PyBA). Functional carboxylic groups from PyBA create covalent amide linkages with amine groups from the enzyme molecule and provide an anchor for the effective immobilization of AOx improving the stability of the whole system. The immobilized enzyme displayed a pair of reversible redox peaks of flavin adenine dinucleotide (FAD) cofactor with the formal potential E0’=?0.451 V. The response showed a surface‐controlled electrode process with the heterogeneous electron transfer rate constant ks=2.7 s?1. Under aerobic conditions AOx(FADH2) can be oxidized to AOx(FAD) by oxygen, which then reacts with ethanol decreasing the cathodic response, which could be used for ethanol detection with a high sensitivity 13.1 μA mM?1 cm?2. The lack of bioactivity towards ethanol in anaerobic conditions suggests the presence of two types of AOx molecules in the system: active with oxygen maintaining the direct electron transfer feature and not active without a redox mediator, due to the deeply embedded FAD cofactor. The polarization curve showed that the electrooxidation current of ethanol appears at ?410 mV and reaches 2.0 µA cm?1 at ?300 mV. In this case, the bioactivity of AOx to ethanol can be observed offering promising solution for the development of mediatorless systems for application to biosensors and biofuel cells.  相似文献   

3.
The present study was aimed at investigating the use of a mixture multiwall carbon nanotube (MWCNT) and thionine (Th) dye in designing of a thionine‐based electrochemical biosensor containing catalase (Ct) enzyme (MWCNT‐Nafion‐Th/Ct) onto a glassy carbon electrode (GCE). The effects of pH, MWCNT concentration and thionine concentration on electrochemical response were explored for optimum analytical performance. The modified electrode exhibited a pair of well‐defined, quasi‐reversible peaks at formal potential (Eo′) = ‐0.218 ± 0.017 V vs. Ag/AgCl corresponding to the Thox/Thred redox couples in the presence of MWCNT, Nafion, and Ct. The electrochemical parameters, including charge‐transfer coefficient (0.36), and apparent heterogeneous electron transfer rate constant (4.28 ± 0.26 s?1) were determined. Using differential pulse voltammetry, the prepared enzyme electrode exhibited a linear response to hydrogen peroxide (H2O2) in the range of 10.0‐100.0 μM with a detection limit 8.7 μM and a sensitivity of 6051.0 μA mM?1 cm?2.  相似文献   

4.
A unique sodium sulfide (Na2S) cathode is developed, which will allow the use of sodium‐free anodes for room‐temperature sodium–sulfur (Na–S) batteries. To overcome the “inert” nature of the Na2S, a special cathode structure is developed by spreading the multi‐walled carbon nanotube (MWCNT)‐wrapped Na2S particles onto MWCNT fabrics. Spectroscopic and electrochemical analyses reveal a series of polysulfide intermediates involved in the charge/discharge of the cell. The Na–S battery prepared in full discharge state with the Na2S/MWCNT cathode provides a remarkable capacity of 500 A h kg?1 (based on sulfur mass) after 50 cycles.  相似文献   

5.
This study develops a simple surface modification process for modifying the MWCNT surface by thiolation reaction after the conventional nitric acid treatment for strong interface attachment of Pt NPs and improved dispersion onto MWCNTs. The thiolated MWCNTs (Pt/MWCNTs) showed significant improvement of methanol electro‐oxidation activity compared with that treated only by nitric acid solution. The prepared electrode with thiolated MWCNTs was used as the cathode for assembling MEA for DMFC single‐cell applications. Testing results indicate that the thiolated MWCNT cathode can improve the power density of MEA by more than 300% (from 4.6 to 20.6 mW cm?2) compared with that treated only by conventional nitric acid reactions. The dual‐step modification process for MWCNT surface treatment showed significant improvement over the convention nitric acid treatment and can be successfully used in DMFC applications.  相似文献   

6.
The nickel tetrasulfonated phthalocyanine (NiTsPc) functionalized multiwalled carbon nanotube (MWCNT) nanocomposite was prepared by a simple sonochemical method. Here, NiTsPc served as a dispersing agent for MWCNT via π? π interaction between MWCNT and NiTsPc. The activated glassy carbon electrode (AGCE) modified with MWCNT‐NiTsPc composite exhibited a good electrocatalytic ability toward dopamine and displayed a good linear dependence in the concentration range of 20 nM–1.384 mM with a sensitivity of 0.17 µA µM?1 cm?2. The detection limit is 1 nM based on the signal‐to‐noise ratio of 3.  相似文献   

7.
Composites of multiwall carbon nanotubes (MWCNTs) and sulfonated polyaniline (SPAN) were prepared through the oxidative polymerization of a mixture of aniline, 2,5‐diaminobenzene sulfonic acid, and MWCNTs. Fe, Pd, or Fe–Pd alloy nanoparticles were embedded into the MWCNT–SPAN matrix by the reduction of Fe, Pd, or a mixture of Fe and Pd ions with γ radiation. Sulfonic acid groups and the emeraldine form of backbone units in SPAN served as the source for the reduction of the metal ions in the presence of γ radiation. The existence of metallic/alloy particles in the MWCNT–SPAN matrix was further ascertained through characterization by high‐resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, thermogravimetric analysis, and conductivity measurements. HRTEM pictures clearly revealed the existence of Fe, Pd, and Fe–Pd nanoparticles of various sizes in the MWCNT–SPAN matrices. There were changes in the electronic properties of the MWCNT–SPAN–M composites due to the interaction between the metal nanoparticles and MWCNT–SPAN. Metal‐nanoparticle‐loaded MWCNT–SPAN composites (MWCNT–SPAN–M; M = Fe, Pd, or Fe–Pd alloy) showed better thermal stability than the pristine polymers. The conductivity of the MWCNT–SPAN–M composites was approximately 1.5 S cm?1, which was much higher than that of SPAN (2.46 × 10?4 S cm?1). Metal/alloy‐nanoparticle‐embedded, MWCNT‐based composite materials are expected to find applications in molecular electronics and other fields. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3355–3364, 2006  相似文献   

8.
A new type of Ni2+-loaded MWCNT composite was prepared by mixing carboxylated multiwalled carbon nanotubes (MWCNTs) and Ni2+ ions and allowing them to interact electrostatically. The resulting composite was subsequently used as an electrocatalyst for glucose (Glu) oxidation. Compared with electrodes modified through the addition of free Ni2+ ions or MWCNTs, the Ni2+/MWCNT composite electrode showed greatly improved properties such as hydrophilicity. Investigations of the Ni2+/MWCNT composite electrode via inductively coupled plasma atomic emission spectroscopy and nitrogen adsorption–desorption isotherms verified that Ni2+ ions had been adsorbed onto the surfaces of the MWCNTs in the composite. As expected, a Ni2+/MWCNT composite-based sensor showed extraordinary electrocatalytic performance in Glu oxidation. In the concentration range 0–4.3 mM, a good linear relationship between the Glu added and the current generated was observed, with a correlation coefficient (R 2) of 0.9988. The detection limit and sensitivity were calculated to be 0.081 μM and 2285 μA mM?1 cm?2, respectively. Finally, the new method was successfully applied to determine the Glu in a human blood sample. Recoveries of >100%, indicative of high reliability, accuracy, and precision, were obtained.  相似文献   

9.
Hydrazines are well‐known for their diverse biological properties but especially for their toxicity. An amperometric hydrazine sensor was developed at multi‐walled carbon nanotubes (MWCNT) and iron tetrasulfonated phthalocyanine (FeTsPc) composite modified electrode for the first time. The TEM and UV‐Vis spectroscopy results revealed the successful formation of MWCNT/FeTsPc composite. Compared with the response of MWCNT and FeTsPc modified electrodes, the MWCNT/FeTsPc composite showed enhanced oxidation current response with lower overpotential for hydrazine. Under optimum conditions, the amperometric it response of hydrazine was linear in the concentration range from 100 nM L?1 to 3 μM L?1 with the detection limit of 7.6 nM L?1. The response time of hydrazine was found as 6 s with a high sensitivity of 7.615 μA/μM L?1 cm?2.  相似文献   

10.
A new voltammetric sensor based on molecularly imprinted poly(acrylic acid)‐MWCNT nanocomposite (MIP‐MWCNT) drop‐coated onto glassy carbon electrode (GCE) was developed and applied to tramadol (TR) determination in pharmaceutical samples. The voltammetric sensor prepared by suspension of MIP‐MWCNT at 1 : 1 (w/w) ratio show an improved performance compared to unmodified GCE. The electrochemical method is based on preconcentration of tramadol onto MIP‐MWCNT modified GCE surface at ?1.5 V vs Ag/AgCl for 180 s in 0.1 Britton‐Robinson buffer (pH 8.0) at stirred solution. Upon preconcentration, the differential anodic voltammogram was recorded under the optimized condition giving rise to an analytical curve varying from 9.0 up to 30.0 μmol L?1 (R2=0.997) and limits of detection and quantification of 1.4 and 4.8 μmol L?1, respectively. The method precision was assessed in terms of intraday (n=6) and interday (two consecutive days) precision, giving relative standard deviations (RSD%) values between 2.8 to 7.4 %. Excipients usually found in pharmaceutical pills (magnesium stearate, microcrystalline cellulose, starch, and silica) and paracetamol were evaluated as potential interferents, however no interference was evidenced in TR determination. The method applicability was evaluated by TR analysis in pharmaceutical samples. Moreover, the method accuracy was attested by comparison of addition and recovery assays with a reference technique (high‐performance liquid chromatography).  相似文献   

11.
Electrochemical capacitive behaviour of the electropolymeric nickel tetra‐aminophthalocyanine (poly‐NiTAPc) supported on multiwalled carbon nanotube (MWCNT) platform is described. From the data in 1 M H2SO4, the MWCNT‐poly‐NiTAPc exhibited superior capacitance (112 mF cm?2 or 777 F g?1). The supercapacitance of the MWCNT‐polyNiTAPc was found to be much better in 1 M H2SO4 than in 1 M NaOH medium. Impedance data proved that most of the stored energy of the MWCNT‐poly‐NiTAPc could be accessible at high frequency (1.6 kHz). The electrode is capable of undergoing continuous charge‐discharge process for more than a 1000 cycles without any significant deterioration in the stability.  相似文献   

12.
Precursor of polyimide, polyamic acid has been prepared sucessfully. Acid‐modified carbon nanotube (MWCNT) was grafted with soluble polyimide then was added to the polyamic acid and heated to 300 °C to form polyimide/carbon nanotube composite via imidation. Morphology, mechanical properties and electrical resistivity of the MWCNT/polyimide composites have been studied. Transmission electron microscope microphotographs show that the diameter of soluble polyimide‐grafted MWCNT was increased from 30–60 nm to 200 nm, that is a thickness of 70–85 nm of the soluble polyimide was grafted on the MWCNT surface. PI‐g‐MWCNT was well dispersed in the polymer matrix. Percolation threshold of MWCNT/polyimide composites has been investigated. PI‐g‐MWCNT/PI composites exhibit lower electrical resistivity than that of the acid‐modified MWCNT/PI composites. The surface resistivity of 5.0 phr MWCNT/polyimide composites was 2.82 × 108 Ω/cm2 (PI‐g‐MWCNT) and 2.53 × 109 Ω/cm2 (acid‐modified MWCNT). The volume resistivity of 5.0 phr MWCNT/polyimide composites was 8.77 × 106 Ω cm (PI‐g‐MWCNT) and 1.33 × 1013 Ω cm (acid‐modified MWCNT).Tensile strength and Young's modulus increased significantly with the increase of MWCNT content. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3349–3358, 2007  相似文献   

13.
The electrochemical reduction of three common insecticides such as cypermethrin (CYP), deltamethrin (DEL) and fenvalerate (FEN) was investigated at glassy carbon electrode (GCE), multiwalled carbon nanotubes modified GCE (MWCNT‐GCE), polyaniline (herein called as modifier M1) and polypyrrole (herein called as modifier M2) deposited MWCNT/GCE using cyclic voltammetry. Influences of pH, scan rate, and concentration were studied. The surface morphology of the modified film was characterized by scanning electron microscopy (SEM) and X‐ray diffraction analysis (XRD). A systematic study of the experimental parameters that affect differential pulse stripping voltammetry (DPSV) was carried out and the optimized experimental conditions were arrived at. The calibration plots were linear over the insecticide's concentration range 0.1–100 mg L?1 and 0.05–100 mg L?1 for all the three insecticides at MWCNT‐GCE and MWCNT(M1)‐GCE respectively. The MWCNT(M2)‐GCE performed well among the three electrode systems and the determination range obtained was 0.01–100 mg L?1 for CYP, DEL and FEN. The limit of detection (LOD) was 0.35 μg L?1, 0.9 μg L?1 and 0.1 μg L?1 for CYP, DEL and FEN respectively on MWCNT(M2)‐GCE modified system. Suitability of this method for the trace determination of insecticide in spiked soil sample was also determined.  相似文献   

14.
A pentacyclic benzodipyrrolothiophene ( BDPT ) unit, in which two outer thiophene rings are covalently fastened with the central phenylene ring by nitrogen bridges, was synthesized. The two pyrrole units embedded in BDPT were constructed by using one‐pot palladium‐catalyzed amination. The coplanar stannylated Sn‐BDPT building block was copolymerized with electron‐deficient thieno[3,4‐c]pyrrole‐4,6‐dione ( TPD ), benzothiadiazole ( BT ), and dithienyl‐diketopyrrolopyrrole ( DPP ) acceptors by Stille polymerization. The bridging nitrogen atoms make the BDPT motif highly electron‐abundant and structurally coplanar, which allows for tailoring the optical and electronic properties of the resultant polymers. Strong photoinduced charge‐transfer with significant band‐broadening in the solid state and relatively higher oxidation potential are characteristic of the BDPT‐based polymers. Poly(benzodipyrrolothiophene‐alt‐benzothiadiazole) ( PBDPTBT ) achieved the highest field‐effect hole mobility of up to 0.02 cm2 V?1 s?1. The photovoltaic device using the PBDPTBT /PC71BM blend (1:3, w/w) exhibited a Voc of 0.6 V, a Jsc of 10.34 mA cm?2, and a FF of 50 %, leading to a decent PCE of 3.08 %. Encouragingly, the device incorporating poly(benzodipyrrolothiophene‐alt‐thienopyrrolodione) ( PBDPTTPD )/PC71BM (1:3, w/w) composite delivered a highest PCE of 3.72 %. The enhanced performance arises from the lower‐lying HOMO value of PBDPTTPD to yield a higher Voc of 0.72 V.  相似文献   

15.
Two small molecules named BT‐TPD and TBDT‐TTPD with a thieno[3,4‐c]pyrrole‐4,6‐dione (TPD) unit were designed and synthesized for solution‐processed bulk‐heterojunction solar cells. Their thermal, electrochemical, optical, charge‐transport, and photovoltaic characteristics were investigated. These compounds exhibit strong absorption at 460–560 nm and low highest occupied molecular orbital levels (?5.36 eV). Field‐effect hole mobilities of these compounds are 1.7–7.7×10?3 cm2 V?1 s?1. Small‐molecule organic solar cells based on blends of these donor molecules and a acceptor display power conversion efficiencies as high as 4.62 % under the illumination of AM 1.5G, 100 mW cm?2.  相似文献   

16.
A biosensor based on conductive poly(pyrrole‐co‐pyrrole‐2‐carboxylic acid) [Poly(Py‐co‐PyCOOH)] copolymer film coated gold electrode was developed for the quantitative phosphate determination. Enzyme pyruvate oxidase was immobilized chemically via the functional carboxylated groups of the copolymer. The potential to be applied which is deficiency of phosphate biosensor studies for precise phosphate detection was clarified by using differential pulse voltammetry technique. Performance of the sensing ability of the biosensor was improved by optimizing cofactor/cosubstrate concentrations, polymeric film density and pH. The biosensor showed a linearity up to phosphate concentration of 5 mM, operational stability with a relative standard deviation (RSD) of 0.07 % (n=7) and accuracy of 101 % at ?0.15 V (vs. Ag/AgCl). Detection limit (LOD) and sensitivity were calculated to be 13.3 μM and 5.4 μA mM?1 cm?2, respectively by preserving 50 % of its initial response at the end of 30 days. It's performance was tested to determine phosphate concentrations in two streams of Zonguldak City in Turkey. Accuracy of phosphate measurement in stream water was found to be 91 %.  相似文献   

17.
A wide variety of 2,5‐di(2‐pyridyl)pyrroles (dppHs) substituted at the C3 and C4 positions of the pyrrole core were obtained by direct condensation of a 2‐pyridylcarboxaldehyde (2 equiv), an α‐methylene ketone with at least one electron‐withdrawing substituent and ammonium acetate. A novel 2,5‐di(1,10‐phenanthrolin‐2‐yl)pyrrole was also characterised. The dppHs provide a direct, quick entry to dipyridylpyrrolato (dpp?)–metal complexes. The meridial tridentate dpp? ligand is a useful anionic analogue of the terpyridyl ligand. The first (dpp)Ru complexes are described; the 3,4‐substitution of the central pyrrole significantly perturbs the potentials of the redox processes of these complexes. A [(dpp)Ru(bpy)(MeCN)]+ (bpy=2,2′‐bipyridine) complex is an electrocatalyst for the reductive disproportionation of carbon dioxide to carbon monoxide and the carbonate ion.  相似文献   

18.
Single‐walled carbon nanotubes (SWCNTs) deposits on glassy carbon and pyrolytic graphite electrodes have dramatically enhanced the direct electron transfer of the multihemic nitrite reductase from Desulfovibrio desulfuricans ATCC 27774, enabling a 10‐fold increase in catalytic currents. At optimal conditions, the sensitivity to nitrite and the maximum current density were 2.4±0.1 A L mol?1 cm?2 and 1500 µA cm?2, respectively. Since the biosensor performance decreased over time, laponite clay and electropolymerized amphiphilic pyrrole were tested as protecting layers. Both coating materials increased substantially the bioelectrode stability, which kept about 90 % and 60 % of its initial sensitivity to nitrite after 20 and 248 days, respectively.  相似文献   

19.
A core‐shell NiAlO@polypyrrole composite (NiAlO@PPy) with a 3D “sand rose”‐like morphology was prepared via a facile in situ oxidative polymerization of pyrrole monomer, where the role of PPy coating thickness was investigated for high‐performance supercapacitors. Microstructure analyses indicated that the PPy was successfully coated onto the NiAlO surface to form a core‐shell structure. The NiAlO@PPy exhibited a better electrochemical performance than pure NiAlO, and the moderate thickness of the PPy shell layer was beneficial for expediting the electron transfer in the redox reaction. It was found that the NiAlO@PPy5 prepared at 5.0 mL L?1 addition amount of pyrrole monomer demonstrated the best electrochemical performance with a high specific capacitance of 883.2 F g?1 at a current density of 1 A g?1 and excellent capacitance retention of 91.82 % of its initial capacitance after 1000 cycles at 3 A g?1. The outstanding electrochemical performance of NiAlO@PPy5 were due to the synergistic effect of NiAlO and PPy, where the uniform network‐like PPy shell with the optimal thickness made electrolyte ions more easily accessible for faradic reactions. This work provided a simple approach for designing organic–inorganic core‐shell materials as high‐performance electrode materials for electrochemical supercapacitors.  相似文献   

20.
The nanocomposite electrode comprising of polypyrrole (PPY) and carboxy functionalized multiwalled carbon nanotubes (MWCNT) has been electrochemically fabricated onto indium–tin–oxide (ITO) electrode using p‐toluene sulfonic acid (PTS). Cholesterol oxidase (ChOx) and cholesterol esterase (ChEt) have been immobilized onto this PPY– MWCNT/ITO nanocomposite electrode using N‐ethyl‐N‐(3‐dimethylaminopropyl) carbodiimide and N‐hydroxy succinimide chemistry for estimation of esterified cholesterol. The ChEt–ChOx/PPY–MWCNT/PTS/ITO bioelectrode has been characterized using Fourier transform infrared spectroscopy, electrochemical techniques, and scanning electron microscope. This ChEt–ChOx/PPY–MWCNT/PTS/ITO nanobioelectrode has a response time of about 9 s, linearity of 4 × 10?4 to 6.5 × 10?3 M/l of cholesterol oleate concentration, Km of 0.02 mM, and thermal stability of upto 45°C. This electrode exhibits improved biosensing characteristics compared with other total cholesterol electrodes reported in literature till date and can be used to estimate cholesterol in blood serum samples. Copyright © 2011 John Wiley & Sons, Ltd.  相似文献   

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