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1.
Electrochemically active ruthenium oxide (RuOx?nH2O), ruthenium oxide/hexachloroiridate (RuOx?nH2O/IrCl62?), and ruthenium oxide/hexachloroiridate/platinum (RuOx?nH2O/IrCl62?/Pt) hybrid films have been prepared from the mixture of Ru3+, IrCl62?, and PtCl62? ions in an acidic aqueous solution. The repetitive cyclic voltammetry (CV) has been used for the film preparation process. The electrochemical properties and the growth mechanism of the above mentioned different kinds of hybrid films have been investigated using CV and electrochemical quartz crystal microbalance. The morphological and quantitative analyses have been carried out using scanning electron microscopy, atomic force microscopy and energy dispersive X‐ray. Among these above mentioned films, RuOx?nH2O/IrCl62?/Pt hybrid film exhibits promising electrocatalytic activity towards the oxidation of arsenic oxide, methanol and reduction of oxygen. Further, detailed study of electrocatalysis using rotating ring disk electrodes and amperometric methods have been carried out for arsenic oxide oxidation and oxygen reduction reactions at the hybrid films. From the results, the sensitivity of RuOx?nH2O/IrCl62?/Pt hybrid film has been calculated for arsenic oxide as 0.7 mA mM?1; and for oxygen as 1.8 mA mM?1.  相似文献   

2.
Jan-Wei Shie 《Talanta》2009,78(3):896-75
A conductive biocomposite film (MWCNTs-NF-Hb) containing multi-walled carbon nanotubes (MWCNTs) incorporated with entrapped haemoglobin (Hb) in nafion (NF) has been synthesized on glassy carbon electrode (GCE), gold (Au), indium tin oxide (ITO) and screen printed carbon electrode (SPCE) separately by potentiostatic methods. The presence of both MWCNTs and NF in the biocomposite film enhances the surface coverage concentration (Γ), and increases the electron transfer rate constant (Ks) to 132%. The biocomposite film exhibits a promising enhanced electrocatalytic activity towards the reduction of O2, H2O2 and CCl3COOH. The cyclic voltammetry has been used for the measurement of electrocatalysis results of analytes by means of biocomposite film-modified GCEs. The MWCNTs-NF-Hb-modified GCEs’ sensitivity values are higher than the values obtained for other film modified GCEs. The surface morphology of the biocomposite films which have been deposited on ITO has been studied using scanning electron microscopy and atomic force microscopy. The studies have revealed that there was an incorporation of NF and immobilization of Hb on MWCNTs. Finally, the flow injection analysis has been used for the amperometric studies of analytes at MWCNTs-Hb and MWCNTs-NF-Hb film modified SPCEs. The amperometric study results have shown higher slope values for MWCNTs-NF-Hb biocomposite film.  相似文献   

3.
An electrode of hydrated tungsten oxide (WO3?nH2O) embedded chitosan‐co‐polyaniline (CHIT‐co‐PANI) composite was electrochemically prepared on an indium tin oxide (ITO) coated glass surface using mineral acid as a supporting electrolyte. The resulting CHIT‐co‐PANI/WO3?nH2O/ITO electrode was characterized using ultraviolet‐visible spectroscopy (UV‐vis), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV), and scanning electron microscopy (SEM). The composite electrode exhibited a three‐dimensional nanofibrous structure with the diameter of the nanofibers ranging from 20 to 100 nm. The CHIT‐co‐PANI/WO3?nH2O/ITO electrode allowed for the low potential detection of NO2 gas in acidic medium. The NO2 gas sensing characteristics were studied by measuring change in the current with respect to concentration and time. Using the CHIT‐co‐PANI/WO3?nH2O/ITO electrode, NO2 gas was detected electrochemically without interference at pH 2.0 and 0.25 V vs. Ag/AgCl. The current of the electrochemical cell with the CHIT‐co‐PANI/WO3?nH2O/ITO electrode decreased linearly with an increase in NO2 gas concentration in a range from 100 to 500 ppb with a response time of eight seconds.  相似文献   

4.
The amorphous hydrous ruthenium oxide/mesoporous carbon composites (denoted as RuO2·xH2O/MC), obtained by loading small amount of amorphous hydrous ruthenium oxide nanoparticles ranged from 0.9 to 5.4% by weight of Ru (denoted as RuO2·xH2O) on mesoporous carbon (MC), were investigated for the first time and were used for supercapacitors. Electrochemical measurements showed that RuO2·xH2O/MC composites not only have an enhanced specific capacitance but also retain the superior rate capability of MC. The RuO2·xH2O/MC composite with Ru loading of 3.6 wt% exhibited an increase of the specific capacitance of approximately 57% (from 115 to 181 F/g) at the scan rate of 25 mV s−1 in 0.1 M H2SO4 aqueous electrolyte. The specific capacitance based on the mass of RuO2 was estimated to be 1,527 F/g, by subtracting the contribution from MC in the composite. Cycle performance tests for RuO2·xH2O/MC composite (3.6 wt% Ru) showed that approximately 2.8% loss of the total capacitance was observed after 1,000 cycles.  相似文献   

5.
Summary. The thermal and photoassisted catalytic oxidation of CO at metal oxide supported RuO2·xH2O was studied at room temperature. Contrary to neat RuO2·xH2O the supported catalysts suffer from fast deactivation attributed to strong adsorption of the reaction product carbon dioxide. The latter can be efficiently removed from the catalyst surface at elevated temperatures. In some cases, i.e. for catalysts supported with selected n-type semiconductors (TiO2, SnO2, WO3), efficient CO2 desorption and good, constant catalytic activity was observed upon visible light irradiation. Under such conditions the CO to CO2 conversion observed for RuO2·xH2O/TiO2 was nearly as good and stable as for the unsupported catalyst. It is suggested that light absorption promotes carbon dioxide desorption through positive charging of the catalyst surface.  相似文献   

6.
A composite film (MWCNTs-PNF) which contains multi-walled carbon nanotubes (MWCNTs) along with the incorporation of poly(new fuchsin) (PNF) has been synthesized on glassy carbon electrode (GCE), gold (Au) and indium tin oxide (ITO) by potentiostatic methods. The presence of MWCNTs in the composite film enhances surface coverage concentration (Γ) of PNF to ≈176.5%, and increases the electron transfer rate constant (ks) to ≈346%. The composite film also exhibits promising enhanced electrocatalytic activity towards the mixture of biochemical compounds such as adenine (AD), guanine (GU) and thymine (THY). The surface morphology of the composite film deposited on ITO has been studied using scanning electron microscopy and atomic force microscopy. These two techniques reveal that the PNF incorporated on MWCNTs. Electrochemical quartz crystal microbalance study reveals the enhancement in the functional properties of MWCNTs and PNF. The electrocatalytic responses of analytes at MWCNTs and MWCNTs-PNF films were measured using both cyclic voltammetry (CV) and differential pulse voltammetry (DPV). From electrocatalysis studies, well separated voltammetric peaks have been obtained at the composite film for AD, GU and THY, with the peak separation of 320.3 and 132.7 mV between GU-AD and AD-THY respectively. The sensitivity of the composite film towards AD, GU and THY in DPV technique is 218.18, 12.62 and 78.22 mA M−1 cm−2 respectively, which are higher than MWCNTs film. Further, electroanalytical studies of AD, GU and THY present in single-strand deoxyribonucleic acid (ssDNA) have been carried out using semi-derivative CV and DPV.  相似文献   

7.
Shie JW  Yogeswaran U  Chen SM 《Talanta》2008,74(5):1659-1669
A novel conductive biocomposite film (MWCNTs–DNA–cyt c) which contains multi-walled carbon nanotubes (MWCNTs) along with the incorporation of DNA and cytochrome c (cyt c) has been synthesized on glassy carbon electrode (GCE), gold (Au), indium tin oxide (ITO) and screen printed carbon electrode (SPCE) by potentiostatic methods. The presence of both MWCNTs and DNA in the biocomposite film enhances the surface coverage concentration (Γ), increases the electron transfer rate constant (Ks) up to 21% and decreases the degradation of cyt c during the cycling. The biocomposite film also exhibits a promising enhanced electrocatalytic activity towards the reduction of halogen oxyanions and oxidation of biochemical compounds such as ascorbic acid and l-cysteine. The cyclic voltammetry has been used for the measurement of electroanalytical properties of analytes by means of biocomposite film modified GCEs. The sensitivity of MWCNTs–DNA–cyt c modified GCE possess higher values than the values obtained for DNA–cyt c film modified GCE. Further, the reduction potentials of halogen oxyanions Epc, clearly shows that the activity of the biocomposite is dependent on the electronegativity of halogen oxyanions. Electrochemical quartz crystal microbalance studies revealed the enhancements in the functional properties of MWCNTs, DNA and cyt c. We have studied the surface morphology of the biocomposite films using scanning electron microscopy and atomic force microscopy, which revealed that DNA and cyt c have been incorporated on MWCNTs. Finally, the flow injection analysis has been used for the amperometric detection of analytes at MWCNTs–DNA–cyt c film modified SPCE.  相似文献   

8.
Owing to the synergy between metals, trimetal oxalate micropolyhedrons have been synthesized by means of a room‐temperature coprecipitation strategy. The effect of their nanoscale size on their electrochemical performance toward glucose oxidation was investigated. In particular, the Co0.5Mn0.1Ni0.4C2O4?n H2O micropolyhedrons illustrated prominent electrocatalytic activity for the glucose oxidation reaction. Additionally, the Co0.5Mn0.1Ni0.4C2O4?n H2O micropolyhedrons, when used as an electrode material, illustrated an excellent lower limit of detection (1.5 μm ), a wide detection concentration range (0.5–5065.5 μm ), and a high sensitivity (493.5 μA mm ?1 cm?2). Further analysis indicated that the effectively improved conductivity may have been due to the small size of the materials, and it was easier to form a flat film when Nafion was coated onto the glassy carbon electrode.  相似文献   

9.
《Electroanalysis》2005,17(7):579-587
Organic/inorganic hybrid films of poly(new fuchsin) and phosphomolybdate (PMo12O ) have been prepared in acidic aqueous solutions. These new combination films are stable, electrochemically active, and can be produced on glassy carbon, platinum, gold, and transparent semiconductor tin oxide electrodes. An electrochemical quartz crystal microbalance along with cyclic voltammetry and UV‐visible absorption spectroscopy were used to study the in situ growth of the hybrid films. The hybrid poly(new fuchsin) and PMo12O films showed four obvious redox couples, and when transferred to various acidic aqueous solutions, the formal potentials of the four redox couples were found to be pH dependent. The electrocatalytic reduction of ClO , BrO , IO , SO , S2O , H2O2, and NO by the hybrid poly(new fuchsin) and PMo12O films was achieved in acidic aqueous solutions. In an aqueous solution at pH 1.5, a hybrid poly(new fuchsin) and PMo12O film showed a higher electrocatalytic reduction activity of IO than BrO or ClO , and the order of electrocatalytic activity was IO >BrO >ClO . The order of electrocatalytic reduction of SO , S2O , H2O2, and NO by hybrid poly(new fuchsin) and PMo12O films in an aqueous solution at pH 1.5 was NO >H2O2>S2O and SO . The electrocatalytic reactions of the poly(new fuchsin) and PMo12O films were investigated using the rotating ring‐disk electrode method.  相似文献   

10.
A novel nanocomposite designed by the assembly of the positively charged poly(diallyldimethylammonium chloride) protected gold nanoparticles (PDDA‐GNPs), and the negatively charged multi‐walled carbon nanotubes (MWCNTs) on ITO electrode via electrostatic interaction, was used as a supporting matrix for immobilizing hemoglobin (Hb) to develop a high‐performance hydrogen peroxide (H2O2) biosensor. The cyclic voltammetrys of immobilized Hb showed a pair of well‐defined and quasi‐reversible redox peaks with the formal potential of ‐0.205V (vs. SCE) and the peak‐to‐peak potential separation of 44 mV at a scan rate of 100 mV×s?1 in 0.1 mol×L?1 pH 7.0 PBS. Under the optimized experimental conditions, a linearity range for determination of H2O2 was from 2.0 × 10?6 to 5.2 × 10?4 mol×L?1 with a correlation coefficient of 0.9994 (n = 37) and a detection limit of 8.4 × 10?7 mol×L?1. The biosensor displayed excellent electrochemical and electrocatalytic response to the reduction of H2O2, high sensitivity, long‐term stability, good bioactivity and selectivity.  相似文献   

11.
A promising nitrite sensor based on one‐dimensional polyoxometalate hybrid nanofibers was prepared and developed by electrospinning of a mixture of poly(vinyl alcohol) and α‐K6[P2W18O62]?14H2O (P2W18) onto the surface of an indium tin oxide (ITO) electrode. After thermal crosslinking, the P2W18 hybrid nanofibers are insoluble in aqueous solutions even after a period of 24 hours, which ensures the electrochemical stability of the P2W18 hybrid nanofiber‐modified ITO electrode. The cyclic voltammetry results have demonstrated that the P2W18 hybrid nanofiber‐modified ITO electrode exhibits excellent electrocatalytic activity toward the reduction of nitrite in acidic solutions. Additionally, long‐term stability and reproducibility have been observed.  相似文献   

12.
Two vic-dioxime ligands (LxH2) containing morpholine group have been synthesized from 4-[2-(dimethylaminoethyl)] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O (M: Ni, Cu or Co and n=2 or 6) salts in 1 : 2 molar ratio afforded metal complexes of type [M(LxH)2] or [M(LxH)2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities (Am) in DMF (dimethyl formamide) at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.  相似文献   

13.
Thermal gas-phase reactions of the ruthenium-oxide clusters [RuOx]+ (x=1–3) with methane and dihydrogen have been explored by using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. For methane activation, as compared to the previously studied [RuO]+/CH4 couple, the higher oxidized Ru systems give rise to completely different product distributions. [RuO2]+ brings about the generations of [Ru,O,C,H2]+/H2O, [Ru,O,C]+/H2/H2O, and [Ru,O,H2]+/CH2O, whereas [RuO3]+ exhibits a higher selectivity and efficiency in producing formaldehyde and syngas (CO+H2). Regarding the reactions with H2, as compared to CH4, both [RuO]+ and [RuO2]+ react similarly inefficiently with oxygen-atom transfer being the main reaction channel; in contrast, [RuO3]+ is inert toward dihydrogen. Theoretical analysis reveals that the reduction of the metal center drives the overall oxidation of methane, whereas the back-bonding orbital interactions between the cluster ions and dihydrogen control the H−H bond activation. Furthermore, the reactivity patterns of [RuOx]+ (x=1–3) with CH4 and H2 have been compared with the previously reported results of Group 8 analogues [OsOx]+/CH4/H2 (x=1–3) and the [FeO]+/H2 system. The electronic origins for their distinctly different reaction behaviors have been addressed.  相似文献   

14.
An organic–inorganic poly(3,4-ethylenedioxythiophene) (PEDOT)/RuO2·xH2O nanocomposite (approximately 1 wt.% RuO2) has been successfully prepared for the first time under microwave irradiation within 5 min with power 900 W via in situ chemical polymerization. The morphology and structure of the resultant material is characterized by transmission electron microscope and Fourier transform infrared. Moreover, the electrochemical properties of the synthesized nanocomposite can be controlled by adjusting the annealing temperature, which is definitely illustrated by cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectra. Electrochemical data have shown that the PEDOT/RuO2·xH2O nanocomposite annealed at 150 °C possesses the most favorable charge/discharge ability with a specific capacitance of 153.3 F g−1 at a current density of 150 mA g−1 and the high efficient utilization of PEDOT at various current densities. Furthermore, such composite has a less capacitance degradation of 23.8% after 1,000 continuous cycles. The improved electrochemical performance are mainly attributed to the large electroactive surface of nanocomposite and the existence of amorphous RuO2·xH2O particles as well as a synergistic effect of the polymer PEDOT and annealed RuO2·xH2O. Thus, the PEDOT/RuO2·xH2O nanocomposite annealed at 150 °C can act as a promising electroactive material for supercapacitor application.  相似文献   

15.
The present work describes reduction of iodate (IO3?), and periodate (IO4?) at silicomolybdate‐doped‐glutaraldehyde‐cross‐linked poly‐L ‐lysine (PLL‐GA‐SiMo) film coated glassy carbon electrode in 0.1 M H2SO4. In our previous study, we were able to prepare the PLL‐GA‐SiMo film modified electrode by means of electrostatically trapping SiMo12O404? mediator in the cationic film of PLL‐GA, and the voltammetric investigation in pure supporting indicated that the charge transport through the film was fast. Here, the electrocatalytic activity of PLL‐GA‐SiMo film electrode towards iodate and periodate was tested and subsequently used for analytical determination of these analytes by amperometry. The two electron reduced species of SiMo12O404? anion was responsible for the electrocatalytic reduction of IO3? at PLL‐GA‐SiMo film electrode while two and six electron reduced species were showed electrocatalytic activity towards IO4? reduction. Under optimized experimental conditions of amperometry, the linear concentration range and sensitivity are 2.5×10?6 to 1.1×10?2 M and 18.47 μA mM?1 for iodate, and 5×10?6 to 1.43×10?4 M and 1014.7 μA mM?1 for periodate, respectively.  相似文献   

16.
Mesoporous silica thin films encapsulating a molecular iron‐triazole complex, Fe(Htrz)3 (Htrz=1,2,4,‐1H‐triazole), have been generated by electrochemically assisted self‐assembly (EASA) on indium‐tin oxide (ITO) electrode. The obtained modified electrodes are characterized by well‐defined voltammetric signals corresponding to the FeII/III centers of the Fe(Htrz)3 species immobilized into the films, indicating fast electron transfer processes and stable operational stability. This is due to the presence of a high density of redox probes in the material (1.6×10?4 mol g?1 Fe(Htrz)3 in the mesoporous silica film) enabling efficient charge transport by electron hopping. The mesoporous films are uniformly deposited over the whole electrode surface and they are characterized by a thickness of 110 nm and a wormlike mesostructure directed by the template role played by Fe(Htrz)3 species in the EASA process. These species are durably immobilized in the material (they are not removed by solvent extraction). The composite mesoporous material (denoted Fe(Htrz)3@SiO2) is then used for the electrocatalytic detection of hydrogen peroxide, which can be performed by amperometry at an applied potential of ?0.4 V versus Ag/AgCl and by flow injection analysis. The organic‐inorganic hybrid film electrode displays good sensitivity for H2O2 sensing over a dynamic range from 5 to 300 μM, with a detection limit estimated at 2 μM.  相似文献   

17.
Here we report the synthesis, structure and detailed characterisation of three n‐membered oxovanadium rings, Nan[(V=O)nNan(H2O)n(α, β, or γ‐CD)2]?m H2O (n=6, 7, or 8), prepared by the reactions of (V=O)SO4?x H2O with α, β, or γ‐cyclodextrins (CDs) and NaOH in water. Their alternating heterometallic vanadium/sodium cyclic core structures were sandwiched between two CD moieties such that O‐Na‐O groups separated the neighbouring vanadyl ions. Antiferromagnetic interactions between the S=1/2 vanadyl ions led to S=0 ground states for the even‐membered rings, but to two quasi‐degenerate S=1/2 states for the spin‐frustrated heptanuclear cluster.  相似文献   

18.
A series of five l ‐di‐p‐toluoyl‐tartaric acid (l ‐DTTA) lanthanide coordination polymers, namely {[Ln4K4 L6(H2O)x]?yH2O}n, [Ln=Dy ( 1 ), x=24, y=12; Ln=Ho ( 2 ), x=23, y=12; Ln=Er ( 3 ), x=24, y=12; Ln=Yb ( 4 ), x=24, y=11; Ln=Lu ( 5 ), x=24, y=12] have been isolated by simple reactions of H2L (H2L= L ‐DTTA) with LnCl3?6 H2O at ambient temperature. X‐ray crystallographic analysis reveals that complexes 1 – 5 feature two‐dimensional (2D) network structures in which the Ln3+ ions are bridged by carboxylate groups of ligands in two unique coordinated modes. Luminescent spectra demonstrate that complex 1 realizes single‐component white‐light emission, while complexes 2 – 4 exhibit a characteristic near‐infrared (NIR) luminescence in the solid state at room temperature.  相似文献   

19.
A robust and effective composite film combined the benefits of Nafion, room temperature ionic liquid (RTIL) and multi‐wall carbon nanotubes (MWNTs) was prepared. Hemoglobin (Hb) was successfully immobilized on glassy carbon electrode surface by entrapping in the composite film. Direct electrochemistry and electrocatalysis of immobilized Hb were investigated in detail. A pair of well‐defined and quasi‐reversible redox peaks of Hb was obtained in 0.10 mol·L?1 pH 7.0 phosphate buffer solution (PBS), indicating that the Nafion‐RTIL‐MWNTs film showed an obvious promotion for the direct electron transfer between Hb and the underlying electrode. The immobilized Hb exhibited an excellent electrocatalytic activity towards the reduction of H2O2. The catalysis current was linear to H2O2 concentration in the range of 2.0×10?6 to 2.5×10?4 mol·L?1, with a detection limit of 8.0×10?7 mol·L?1 (S/N=3). The apparent Michaelis‐Menten constant (Kmapp) was calculated to be 0.34 mmol·L?1. Moreover, the modified electrode displayed a good stability and reproducibility. Based on the composite film, a third‐generation reagentless biosensor could be constructed for the determination of H2O2.  相似文献   

20.
Heteropoly acids Cs x H3 − x PW12O40 · nH2O with different cesium content are synthesized as nanostructured compositions. Their actual composition and specific surface are determined, microstructure studied and proton conductivity measured. Composite electrocatalytic systems based on platinized cesium salt of phosphorus-tungsten heteropolyacid Cs2.3H0.7PW12O40 · nH2O are prepared with admixture of Vulcan XC-72 carbon black. Mixed electronic-ionic conduction of the composite systems with different carbon black content is studied. Platinum-based nanostructured electrocatalyst based on the Cs2.3H0.7PW12O40 · nH2O-materials as support is synthesized and studied. The possible effective using of the studied nanocomposite as electrode for low-temperature hydrogen-air fuel cells is demonstrated. Electrochemical studies of catalytic properties of the Pt-Cs2.3H0.7PW12O40 · nH2O-C-electrodes in hydrogen and air are carried out by example of the prepared materials with different carbon black content.  相似文献   

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