首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献,搜索用时 15 毫秒
1.
The voltammetric behavior of 1-naphthol was studied with a poly (acridine orange) (PAO) film modified glass carbon electrode (GCE). The electrooxidation of 1-naphthol was an irreversible process with its oxidation overpotential at the PAO electrode 180 mV lower than that on the GCE. PAO electrode demonstrated electrocatalytic activity to the electrooxidation of 1-naphthol giving a greatly improved detection limit down to 8 × 10−8 mol L−1(S/N = 3). At the optimal experimental condition, the oxidation peak current from the PAO electrode was linearly proportional to the concentration of 1-naphthol in the range of 2 × 10−7 to 3.2 × 10−6 mol L−1 and 5.2 × 10−6 to 1.2 × 10−4 mol L−1. The differences of the oxidation peak potentials between 1-naphthol and the coexisted 2-naphthol was 170 mV allowing the selective detection of 1-naphthol in a mixed solution with 2-naphthol. The detection of 1-naphthol in tap water and river water was carried out with satisfactory results.  相似文献   

2.
The electrochemical behaviour of UCl4 (0.01 mol L−1 up to 0.05 mol L−1) in 0.1 mol L−1 TBAPF6/DMF solution at vitreous carbon was studied, at room temperature, by cyclic voltammetry and potentiostatic techniques. The electrolytic solutions were analyzed by UV spectroscopy (UV), and the electrodeposited films were characterized by Rutherford Backscattering Spectroscopy (RBS) and X-ray diffraction (XRD). The cyclic voltammetric results, at low UCl4 concentrations (0.01 mol L−1), point that the reduction of U(IV) to U(0) occurs in two steps involving mainly U(IV) and U(III) species. The first electron transfer reaction is quasi-reversible and the second irreversible. The diffusion coefficient of U(IV) in DMF and the charge rate constant were determined to be 4.78 × 10−7 cm2 s−1 and 1.93 × 10−3 cm s−1 (at 0.02 V s−1), respectively.RBS data obtained from samples prepared at constant potential (−3.10 V) during 3 h at room temperature, indicated the presence of uranium particles deposited all over the vitreous carbon surface with aggregates in some places, confirming that the second reduction step corresponds to uranium electrodeposition. No crystallographic ordering could be seen by XRD, pointing to an amorphous character of the uranium films.  相似文献   

3.
Solution studies showed the strong interaction of [5-(dimethylamino) naphthalene-1-sulfonyl 4-phenylsemicarbazide] (NSP) with Er(III) ions. NSP was used as a sensing material during construction of carbon paste Er(III) sensors. The electrodes were modified with 1-n-butyl-3-methylimidazolium tetrafluoroborate, [bmim]BF4, as room temperature ionic liquid (RTIL) and multi-walled carbon nanotube (MWCNT). Potentiometric sensors constructed with [bmim]BF4 and MWCNTs show better sensitivity, selectivity, response time, and response stability compared to Er(III) carbon paste sensors. The best performance for the modified sensor was obtained with an electrode composition of 20% [bmim]BF4, 20% NSP, 45% graphite powder and 15% MWCNT. This particular sensor formulation exhibits a Nernstian response (19.8 ± 0.3 mV decade−1) toward Er(III) ions in the range of 1.0 × 10−7 to 1.0 × 10−1 mol L−1 with a detection limit of 5.0 × 10−8 mol L−1. The proposed modified Er(III) sensor can be used over the pH range from 3.5 to 9.0.  相似文献   

4.
The activation of 3,5-dinitrobenzoic acid (3,5-DNBA) in situ is proposed for electrocatalytic detection of NADH at low overpotentials. Thus, 3,5-DNBA was strategically connected to a nanostructured surface based on MWCNTs and PEI (an amine rich polymer). Then, R–NO/R–NHOH was electrogenerated in situ by cycling the potential between 0.15 and −0.55 V versus SCE. The formation of an intermediate charge transfer complex is proposed for the reaction between NADH and redox mediator. The apparent Michaelis–Menten constant (KM) obtained by RDE voltammetry and amperometry was in good agreement, around 10−5 mol L−1. The kobs for the catalytic reaction evaluated by chronoamperometry and RDE voltammetry, was in good agreement and was found to be around 104 L mol−1 s−1. The sensor provides a linear response range for NADH from 4.0 up to 42.0 μmol L−1 with a sensitivity of 71 nA L μmol−1, detection and quantification limits of 1.2 and 4.0 μmol L−1 respectively, with a response time of 0.16 s.  相似文献   

5.
Highly organized (3-mercaptopropyl)trimethoxysilane (3-MPT) films have been prepared via self-assembled coupled with sol–gel linking technology. Horseradish peroxidase (HRP) is successfully immobilized onto the densely packed three-dimensional (3D) 3-MPT network and the direct electrochemistry of HRP is achieved without any electron mediators or promoters. Redox thermodynamics of HRP on the 3-MPT films, which is obtained from the temperature dependence of the reduction potential, suggests that the positive shift of redox potentials of HRP at the interface of 3-MPT originates from the solvent reorganization effects and conformational change of the polypeptide chain of HRP. Based on the direct electrochemistry and electrocatalytic ability of HRP, a sensitive third-generation amperometric H2O2 biosensor is developed with two linear dependence ranges of 5.0 × 10−7 to 1.0 × 10−4 and 1.0 × 10−4 to 2.0 × 10−2 mol L−1.  相似文献   

6.
A bismuth film electrode (BiFE) prepared ex-situ on a supporting glassy carbon electrode exhibited convenient electroanalytical performance for voltammetric measurement of selected aminosalycilate drugs. The reduction behaviour of aminosalycilate drugs was studied in aqueous solutions within the pH range of 4–6. The voltammetric responses were compared with those obtained at the bare glassy carbon electrode under identical conditions. In the square-wave voltammetric operation mode the BiFE showed a linear response in the concentration range of 5 × 10−6 to 3.5 × 10−4 and 1 × 10−6 to 5 × 10−4 M for sulfasalazine and olsalazine, respectively. Its electrode surface revealed auspiciously high stability and remarkable reproducibility in the rapid analysis of aminosalycilate drugs. Finally, the BiFE was satisfactorily applied for direct quantitation of azo prodrugs in real pharmaceutical samples.  相似文献   

7.
Highly ordered SBA-15 and Sn-SBA-15 mesoporous molecular sieves with Si/Sn = 80, 60, 40 and 10 have been prepared through direct synthesis route under milder acidic conditions, which were used for the in situ high temperature X-ray diffraction (HTXRD) studies in the temperature range 298–1573 K for the first time in the literature. SBA-15 is found to be thermally stable up to 1473 K and appearance of α-cristobalite was observed at 1573 K also supported by the thermogravimetric (TG) data. A strong negative thermal expansion was observed on heating from 298 to 1573 K (αa = −4.3 × 10−6 K−1). Sn containing samples (Si/Sn = 80 and 60) showed a positive thermal expansion (6.75 × 10−6 K−1 and 9.04 × 10−6 K−1, respectively). On the other hand, the samples with Si/Sn = 40 and 10 showed a strong negative thermal expansion (−4.12 × 10−6 K−1 and −7.56 × 10−6 K−1) similar to SBA-15. The linear thermal expansion coefficient varied in the order: Si/Sn = 60 > 80 > 40 > 0 > 10. Sn4+ ions exhibit both tetrahedral and octahedral coordination depending upon the location of these ions either on the walls of the silica (Si/Sn = 80 and 60) or in the corona region of the structure (Si/Sn = 40 and 10), respectively. The thermal decomposition of the samples (TG data) is correlated to the thermal expansion behavior (HTXRD data). The decomposition behavior of template ions located within the pores is strongly influenced by the presence of Sn in the framework and a ‘soft’ interaction probably exists between the template ions and the Sn sites.  相似文献   

8.
Each year in France, about 1300 tons of spent Ni–Cd batteries are collected. Their treatment consists of crushing, physical separation, acidic leaching of electrode materials, separation and recovery of metals leached with different processes. In this work, the selective precipitation of cadmium in synthetic Ni–Cd mixtures was investigated using sodium decanoate as precipitant. A factorial design of experiments was used to improve the separation using variables such as cadmium concentration, pH, molar ratio between decanoate and cadmium, time of addition of precipitant and rest time of the solution. In the best conditions defined by a 25−2 fractional factorial design, starting with concentrations of 0.1 mol L−1 of nickel (5.9 g L−1) and 0.05–0.15 mol L−1 of cadmium (5.6–16.8 g L−1) it is possible to recover in only one stage about 99% of cadmium without precipitating more than 5% of nickel. The results of the separation are on one side a pure solution of nickel at 2.39 × 10−2 mol L−1 (1.4 g L−1) containing 3.44 × 10−4 mol L−1 of cadmium (about 40 mg L−1) and on the other side a precipitate of cadmium decanoate with a cadmium content equal to 23.6 wt% and nickel content lower than 0.8 wt%. These results demonstrated the viability of this separation.  相似文献   

9.
A novel gadolinium selective coated graphite electrode based on 2,6-bis-[1-{N-cyanopropyl,N-(2-methylpridyl)}aminoethyl]pyridine [P] is described. The best performance was exhibited by the electrode having membrane composition P:NaTPB:PVC:NPOE as 8:4:30:58 (%, w/w). The electrode demonstrates excellent potentiometric characteristics towards gadolinium ion over several interfering ions. The electrode exhibited a Nernstian response to Gd3+ ion over a wide concentration range 2.8 × 10−7 to 5.0 × 10−2 M with a detection limit (6.3 ± 0.1) × 10−8 M and slope 19.6 ± 0.1 mV decade−1 of aGd3+. Furthermore, it showed a fast response time (12 s) and can be used for 2.5 months without significant divergence in its characteristics. Noticeably, the electrode can tolerate the concentration of different surfactants up to 1.0 × 10−4 M and can be used successfully in 30% (v/v) ethanol media and 10% (v/v) methanol and acetonitrile water mixture. The useful pH range of this sensor is 2.0 to 8.0. It is sufficiently selective and can be used for the determination of Gd3+ ions in waste water and rock samples. It also serves as a good indicator in the potentiometric titration of GdCl3 with EDTA.  相似文献   

10.
The electrochemical behaviour of N-acetyl-l-cysteine (NAC) has been investigated by linear and cyclic voltammetry on gold electrode at room temperature. The results showed two oxidation peaks under acid and neutral conditions and only one in basic medium. For each oxidation, as many electron was exchanged as proton. The influence of both the concentration and the potential scan rate on the peak currents highlighted a diffusion-controlled phenomenon for the first peak and an adsorption-limited reaction rate for the second one. The diffusion coefficient of NAC in solution and the surface concentration of the adsorbed species at pH 3 and 7 were close to 2 × 10−4 to 2 × 10−5 cm2 s−1 and 6 × 10−9 to 6 × 10−10 mol cm−2, respectively. Film transfer experiments resulted in an irreversible adsorption of NAC on gold electrode, and the formation of a self-assembled monolayer (SAM).  相似文献   

11.
The interaction of the anthraquininoid dye, Purpurin (C.I. 58 205) with fish-sperm DNA was electrochemically investigated in 0.02 mol L−1 pH 7.0 Britton–Robinson (B–R) buffer. After interaction with DNA, the irreversible oxidation peak of the dye decreased and underwent a positive shift of potential, suggesting intercalation between the dye and DNA, this being consistent with fluorescence quenching results. The binding constant (K) and binding site size (s) of the two species were 9.6 × 106 L mol−1 and 1.7 respectively, as determined using voltammetric titration, indicating that the dye was strongly bound to the DNA.  相似文献   

12.
A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with nickel oxide (NiOx) nanoparticles and water-soluble dyes. By immersing the GC/NiOx modified electrode into thionine (TH) or celestine blue (CB) solutions for a short period of time (5–120 s), a thin film of the proposed molecules was immobilized onto the electrode surface. The modified electrodes showed stable and a well-defined redox couples at a wide pH range (2–12), with surface confined characteristics. In comparison to usual methods for the immobilization of dye molecules, such as electropolymerization or adsorption on the surface of preanodized electrodes, the electrochemical reversibility and stability of these modified electrodes have been improved. The surface coverage and heterogeneous electron transfer rate constants (ks) of thionin and celestin blue immobilized on a NiOx-GC electrode were approximately 3.5 × 10−10 mol cm−2, 6.12 s−1, 5.9 × 10−10 mol cm−2 and 6.58 s−1, respectively. The results clearly show the high loading ability of the NiOx nanoparticles and great facilitation of the electron transfer between the immobilized TH, CB and NiOx nanoparticles. The modified electrodes show excellent electrocatalytic activity toward hydrogen peroxide reduction at a reduced overpotential. The catalytic rate constants for hydrogen peroxide reduction at GC/NiOx/CB and GC/NiOx/TH were 7.96 (±0.2) × 103 M−1 s−1 and 5.5 (±0.2) × 103 M−1 s−1, respectively. The detection limit, sensitivity and linear concentration range for hydrogen peroxide detection were 1.67 μM, 4.14 nA μM−1 nA μM−1 and 5 μM to 20 mM, and 0.36 μM, 7.62 nA μM−1, and 1 μM to 10 mM for the GC/NiOx/TH and GC/NiOx/CB modified electrodes, respectively. Compared to other modified electrodes, these modified electrodes have many advantages, such as remarkable catalytic activity, good reproducibility, simple preparation procedures and long-term stabilities of signal responses during hydrogen peroxide reduction.  相似文献   

13.
Removal/preconcentration of thallium(I) ions from aqueous solution by sawdust; a waste material derived from the commercial processing of Cedrus Deodar wood for furniture production was investigated. A simple and low-cost modification results in increasing the sorption capacity of raw sawdust from 2.71 to 13.18 mg g−1. Sorption was found to be rapid (98% within 8 min). The binding of metal ions was found to be pH dependent, optimal sorption accruing at around pH 6–9. Potentiometeric titrations of sawdust revealed two distinct pKa values, the first having the value similar to carboxylic groups (3.3–4.8) and second comparable with that of amines (8.53–10.2) with the surface site densities of 1.99 × 10−4 and 7.94 × 10−5 mol g−1, respectively. Retained Tl(I) ions were eluted with 5 ml 0.1 mol l−1 HCl. Detection limit of 0.0125 μg ml−1 was achieved with an enrichment factor of 160. Recovery was quantitative using sample volume of 800 ml. The Langmuir, Freundlich and D–R isotherm equations were used to describe partitioning behavior for the system at different temperatures. Kinetic and thermodynamic behavior of sawdust for Tl(I) ions removal was also studied.  相似文献   

14.
A new fluorescence macrocyclic receptor based on the Zn(II) complex of a C2-terpyridine and a crown ether has been developed for molecular recognition of zwitterionic amino acids in water/DMF solution with remarkable selectivity towards l-aspartate (K = 4.5 × 104 M−1) and l-cysteine (K = 2.5 × 104 M−1).  相似文献   

15.
The focus of this investigation is the development of a solvent impregnated resin for phenol removal from dilute aqueous solutions. Using a solvent impregnated resin (SIR) eliminates the problem of emulsification encountered in liquid–liquid extraction. Impregnated MPP particles and impregnated XAD16 particles are successfully used for phenol extraction. Impregnated MPP particles are preferred, as impregnated XAD16 particles show less mechanical strength and are more expensive. Impregnated MPP particles perform better compared to other synthetic adsorbents and basic ion exchangers. The maximum phenol capacity of impregnated MPP particles with 0.99 mol Cyanex 923 kg−1 SIR is 4.1 mol kg−1 SIR (386 mg g−1 SIR) and of MPP particles containing 1.47 mol Cyanex 923 kg−1 SIR it is 5.08 mol kg−1 SIR (478 mg g−1 SIR). The regenerability of impregnated MPP particles is easy and complete, and the particles are stable during several cycles. The equilibrium constants for the extraction of phenol are determined as Kchem = 37 L mol−1 and Kphys = 18 (mol L−1) (mol L−1)−1. With these values the SIR isotherms can be satisfactorily described.The results indicate that SIR technology is a promising alternative for the conventional phenol removal technologies at low phenol concentration levels.  相似文献   

16.
Spontaneous adsorption of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) on glassy carbon (GC) electrode leads to the formation of a stable self-assembled monolayer (SAM). Since the SAM of 4α-CoIITAPc is redox active, its adsorption on GC electrode was followed by cyclic voltammetry. SAM of 4α-CoIITAPc on GC electrode shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) value, calculated by integrating the charge under CoII oxidation, was used to study the adsorption thermodynamics and kinetics of 4α-CoIITAPc on GC surface. Cyclic voltammetric studies show that the adsorption of 4α-CoIITAPc on GC electrode has reached the saturation coverage (Γs) within 3 h. The Γs value for the SAM of 4α-CoIITAPc on GC electrode was found to be 2.37 × 10−10 mol cm−2. Gibbs free energy (ΔGads) and adsorption rate constant (kad) for the adsorption of 4α-CoIITAPc on GC surface were found to be −16.76 kJ mol−1 and 7.1 M−1 s−1, respectively. The possible mechanism for the self-assembly of 4α-CoIITAPc on GC surface is through the addition of nucleophilic amines to the olefinic bond on the GC surface in addition to a meager contribution from π stacking. The contribution of π stacking was confirmed from the adsorption of unsubstituted phthalocyanatocobalt(II) (CoPc) on GC electrode. Raman spectra for the SAM of 4α-CoIITAPc on carbon surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Raman and CV studies suggest that 4α-CoIITAPc is adopting nearly a flat orientation or little bit tilted orientation.  相似文献   

17.
Several transport parameters (as hydraulic conductivity K, apparent diffusion coefficient Dp and diffusion accessible porosity η of HTO and iodide) have been intensively measured in the laboratory on high-quality cores taken at the Mol-1 borehole of the Mol site, in Belgium. The borehole was cored in 1997 from about 145 to 325 m depth, including the whole thickness of the Boom Formation, a Tertiary clay situated between 186 and 288 m depth (ground level), and part of the surrounding layers.The hydraulic conductivity measurements confirm the low permeability of the Boom Clay. An upper 90-m-thick clay layer within this formation can be considered as homogeneous with respect to the hydraulic conductivity. The vertical hydraulic conductivity Kv (i.e. K perpendicular to the bedding) is in the order of magnitude of 10−12 m s−1 and the average is 2.3×10−12 m s−1. This layer comprises from top to bottom the “Transition Zone”, the Putte Member, the Terhagen Member and the top of the Belsele-Waas Member of the Boom Formation. The 12 m at the base of the Formation, which corresponds to the lower part of the Belsele-Waas Member is characterised by larger Kv values (ranging between 10−11 and 9×10−11 m s−1).The same thick clay layer can also be considered as homogeneous, regarding the values of the apparent diffusion coefficient and the diffusion accessible porosity η of tritiated water (HTO) and iodide. The average value of the diffusion accessible porosity is 0.37±0.03 for HTO and 0.16±0.02 for iodide. The apparent diffusion coefficient varies from 1.1×10−10 to 5.5×10−10 m2 s−1 for HTO and from 9.1×10−11 to 5.2×10−10 m2 s−1 for iodide.  相似文献   

18.
A modified graphite electrode with functionalized ionic liquid (IL) pyridinium derivative of β-cyclodextrin ([CDbPy]BF4) was prepared by layer-by-layer self-assembly technique. With ferrocene as probe, the characterization of the (CDIL/PDDA)n/GE SAMs in the solution of phosphate (PBS, pH 7.0) was investigated by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and chronocoulometry. The electrochemical behavior of p-chloronitrobenzene (p-CNB) at the modified electrode was studied. It was found that the modified electrode could catalyze the reduction of p-CNB and made the cathode peak move about 100 mV in positive direction in the solution of 0.1 mol/L PBS (pH 7.0). Differential pulse voltammetry (DPV) was applied to the determination of p-CNB in waste water with satisfactory results. The detection limit and the linear range of the concentration of p-CNB to the reduction peak current were 8.0 × 10−8 mol/L and 3.0 × 10−7–1.0 × 10−5 mol/L, respectively.  相似文献   

19.
A glucose biosensor, which was based on self-assembled Prussian Blue (PB) modified electrode with glucose oxidase (GOD) immobilized in cross-linked glutaraldehyde matrix, was developed. Fourier-transform infrared spectroscopy shows that the immobilized GOD retains its native conformation. Cyclic voltammetry was used to examine the electrocatalytic property of the enzyme electrode. The prepared glucose biosensor exhibits fast response (<4 s) and low detection limit of 5 × 10−6 M. The calculated apparent Michaelis constant KM was 6.3 ± 1.2 mM, indicating a high affinity between the GOD and glucose. The effects of glutaraldehyde concentration and GOD loading on the sensitivity of the glucose biosensor have also been investigated. Under the optimal conditions, the biosensor shows a high sensitivity of about 80 mA M−1 cm−2 in a concentration range up to 1 × 10−3 M. The relative standard deviation (RSD) for intra-electrode and inter-electrode were 4% and 5%, respectively. In addition, the anti-interferent ability and stability of the biosensor were also discussed.  相似文献   

20.
The photochemical behavior of [Ru(NO)(NO)2pc] (pc = phthalocyanine) is reported in this paper. In addition to ligand localized absorption bands (λ < 300 nm), the electronic spectrum of this complex in dichloromethane solution was dominated by an intense absorption at 640 nm characterized as Q-bands. Irradiation of [Ru(NO)(NO)2pc] at 366 and 660 nm led to the production of nitric oxide (NO) as detected by a NO-sensor. NO production by light irradiation at high energy involved excitation of dπ–π* transition, while a photoinduced electron transfer occurred at long wavelength irradiation. The NO quantum yields varied from 1.4 × 10−3 to 2.3 × 10−2 mol einstein−1, depending on oxygen concentration.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号