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1.
The simultaneous voltammetric determination of adenosine (ADS) and dopamine (DA) using a single wall carbon nanotube (SWCNT) modified glassy carbon electrode (GCE) is reported. This has physiological importance in controlling Parkinson’s disease. In phosphate buffer medium of pH 7.2, the concentration vs. peak current plots were linear in the range 1–100 μM for ADS and DA. A comparison of the voltammetric response of DA at acid-treated (purified and super-purified) and untreated SWCNT modified GCE indicates that the oxidation peak current of DA decreases considerably at the treated SWCNT modified GCE. This indicates that metallic impurities in nanotubes play a large role in enhancing the electrochemical current. The detection limit (3σ) and sensitivity observed for ADS and DA were 34.7 μM, 7 μM and 9.5 nA μM−1, 77.9 nA μM−1, respectively.  相似文献   

2.
The two novel ion-pairs (PB-TPB and NB-TPB) of quaternary ammonium drugs; propantheline bromide (PB), N,N-Diisopropyl-N-methyl-N-[2-(xanthen-9ylcarbonyloxy)ethyl] ammonium bromide and neostigmine bromide (NB), 3-(dimethylcarbamoyloxy) phenyl]-trimethylazanium have been synthesized, respectively and incorporated in poly (vinyl chloride)-based membrane electrodes for the quantification of propantheline bromide and neostigmine bromide in different pharmaceutical preparations. The influences of membrane compositions on the potentiometric responses of membrane electrodes have been found to substantially improve the performance characteristics. The best performance was reported with membranes having composition (w/w) of PB-TPB or NB-TPB (6%): PVC (34%): o-NPOE (60%). The proposed electrodes exhibit nernstian response in the concentration ranges of 2.1 × 10−7 M to 1.0 × 10−2 M and 4.4 × 10−7 M to 1.0 × 10−2 M with detection limit of 1.5 × 10−7 M and 3.3 × 10−7 M, respectively. Both the membrane electrodes perform satisfactorily over pH ranges of (3.5–7.5 and 4.0–7.0) with fast response times (11 s and 13 s), respectively. These drugs (PB and NB) were further utilized as different ion-pairs of Prostaglandin E1 (PGE1) and Deoxycholate (DOC) in poly (vinyl chloride)-based membrane electrodes for the determination of bioavailability of Prostaglandin E1 and Deoxycholate in plasma of different patients.  相似文献   

3.
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   

4.
A novel one-shell high temperature and high pressure semi-continuous reactor has been developed for the study of the Boudouard reaction at temperatures up to 820 °C and pressures up to 32.5 MPa. Semicontinuous gasification of charcoal using supercritical CO2 has been achieved at conversions up to 90.8% (w/w) at LSHV between 20 and 30 h−1 after 5–9 h. A gasification model is proposed and validated. Effective rates of gasification (1.32 ± 0.12) × 10−6 to (6.10 ± 2.03) × 10−5 s−1 were obtained. The results indicated that this method is technically feasible for the on-line production of high pressures streams of CO/CO2 in the lab for carrying out further chemistries, avoiding the use of CO high pressure bottles.  相似文献   

5.
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   

6.
A type of Pd–ZnO catalysts supported on multi-walled carbon nanotubes (MWCNTs) were developed, with excellent performance for CO2 hydrogenation to methanol. Under reaction conditions of 3.0 MPa and 523 K, the observed turnover-frequency of CO2 hydrogenation reached 1.15 × 10−2 s−1 over the 16%Pd0.1Zn1/CNTs(h-type). This value was 1.17 and 1.18 times that (0.98 × 10−2 and 0.97 × 10−2 s−1) of the 35%Pd0.1Zn1/AC and 20%Pd0.1Zn1/γ-Al2O3 catalysts with the respective optimal Pd0.1Zn1-loading. Using the MWCNTs in place of AC or γ-Al2O3 as the catalyst support displayed little change in the apparent activation energy for the CO2 hydrogenation, but led to an increase of surface concentration of the Pd0-species in the form of PdZn alloys, a kind of catalytically active Pd0-species closely associated with the methanol generation. On the other hand, the MWCNT-supported Pd–ZnO catalyst could reversibly adsorb a greater amount of hydrogen at temperatures ranging from room temperature to 623 K. This unique feature would help to generate a micro-environment with higher concentration of active H-adspecies at the surface of the functioning catalyst, thus increasing the rate of surface hydrogenation reactions. In comparison with the “Parallel-type (p-type)” MWCNTs, the “Herringbone-type (h-type)” MWCNTs possess more active surface (with more dangling bonds), and thus, higher capacity for adsorbing H2, which make their promoting action more remarkable.  相似文献   

7.
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   

8.
Blackcurrant seed oil is rich in linoleic and linolenic acids. Selective enzyme-catalysed oil hydrolysis was studied with aim to obtain different levels of α- and/or γ-linolenic acid in the mixture of liberated fatty acids and in the fraction of di- and monoacylglycerols, making them suitable for special dietary needs. The oil was dissolved in supercritical carbon dioxide flowing through a packed bed reactor (temperature 40 °C, pressure 15–28 MPa, and superficial velocity 0.1–0.7 mm s−1) with Lipozyme®, a 1,3-specific lipase from Mucor miehei immobilised on a macroporous ion-exchange resin. The enzyme activity was stable as long as water precipitation in the reactor was prevented. The reaction was found to be controlled by both Michaelis–Menten kinetics and mass transfer. The maximum rate of fatty acids liberation per unit amount of enzyme, 2.6 × 10−3 mol s−1 kg−1, was achieved at the maximum flow velocity and pressure. Compared to oil, the liberated fatty acids contained more α-linolenic, palmitic and stearic acids, while di- and monoacylglycerols contained increased levels of γ-linolenic and stearidonic acids.  相似文献   

9.
The photoassisted degradation (HPLC-UV absorption), dehalogenation (HPLC-IC) and mineralization (TOC decay) of the flame retardants tetrabromobisphenol-A (TBBPA) and tetrachlorobisphenol-A (TCBPA) were examined in UV-irradiated alkaline aqueous TiO2 dispersions (pH 12), and for comparison the parent bisphenol-A (BPA, an endocrine disruptor) in pH 4–12 aqueous media to assess which factor impact most on the photodegradative process. Complete degradation (2.7–2.8 × 10−2 min−1) and dehalogenation (1.8 × 10−2 min−1) of TBBPA and TCBPA occurred within 2 h of UV irradiation, whereas only 45–60% mineralization (2.3–2.7 × 10−3 min−1) was complete within 5 h for the flame retardants at pH 12 and ca. 80% for the parent BPA. Factors examined in the pH range 4–12 that impact the degradation of BPA were the point of zero charge of TiO2 particles (pHpzc; electrophoretic method), particle or aggregate sizes of TiO2 (light scattering), and the relative number of OH radicals (as DMPO–OH adducts; ESR spectroscopy) produced in the UV-irradiated dispersion. Dynamics of BPA degradation (2.0–2.4 × 10−2 min−1) were pH-independent and independent of particle/aggregate size, but did correlate with the number of OH radicals, at least at pHs 4 to 8–9, after which the rates decreased somewhat at pH > 9 with decreasing adsorption owing to Coulombic repulsive forces between the very negative TiO2 surface and the anionic forms of BPA (pKas ca. 9.6–11.3), even though the number of OH radicals continued to increase at the higher pHs.  相似文献   

10.
PTFE-F-PbO2 电极在H2SO4溶液中的析氧行为   总被引:1,自引:0,他引:1  
F-PbO2 electrode and polytetrafluoroethylene (PTFE) doped F-PbO2 electrode (PTFE-F-PbO2) were prepared on a plexiglas sheet substrate by a series of procedure including chemical and electrochemical depositions. The electrochemical activities of these two electrodes for oxygen evolution (OE) reaction were examined by electrochemical tests. In comparison with F-PbO2, PTFE-F-PbO2 electrode exhibited larger active surface area and higher oxygen vacancy deficiency, which resulted in its higher electrocatalytic activity for OE. In addition, both exchange current density and activation energy of the electrodes for OE were calculated in terms of active surface area. The values of exchange current density and activation energy in 0.5 mol·L^-1 H2SO4 aqueous solution were 1.125×10^ -3 mA·cm^-2 and 18.62 kJ·mol^-1 for PTFE-F-PbO2, and 8.384×10^-4 mA·cm^- 2 and 28.98 kJ·mol^-1 for F-PbO2, respectively. Because these values are calculated on the basis of the active surface areas of the electrodes, the enhanced activity of PTFE-F-PbO2 can be attributed to an increase in oxygen vacancy deficiency of PbO2 due to doping by PTFE. The influence of PTFE adulteration on the activity of PbO2 film electrode for OE was investigated in detail in this study.  相似文献   

11.
A silica-supported Ag system made by the incipient wetness impregnation method was investigated in the reaction of heterogeneous catalytic decomposition of ozone. It was established that the catalytic ozone decomposition on Ag/SiO2 proceeded in the temperature interval −40 °C to 25 °C as a first order reaction with activation energy of 65 kJ/mol (pre-exponential factor 5.0 × 1014 s−1). Based on the results from the instrumental methods (SEM, XRD, XPS, EPR, TPD) it can be concluded that in presence of ozone the silver is oxidized to a complicated mixture of Ag2O3 and AgO. Due to the high activity and stability of the Ag/SiO2 catalyst, it is promising for neutralization of waste gases containing ozone.  相似文献   

12.
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   

13.
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   

14.
Electrical conductivity measurements on EUROCAT V2O5–WO3/TiO2 catalyst and on its precursor without vanadia were performed at 300°C under pure oxygen to characterize the samples, under NO and under NH3 to determine the mode of reactivity of these reactants and under two reaction mixtures ((i) 2000 ppm NO + 2000 ppm NH3 without O2, and (ii) 2000 ppm NO + 2000 ppm NH3 + 500 ppm O2) to put in evidence redox processes in SCR deNOx reaction.It was first demonstrated that titania support contains certain amounts of dissolved W6+ and V5+ ions, whose dissolution in the lattice of titania creates an n-type doping effect. Electrical conductivity revealed that the so-called reference pure titania monolith was highly doped by heterovalent cations whose valency was higher than +4. Subsequent chemical analyses revealed that so-called pure titania reference catalyst was actually the WO3/TiO2 precursor of V2O5–WO3/TiO2 EUROCAT catalyst. It contained an average amount of 0.37 at.% W6+dissolved in titania, i.e. 1.07 × 1020 W6+ cations dissolved/cm3 of titania. For the fresh catalyst, the mean amounts of W6+ and V5+ ions dissolved in titania were found to be equal to 1.07 × 1020 and 4.47 × 1020 cm−3, respectively. For the used catalyst, the mean amounts of W6+ and V5+ ions dissolved were found to be equal to 1.07 × 1020 and 7.42 × 1020 cm−3, respectively. Since fresh and used catalysts have similar compositions and similar catalytic behaviours, the only manifestation of ageing was a supplementary progressive dissolution of 2.9 × 1020 additional V5+ cations in titania.After a prompt removal of oxygen, it appeared that NO alone has an electron acceptor character, linked to its possible ionosorption as NO and to the filling of anionic vacancies, mostly present on vanadia. Ammonia had a strong reducing behaviour with the formation of singly ionized vacancies. A subsequent introduction of NO indicated a donor character of this molecule, in opposition to its first adsorption. This was ascribed to its reaction with previously adsorbed ammonia strongly bound to acidic sites. Under NO + NH3 reaction mixture in the absence of oxygen, the increase of electrical conductivity was ascribed to the formation of anionic vacancies, mainly on vanadia, created by dehydroxylation and dehydration of the surface. These anionic vacancies were initially subsequently filled by the oxygen atom of NO. No atoms, resulting from the dissociation of NO and from ammonia dehydrogenation, recombined into dinitrogen molecules. The reaction corresponded to
. In the presence of oxygen, NO did not exhibit anymore its electron acceptor character, since the filling of anionic vacancies was performed by oxygen from the gas phase. NO reacted directly with ammonia strongly bound on acidic sites. A tentative redox mechanism was proposed for both cases.  相似文献   

15.
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   

16.
Degradation of atrazine in model wastewater by UV/FeZSM-5/H2O2 system chosen as optimal for application of advanced oxidation process (AOP) has been studied in a batch photo reactor. The statistical study of the process was performed using two-level full factorial experimental design with the three process parameters. Individual parameters and their interaction effects on atrazine degradation were determined and statistical model of process was developed. The optimal operating conditions were established. This approach has also given a broader insight of the processes that were occurring in the reaction system, and it has finally led to simplification in terms of kinetics. Atrazine degradation was described by pseudo-first-order kinetics with observed rate constant k′ = 2 × 10−3 s−1.  相似文献   

17.
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   

18.
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   

19.
Catalytic efficiency, stability and environmental applicability of five iron(III) oxide nanopowders differing in surface area and crystallinity were tested in degradation of concentrated phenolic aqueous solutions (100 g/L) at mild temperature (30 °C), initially almost neutral pH and equimolar ratio of hydrogen peroxide and phenol. The catalyst properties were easily controlled by varying in reaction time during isothermal treatment of ferrous oxalate dihydrate in air at 175 °C. Although the catalytic efficiency clearly increases with the surface area of the nanopowders, it is not due to the solely heterogeneous catalytic mechanism as would be expected. The amorphous Fe2O3 nanopowders possessing the largest surface areas (401 m2 g−1, 386 m2 g−1) are the most efficient catalysts evidently due to their highest susceptibility to leaching in acidic environment arising as a consequence of phenol degradation products. Thus, these amorphous samples act partially as homogeneous catalysts, which was confirmed by a high concentration of leached Fe(III) ions in the solution (19 ppm). The crystalline hematite (α-Fe2O3) samples, varying in surface area between 337 m2 g−1 and 245 m2 g−1, are generally less efficient when compared to the amorphous powders, however their catalytic action is almost exclusively heterogeneous as only 3 ppm of leached Fe(III) was found in the reaction systems catalyzed by nanohematite samples. A significant difference in relative contributions of heterogeneous and homogenous catalysis was definitely established in buffered reaction systems catalyzed by amorphous Fe2O3 and nanocrystalline hematite. The nanohematite sample exhibiting the highest heterogeneous action was tested at decreased initial phenol concentration (10 g/L), which is closer to the real contents of phenol in waste waters, and at different hydrogen peroxide/phenol molar ratios to consider its environmental applicability. At the hydrogen peroxide/phenol ratio equal to 5, no traces of the leached iron were detected and the phenol conversion of 84% was reached. Moreover, such a high degree of conversion is accompanied by a decrease of the chemical oxygen demand (COD) from the initial value of 11.23 g/L to 4.22 g/L after 125 min. This fact indicates that the considerable fraction of primary reaction products was totally degraded.  相似文献   

20.
Polyethylene glycol (PEG, mean molecular weight of 10,000) has been used to prepare a Li3V2(PO4)3/C cathode material by a simple solid-state reaction. The Raman spectra shows that the coating carbon has a good structure with a low ID/IG ratio. The images of SEM and TEM show that the carbon is dispersed between the Li3V2(PO4)3 particles, which improves the electrical contact between the corresponding particles. The electronic conductivity of Li3V2(PO4)3/C composite is 7.0 × 10−1 S/cm, increased by seven orders of magnitude compared with the pristine Li3V2(PO4)3 (2.3 × 10−8 S/cm). At a low discharge rate of 0.28C, the sample presents a high discharge capacity of 131.2 mAh/g, almost achieving the theoretical capacity (132 mAh/g) for the reversible cycling of two lithium. After 500 cycles, the discharge capacity is 123.9 mAh/g with only 5.6% fading of the initial specific capacity. The Li3V2(PO4)3/C material also exhibits an excellent rate capability with high discharge capacities of 115.2 mAh/g at 1C and 106.4 mAh/g at 5C.  相似文献   

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