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1.
The potential-energy surface for the Li(2S)–HF (? X1Σ+ interaction, where HF is kept rigid, is calculated using the supermolecular unrestricted fourth-order Møller–Plesset perturbation theory. The basis set superposition error corrected potential indicates two minima. The global minimum occurs for the bent Li...FH structure at R=1.95 Å and θ=70° with a relatively deep well of De=1,706 cm?1 and the secondary minimum is found for the linear Li...HF configuration at R=4.11 Å with a well depth ofDe=288 cm?1. A barrier of 177 cm?1 (with respect to the secondary linear minimum) separates these two minima. In this study 27 bound states of the bent Li...FH minimum and eight bound states of the linear Li...HF minimum up to the Li+HF dissociation threshold are calculated. The energy partitioning using the intermolecular perturbation theory scheme shows that the origins of the stability of the structures studied are entirely different. The global minimum is stabilised using the attractive Coulombic interaction and unrestricted Hartree–Fock deformation energy. The latter term originates from the mutual electric polarisation effects. The secondary linear minimum is mostly determined by the anisotropy of the repulsive Heitler–London exchange-penetration and attractive dispersion energies.  相似文献   

2.
An investigation is conducted on enhancing lithium-ion intercalation and conduction performance of transparent organo tantalum oxide (TaO y C z ) films, by addition of lithium via a fast co-synthesis onto 40 Ω/□ flexible polyethylene terephthalate/indium tin oxide substrates at the short exposed durations of 33–34 s, using an atmospheric pressure plasma jet (APPJ) at various mixed concentrations of tantalum ethoxide [Ta(OC2H5)5] and lithium tert-butoxide [(CH3)3COLi] precursors. Transparent organo-lithiated tantalum oxide (Li x TaO y C z ) films expose noteworthy Li+ ion intercalation and conduction performance for 200 cycles of reversible Li+ ion intercalation and deintercalation in a 1 M LiClO4-propylene carbonate electrolyte, by switching measurements with a potential sweep from ?1.25 to 1.25 V at a scan rate of 50 mV/s and a potential step at ?1.25 and 1.25 V, even after being bent 360° around a 2.5-cm diameter rod for 1000 cycles. The Li+ ionic diffusion coefficient and conductivity of 6.2?×?10?10 cm2/s and 6.0?×?10?11 S/cm for TaO y C z films are greatly progressed of up to 9.6?×?10?10 cm2/s and 7.8?×?10?9 S/cm for Li x TaO y C z films by co-synthesis with an APPJ.  相似文献   

3.
The overall adsorption rate of Reactive Black 5 dye (RB5) on chitosan based materials was elucidated using diffusional models. Fundamental aspects, such as, geometry of the adsorbents and swelling effects were considered. Chitosan based materials (powder and film) were prepared from shrimp wastes and characterized regarding to the fundamental features for adsorption. Experimental decay curves were obtained under different conditions of stirring rate and initial dye concentration. The data were modeled according to the external mass transfer and diffusional models. The kL (external mass transfer coefficient), Dep (effective pore diffusion coefficient) and Ds (surface diffusion coefficient) values were estimated. For both adsorbents, it was found that the surface diffusion was the intraparticle diffusion mechanism governing the adsorption rate of RB5, since its contribution was higher than 92 % regardless the position and time. The Ds values ranged from 2.85 × 10?11 to 5.78 × 10?11 for chitosan powder and from 4.15 × 10?11 to 12.12 × 10?11 cm2 s?1 for chitosan films. The RB5 adsorption was faster when chitosan powder was used, mainly at higher stirring rates and initial dye concentrations. The swelling effect was most pronounced for the chitosan films, where, provided an increase of about 65 times in the Ds value.  相似文献   

4.
A mixed oxide-covered mesh electrode composed of NiCo2O4 (MOME-NiCo2O4) was prepared on a stainless-steel substrate using thermal decomposition (slow-cooling rate method). Surface, bulk and electrochemical properties of MOME were studied using different techniques, namely scanning electron microscopy (SEM), X-ray diffraction (XRD), cyclic voltammetry (CV) with determination of the electrochemical porosity (?) and morphology factor (φ) parameters, quasi-stationary polarisation curves (PC) and electrochemical impedance spectroscopy (EIS). SEM images revealed a good coverage of the metallic wires by a compact oxide layer (absence of cracks). XRD analysis confirmed the formation of the spinel NiCo2O4 with the presence of NiO. The ‘in situ’ surface parameters denoted as ? and φ exhibited values of 0.39 and 0.33, respectively, revealing that the electrochemically active surface area is mainly confined to the ‘outer/external’ surface regions of the oxide layer. The PC was characterised by two Tafel slopes distributed in the low (b 1 = 46 mV dec?1) and high (b 2 = 59 mV dec?1) overpotential domains. The corresponding apparent exchange current densities were j 0(1) = (3.43 ± 0.11) × 10?6 A cm?2 and j 0(2) = (6.70 ± 0.08) × 10?6 A cm?2, respectively. The EIS study accomplished in the low-overpotential domain revealed a Tafel slope (b 1) of 51 mV dec?1. According to the spin-trapping reaction using N,N-dimethyl-p-nitrosoaniline (RNO), the MOME-NiCo2O4 electrode exhibited good performance for the generation of weakly adsorbed hydroxyl radicals (HO?) during the OER in electrolyte-free water.  相似文献   

5.
A new electrochemical sensor was developed for determination of D-penicillamine using glassy carbon electrode which had been modified by gold nanoparticles–reduced graphene oxide nanocomposite (AuNPs/RGO/GCE) in aqueous solution. Cyclic voltammetry, transmission electron microscopy and electrochemical impedance spectroscopy were used for characterization of the modified electrode. The results indicated that the kinetic of oxidation reaction of D-penicillamine at the surface of the electrode was controlled by both diffusion and adsorption processes. In 0.1 mol L?1 phosphate buffer (pH 2.0), the oxidation current increased linearly with concentration of D-penicillamine with a linear range of 5.0 × 10?6 to 1.1 × 10?4 mol L?1 and regression coefficient of R 2 = 0.9972. Theoretical detection limit, defined based on 3σ of the blank signal (n = 9) divided by the slope of the linear regression equation, was 3.9 × 10?6 mol L?1 D-penicillamine using differential pulse voltammetry. The developed method was successfully applied to the determination of D-penicillamine in pharmaceutical formulation and blood serum samples.  相似文献   

6.
For many years, the traditional process of gardenia yellow pigment extraction has produced wastewater containing significant quantities of Geniposidic acid (GSA), a substance that could be put to pharmacological uses if it could be effectively recovered. This study aimed to provide an efficient adsorption material, D08, for recycling GSA. Batch experiments showed that adsorption capacity depends on initial concentration and temperature. The maximal adsorption capacity of GSA onto an anionic exchanger reached 310 mg/g. The pK a value of GSA was determined to be 4.21. Pore diffusion coefficients (D p) of GSA for 283, 298 and 313 K were 3.274 × 10?10, 5.069 × 10?10 and 7.356 × 10?10 m2/s, respectively. Recovery efficiency of GSA was achieved to 99.81 %. In comparison with pseudo first-order and pseudo second-order equations, the PDM model demonstrated the best fit to the kinetics data of GSA adsorption. Adsorption/desorption experiments proved that D08 offers great adsorption capacity, high adsorption rate and good repeatability. In order to help us to accurately comprehend the mass transfer process, numerical simulation and post-processing to variables c(r, t) and q(r, t) were performed to clarify the adsorption process.  相似文献   

7.
An approximate analytical solution of the Schrödinger equation is obtained to represent the rotational–vibrational (ro-vibrating) motion of a diatomic molecule. The ro-vibrating energy states arise from a systematical solution of the Schrödinger equation for an empirical potential (EP) V ±(r) = D e {1 ? (?/δ)[coth (ηr)]±1/1 ? (?/δ)}2 are determined by means of a mathematical method so-called the Nikiforov–Uvarov (NU). The effect of the potential parameters on the ro-vibrating energy states is discussed in several values of the vibrational and rotational quantum numbers. Moreover, the validity of the method is tested with previous models called the semiclassical (SC) procedure and the quantum mechanical (QM) method. The obtained results are applied to the molecules H2 and Ar2.  相似文献   

8.
The expansion of an oxygen low-pressure microwave plasma was investigated in order to determine the optimal plasma parameters for the growth of functional oxide semiconductors. Langmuir probe measurements show that the electron density (n e ) increases with the injected power up to a saturation value of 3.0 × 109 cm?3 determined at 10 mTorr while electron temperature (T e ) remains constant at a value of 1.5 eV. When pressure is varied, n e shows a maximum value at a range from 12 to 20 mTorr while T e decreases monotonously with increasing pressure. In addition, both n e and T e decrease with the axial distance from the plasma source. These effects were discussed through the loss mechanisms in the remote plasma. For a pressure of 13 mTorr and at a substrate temperature of 500 °C, plasma enhanced oxidation of pure metallic Ti thin films lead to the formation of a pure TiO2 anatase phase compared to a mixed phase of TiO2 and TiO in the absence of plasma activation. For Mn thin films, the exposure to oxygen remote plasma led to the formation of MnO2 as opposed to obtaining Mn3O4 when oxidation is performed in the oxygen gas ambient. Remote plasma processing was thus found to provide selective pathways to control oxidation states, stoichiometry and phase composition of technologically attractive oxide thin films.  相似文献   

9.
From studies using different experimental techniques employed to determine the presence of aggregates e.g. isothermal titration calorimetry, surface tension, electrical conductivity, UV–Vis spectrophotometry, dynamic and static light scattering, it is clearly demonstrated that the compound [Cu(4, 4′-dimethyl-2, 2′-bipyridine)(acetylacetonato)H2O]NO3 (Casiopeína III-ia), promising member of a family of new generation compounds for cancer treatment, is able to auto associate in aqueous media. Physicochemical properties associated with the formation of the aggregates were determined in pure water and in phosphate buffer media in order to simulate physiological conditions. From isothermal titration calorimetry and electrical conductivity measurements we calculated the dissociation constant of the aggregates, K D . For pure water the values obtained in both techniques are 2.73 × 10?4 and 5.93 × 10?4 M respectively while for the buffer media we obtained 4.61 × 10?4 and 1.57 × 10?3 M. The enthalpy of dissociation, ?H D , calculated from the calorimetric data shows that the presence of the phosphate ions has an energetic effect on the aggregate stability since in pure water a value of 18.79 kJ mol?1 was obtained in comparison with the buffer media where a value 4 times bigger was found (70.48 kJ mol?1). With the data collected from these techniques the number of monomers calculated which participate in the formation of the aggregates is around two. From our surface tension, electrical conductivity and UV–Vis spectrophotometry measurements the critical aggregate concentration, cac, was determined. For each technique specific concentration ranges were obtained but we can summarize that the cac in pure water is between 3 and 3.5 mM and for the buffer media is between 3.5 and 4 mM. Dynamic light scattering measurements provide us with the hydrodynamic diameter of the aggregates and from static light scattering measurements we determined the molecular weight of the Casiopeína III-ia aggregates to be of 1000.015 g mol?1 which is two times the molecular weight of the Casiopeína III-ia molecule. This value is in agreement with the number of monomers which participate in the formation of the aggregates obtained from isothermal titration calorimetry and electrical conductivity data analysis.  相似文献   

10.
A new V6O13-based material has been synthesized via the sol–gel route. This sol–gel mixed oxide has been obtained from an appropriate heat treatment of the chromium-exchanged V2O5 xerogel performed under reducing atmosphere. This new compound, with the chemical formula Cr0.36V6O13.50, exhibits a monoclinic structure (C2/m) with the following unit cell parameters, a=11.89 Å, b=3.68 Å, c=10.14 Å, β=101.18°. The electrochemical characterization of this compound has been performed using galvanostatic discharge–charge experiments in the potential range 4–1.5 V and completed by ac impedance spectroscopy measurements. It exhibits a specific capacity of about 370 mAh g?1, which makes the compound Cr0.36V6O13.50 the best one in the V6O13-based system: 85% of the initial capacity (315 mAh g?1) after the 35th cycle is still available at C/25 without any polarization. From impedance spectroscopy, a high kinetics of Li transport (D Li=1.8×10?9 cm2 s?1) is found at mid-discharge.  相似文献   

11.
Polyaminopolycarboxylate EDTA with powerful metal-binding property, which often presents in low and intermediate-level waste, can enhance the radionuclide migration. The effect of EDTA on the diffusion behavior of 99TcO4 ? and ReO4 ? in Gaomiaozi (GMZ) bentonite was investigated by using through-diffusion method. For 99TcO4 ? in present of EDTA, the D e values was (1.2 ± 0.1) × 10?11 m2/s, which was 4 times higher than that in absent of EDTA. It can be explained that the complexation between 99TcO4 ? and EDTA might be formed. By contrast, the D e values of ReO4 ? remained unchanged in present or absent of EDTA, indicating that ReO4 ? could not complex with EDTA. However, the diffusion of ReO4 ? could be increased in present of EDTA, the D a value was found to be increased from 1.8 × 10?10 to 5.4 × 10?10 m2/s. It demonstrated that ReO4 ? need more drastic conditions to form the Re(VII)–EDTA complexes than those used for 99TcO4 ?. For both ReO4 ? and 99TcO4 ?, the rock capacity factor α is less than the total porosity ε tot, indicating that they has little retention/sorption on the surface of bentonite.  相似文献   

12.
p-Phenylenediamine was oxidized with p-benzoquinone in the aqueous solutions of methanesulfonic acid (MSA). The conductivity of the products increased with increasing concentration of MSA from 1.5?×?10?12 S cm?1 in 0.1 M MSA up to 3.4?×?10?4 S cm?1 in 5 M MSA. The low-molecular-weight products are basically composed of one p-benzoquinone and two p-phenylenediamine molecules. Their molecular structure is discussed on the basis of mass, Fourier-transform infrared, Raman, NMR and electron paramagnetic resonance (EPR) spectroscopies. The formation of 2,5-di(p-phenylenediamine)-p-benzoquinone protonated with methanesulfonic acid best complies with the information provided by spectroscopic techniques. Its conversion to hydroquinone tautomer explains the formation of unpaired spins observed by EPR and their potential contribution to the conduction.  相似文献   

13.
Flower-like CuO hierarchical nanostructures were synthesized on copper foil substrate through a simple wet chemical route in alkaline media at room temperature. SEM images collected at different reaction times revealed the transformation of initially formed Cu(OH)2 nanowires to flower-like CuO nanostructures. The hierarchical structure of the as-prepared CuO showed high electrocatalytic activity towards the oxidation of glucose making it a promising electrode material for the development of non-enzymatic glucose sensor. The amperometric sensor exhibited a wide linear response to glucose ranging from 4.5 × 10?5 to 1.3 × 10?3 mol L?1 (R 2 = 0.99317) at fixed potential of 0.3 V. The detection limit was 6.9 × 10?6 mol L?1 (LOD = 3σ/s) with a sensitivity of 1.71 μA μmol?1 cm?2. Moreover, the developed sensor offers a fast amperometric response, good selectivity and stability.  相似文献   

14.
Oxygen surface exchange kinetics and diffusion were studied in Pr2NiO4?+?δ (PNO) by the isotope exchange method with gas phase equilibration in the temperature range of 600–800 °C and oxygen pressure range of 0.33–1.62 kPa. The oxygen heterogeneous exchange rate (rH), oxygen diffusion coefficient (D), rates of oxygen dissociative adsorption (ra), and oxygen incorporation (ri) were calculated along with the apparent activation energies of oxygen surface exchange and diffusion processes. The temperature dependence of rH was found to benon-linear in Arrhenius coordinates. The apparent activation energy changed from 1.4?±?0.2 eV at T?>?700 °C to 2.0?±?0.1 eV. This might be attributed to the change in the rate-determining stage of oxygen exchange for Pr2NiO4?+?δ at T ~?700 °C, because of a shift in the ratio between ra and ri caused by the difference in their activation energies. Possible reasons for the observed changes in the rate-determining stage are discussed.  相似文献   

15.
This paper describes an application of a new electro-deposition method in a modulated electrical field in order to have an efficient semiconductor coating on a conductive substrate. The prepared film was used as a photoanode of dye-sensitized solar cells (DSSCs). Electro-deposition of nanoparticles usually was performed by applying a DC electrical field in a suspension. In the DC field, a homogeneous layer could not be performed because of unwanted electrochemical reactions that might occur on the substrate surface. Modulated electrical fields based on pulsed AC and a sweeping voltage profile were used. The photovoltaic performance of the assembled solar cells showed a significant difference between the films produced in different electrical field conditions. Under the illumination of simulated AM 1.5 sunlight (100 mW cm?2) with an aperture black mask, the energy conversion efficiency of 2.45% (V OC = 768 mV, J SC = 4.74 mA cm?2, FF = 67%) was obtained with a thin layer of TiO2 nanoparticles deposited in a pulsed waveform voltage. A crack-free and uniform porous layer produced in this condition showed an enhancement of about seven times over the photoanode prepared using conventional DC electrical field with the same voltage amplitude. The solar cell efficiency was increased to 4.22% (V OC = 735 mV, J SC = 7.92 mA cm?2, FF = 72%) by just increasing the TiO2 film thickness and using a blocking layer beneath the semiconductor layer. Moreover, a higher electron recombination lifetime presented better electron transport and collection efficiency of the film deposited in the pulsed electrical field conditions.  相似文献   

16.
Properties of CF x /Li and CF x /Na cells were examined while using galvanostatic charging/discharging, electrochemical impedance spectroscopy and scanning electron microscopy (SEM). The capacity during the first cycle was as high as ca. 1000 mAh g?1. Such an electrode is suitable for primary CF x /Li and CF x /Na batteries. SEM images of CF x cathode showed that during discharging it was transformed into amorphous carbon and LiF or NaF crystals (of diameter of ca. 5–20 μm). These systems (C?+?LiF or C?+?NaF) cannot be reversibly converted back into CF x /Li or CF x /Na, respectively. Exchange current densities are between 10?7 Acm?2 and 10?9 Acm?2 when working with LiPF6 and NaPF6 electrolytes (1.12?×?10?7 Acm?2 and 6.82?×?10?9 Acm?2, respectively). Those values are low and indicate that the charge transfer process may be the rate-determining step. Activation energies for the charge transfer process were 57 and 72 kJ mol?1 for CF x /LiPF6 and CF x /NaPF6 systems, respectively. Higher activation energy barrier for the CF/Na+?+?e??→?C?+?NaF reaction results in lower observed exchange current density in comparison to the system with lithium ions.  相似文献   

17.
We have reported the semi conducting and photoelectrochemical properties of SrWO4 prepared by chemical route. The phase purity is confirmed by X-ray diffraction and the oxide is characterized by scanning electron microscopy, diffuse reflectance, and electrochemical impedance spectroscopy. SrWO4 crystallizes in the scheelite structure with an average crystallite size of 378 ± 6 nm. The Raman spectrum gives an intense peak at 920 cm?1 assigned to A g mode while the infrared analysis confirms the hexagonal coordination of tungsten. The UV-visible spectroscopy shows an indirect optical transition at 2.60 eV. SrWO4 exhibits n-type conduction by oxygen deficiency, confirmed by the chrono-amperometry and the intensity potential J(E) curve shows a small hysteresis. The Mott-Schottky plot gives electrons density of 5.72 × 1018 cm?3 and a flat band potential of 0.27 VSCE, indicating that the conduction band derives mainly from W6+: 6s orbital. The electrochemical impedance spectroscopy (EIS), measured in the range (1–105 Hz), shows the predominance of the bulk contribution with a dark impedance of 38 kΩ cm2. As application, the ibuprofen is degraded by electrocatalysis on SrWO4 with a conversion rate of 42%. An improvement up to 77% has been obtained by electrophotocatalysis under UV light; the conversion follows a first order kinetic with a rate constant of 2.32 × 10?4 min?1.  相似文献   

18.
Carboxyl methylcellulose (CMC) solid polymer electrolytes were prepared by utilizing oleic acid (OA) and different wt.% of propylene carbonate (PC) by using the solution casting technique. An ionic conductivity study of the films was done by using impedance spectroscopy. The highest ionic conductivity gained is 2.52 × 10?7 S cm?1 at ambient temperature for sample CMC-OA-PC 10 wt.%. From transference number measurement (TNM), the value of cation diffusion coefficient, D+, and ionic mobility, μ+, was higher than the value of anion diffusion coefficient, D?, and ionic mobility, μ?. Thus, the results prove that the present samples were proton conductors.  相似文献   

19.
A nickel(II) complex, [Ni(taetacn)](ClO4)2 ? H2O, where taetacn = 1,4,7-tris(2-aminoethyl)-1,4,7-triazacyclononane was synthesized. The crystal structure was determined by the single-crystal X-ray diffraction method at 293 K. The complex crystallizes in the orthorhombic space group Pna21 with a = 16.004(2) Å, b = 10.186(1) Å, c = 13.937(2) Å, V = 2271.9(5) Å3, Dx = 1.56 g cm?3, Dm = 1.59 g cm?3 (floatation method), and Z = 4. The R1 [I > 2σ(I)] and wR2 (all data) values are 0.0636 and 0.1672, respectively, for all 4845 independent reflections. The compound is composed of octahedral nickel(II) cation with three 2-aminoethyl pendant groups of taetacn, tetrahedral ClO 4 ? anion, and a water molecule of crystallization. Electronic spectra are consistent with the octahedral geometry. Temperature dependence of the magnetic susceptibility (4.5–300 K) can be interpreted considering the zero-field splitting of the nickel(II) ion (g = 2.14, D = 3.72 cm?1, and = 300 × 10?6 cm3 mol?1). Cyclic voltammetry in DMF showed quasi-reversible and irreversible oxidation waves (Epa = 0.54 V, Epc = 0.45 V; Epa = 1.16 V, Epc = 0.71 V vs. Ag/Ag+).  相似文献   

20.
In this paper, the use of molecular self-assembled monolayers of 5-(1,3-dithiolan-2-eyl)-3-methyl banzen-1,2-diol (DMD) on gold nanoparticles was described (DMD-AuNPs). The redox properties of modified electrode at various scan rates were investigated by cyclic voltammetry. A pair of well-defined quasi-reversible redox peaks of DMD were obtained at the modified electrode. Dramatically enhanced electrocatalytic activity was exemplified at the DMD-AuNPs, as an electrochemical sensor to investigate the electro-oxidation of isoprenaline (IP). With this modified electrode, the oxidation potential of the IP was shifted about 235 mV toward a less positive potential value than that of an unmodified electrode. The values of electron transfer coefficients (α = 0.5), catalytic rate constant (ks = 9.2 s?1) and diffusion coefficient (D = 8.9 × 10?5 cm2 s?1) were calculated for IP. The response of catalytic current with IP concentration showed a linear relation in the range from 0.5 to 800 µM with a detection limit of 0.21 µM. Finally, this modified electrode was used for the determination of IP in IP injections.  相似文献   

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