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1.
Self-assembled monolayers (SAMs) obtained by adsorption of n-organothiols molecules have been formed onto polycrystalline copper surfaces in order to build up barrier films protecting copper from oxidation. In this context, formation of n-dodecanethiol (DT), (3-mercaptopropyl)trimethoxysilane (MPTS) and 11-perfluorobutylundecanethiol (F4H11) monolayers has been elaborated on copper and evaluated by X-ray photoelectron spectroscopy while polarization and cyclic voltammetry curves were used to compare the inhibition efficiency of the three organic coatings. Furthermore, atomic absorption spectrometry measurements were carried out in domestic water and in NaCl 0.5 M solutions in order to evaluate and quantify the dissolution of copper electrodes before and after protection. Results showed evidences that, among the three organic compounds assessed, F4H11 is the most suitable candidate to slow down the copper oxidation process.  相似文献   

2.
New functionalized ionic liquids (ILs), comprised of multi-methoxyethyl substituted quaternary ammonium cations (i.e. [N(CH2CH2OCH3)4−n(R)n]+; n = 1, R = CH3OCH2CH2; n = 1, R = CH3, CH2CH3; n = 2, R = CH3CH2), and two representative perfluorinated sulfonimide anions (i.e. bis(fluorosulfonyl)imide (FSI) and bis(trifluoromethanesulfonyl)imide (TFSI)), were prepared. Their fundamental properties, including phase transition, thermal stability, viscosity, density, specific conductivity and electrochemical window, were extensively characterized. These multi-ether functionalized ionic liquids exhibit good capability of dissolving lithium salts. Their binary electrolytes containing high concentration of the corresponding lithium salt ([Li+] >1.6 mol kg−1) show Li+ ion transference number (tLi+) as high as 0.6-0.7. Their electrochemical stability allows Li deposition/stripping realized at room temperature. The desired properties of these multi-ether functionalized ionic liquids make them potential electrolytes for Li (or Li-ion) batteries.  相似文献   

3.
5-Methoxy-2-(octadecylthio)benzimidazole (MOTBI) monolayer was self-assembled on fresh copper surface obtained after etching with nitric acid at ambient temperature. The optimum conditions for formation of self-assembled monolayer (SAM) were established using impedance studies. The optimum conditions are methanol as solvent, 10 mM concentration of the organic molecule and an immersion period of 24 h. The MOTBI SAM on copper surface was characterized by contact angle measurements, X-ray photoelectron spectroscopy and reflection absorption FTIR spectroscopy and it is inferred that chemisorption of MOTBI on copper surface is through nitrogen. Corrosion protection ability of MOTBI SAM was evaluated in aqueous NaCl solution using impedance, electrochemical quartz crystal nanobalance, potentiodynamic polarization and weight-loss studies. While bare copper showed a charge-transfer resistance (Rct) value of 1.89 kΩ cm2 in 0.20 M NaCl aqueous environment, the Rct value for SAM covered copper surface is 123.4 kΩ cm2. The MOTBI SAM on copper afforded corrosion inhibition efficiency of 98-99% in NaCl solution in the concentration range and in the temperature range studied. The SAM functions as a cathodic inhibitor. Quantum chemical calculations showed that MOTBI has relatively small ΔE between HOMO and LUMO and large negative charge in its benzimidazole ring, which facilitate formation of a polymeric [Cu+-MOTBI] complex on copper surface.  相似文献   

4.
The lateral diffusion constants of two water insoluble redox surfactants, 4-alkaneamide derivatives of 2,2,6,6-tetramethyl-1-piperidynyloxy radical (CnTempo where n = 14 or 18) were measured using 2D voltammetry with 500 μm long line electrodes positioned in the plane of the air/water interface. In order to extend these measurements into a region of low surface concentrations, we first examined the line micro-band electrodes as well as the stability of the Tempo surfactants on the water surface. Only C18Tempo proved to be sufficiently insoluble in water to form stable monolayer films over sufficiently long periods of time to assure reproducible measurements in the range of mean molecular areas (MMA) of 50-750 Å2/molecule. In this range, its diffusion constant increases linearly with MMA. At MMA of ca. 450 Å2/molecule, this dependence becomes significantly weaker suggesting proximity of a plateau region with a D of ca. 1.5 × 10−5 cm2/s. The orientation of C18Tempo on the water surface in a compressed monolayer at 52 Å2/molecule was determined by X-ray reflectivity using a synchrotron source. Only the amide group of C18Tempo appears to be immersed in the aqueous subphase while the alkane chain and the piperidine ring are located above the water surface pointing upwards.  相似文献   

5.
In this study we report the characterization of a prototype solid-state electrochromic device based on poly(ethylene oxide) (PEO)/siloxane hybrid networks doped with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The polymer networks prepared, designated as di-ureasils and represented as d-U(2000), were produced by a sol-gel procedure and are composed of a siliceous framework to which both ends of polyether chains containing about 40 CH2CH2O units are covalently bonded through urea linkages. Samples with compositions of 200 ≥ n ≥ 0.5 (where n is the molar ratio of CH2CH2O to Li+) were characterized by thermal analysis, complex impedance measurements and cyclic voltammetry at a gold microelectrode. Electrolyte samples were obtained as self-supporting, transparent, amorphous films and at room temperature the highest conductivity was observed with the d-U(2000)35LiTFSI composition (3.2 × 10−5 Ω−1 cm−1). We report the results of preliminary evaluation of these polymer electrolytes as multi-functional components in prototype electrochromic displays. Device performance parameters such as coloration efficiency, optical contrast and image stability were also evaluated. The electrolytes with n > 8 presented an optical density above 0.56 and display assemblies exhibited good open-circuit memory and stable electrochromic performances.  相似文献   

6.
Aziz Ya?an 《Electrochimica acta》2006,51(14):2949-2955
Poly(N-ethylaniline) (PNEA) coatings on the mild steel electrode were synthesized by electrochemical oxidation of N-ethylaniline using aqueous oxalic acid solutions as reaction medium. Electrodeposition was carried out by potentiodynamic, potentiostatic and galvanostatic synthesis techniques. Smooth, adhesive and thick PNEA coatings on mild steel could be electrosynthesized during sequential scanning of the potential region between −0.5 and 1.4 V versus SCE, with scan rate of 20 mV s−1. The electrodeposited coatings were characterized by cyclic voltammetry, FT-IR and UV-vis techniques. Corrosion behavior of PNEA coated steels was investigated by linear anodic potentiodynamic polarization technique and Tafel test. Anodic potentiodynamic polarization results showed that electrodissolution current value of PNEA coated steel decreased about 90% compared to that of the uncoated steel in 0.5 M H2SO4 aqueous solution. Tafel plots showed also strong decrease of corrosion current for the PNEA coated electrode compared to the uncoated steel electrode in 3% NaCl as corrosive medium.  相似文献   

7.
Pure and mixed gas n-C4H10 and CH4 sorption and dilation in poly(1-trimethylsilyl-1-propyne) (PTMSP) are reported at temperatures ranging from −20 to 35 °C. The presence of n-C4H10 in the mixture considerably reduces CH4 solubility. For example, CH4 solubility (in the limit of zero CH4 fugacity) at 25°C decreases from 4.0 (pure gas) to 0.78 cm3(STP)/(cm3 polymer atm) in the presence of n-C4H10 at an activity of 0.60. At −20 °C, CH4 solubility decreases by almost an order of magnitude, from 10.2 (pure gas) to 1.22 cm3(STP)/(cm3 polymer atm) in the presence of n-C4H10 at an activity of 0.61. In contrast, n-C4H10 mixture sorption properties are not measurably affected by the presence of CH4. The dual mode sorption model parameters for CH4 and n-C4H10 in PTMSP were determined from pure and mixed gas sorption measurements, and this model can adequately describe the sorption data. The n-C4H10/CH4 mixed gas solubility selectivity in PTMSP decreases as temperature increases and as n-C4H10 activity increases. For example, at 25 °C, the n-C4H10/CH4 solubility selectivity decreases from 250 to 120 as n-C4H10 activity increases from 0.02 to 0.25. At −20 °C and an n-C4H10 activity of 0.24, the n-C4H10/CH4 solubility selectivity is 590. Penetrant-induced volume dilation of PTMSP can be adequately modeled by assuming that all swelling is caused by penetrant molecules sorbed in the polymer's dense equilibrium region (i.e., the Henry's law region) during sorption. However, the best fit partial molar volumes in the Henry's law region for the dilation data are considerably lower than the penetrant partial molar volumes in liquids, suggesting that further theoretical efforts are needed to develop predictive models of volume dilation in high free volume glassy polymers.  相似文献   

8.
Poly(ethylene glycol)dimethyl ethers [(CH3O(CH2CH2O)nCH3, n = 1, 2, 3, and 4)] are generally known as “glymes”. This study examines the conductivity, lithium ion solvation state and charge-discharge cycling efficiency of lithium metal anodes in glyme-based electrolytes for rechargeable lithium cells. 1 M (M: mol l−1) LiPF6 was used as the solute. The properties of the glymes were investigated by using a ternary mixed solvent consisting of n-glyme, ethylene carbonate (EC) and methylethylcarbonate (MEC). This was because the solubility of LiPF6 is far less than 1 M in an n-glyme single solvent. The glyme solutions exhibited higher conductivity and higher lithium cycling efficiency than EC/MEC. The conductivity tended to increase with decreases in ethylene oxide chain number (n) and solution viscosity. The decrease in the solution viscosity resulted from the change in the lithium ion solvation structure that occurred when a glyme was added to EC/MEC. The selective solvation of the glyme with respect to lithium ions was clearly demonstrated by -NMR measurements. The lithium cycling efficiency value depended on the charge-discharge current (Ips). When n increased there was an increase in lithium cycling efficiency at a low Ips and a decrease in the reduction potential of the glymes. When the conductivities including those at low temperature (below 0 °C), and charge-discharge cycling at a high current are taken into account, di- or tri-glyme is superior to the other glymes tested here.  相似文献   

9.
The electrochemical behavior of CCl4, CHCl3 and CH2Cl2 has been investigated by cyclic voltammetry at glassy carbon and silver electrodes in DMF + 0.1 M Et4NClO4 in the absence and presence of a good proton donor. At both electrodes, each compound exhibits a series of reduction peaks which represent sequential hydrodechlorination steps up to methane. The nature of the electrode material and the proton availability of the medium affect drastically the voltammetric pattern of the compounds. Silver exhibits extraordinary electrocatalytic properties toward the reduction process, with positive shifts of the peak potentials of about 0.57-0.95 V as compared to glassy carbon. Reduction of any polychloromethane, CHnCl(4−n) (n = 0-2), yields the carbanion CHnCl(3−n) which partitions into two reaction channels: (i) protonation and (ii) Cl elimination to give a carbene :CHnCl(2−n). If a strong proton donor is added into the solution, sequential hydrodechlorination becomes the principal reaction route at both electrodes. When, instead, purposely added acid is not present in solution, both reaction pathways ought to be considered. In these conditions, when possible, self-protonation reactions play an important role in the overall reduction process.  相似文献   

10.
The paper reports on the corrosion behavior of carbon steel coated with thin SiOx-like oxide films. The SiOx-like coatings were deposited by plasma-enhanced chemical vapor deposition (PECVD) and their thickness was varied between 20 and 200 nm. The coated carbon steel interfaces were investigated for their corrosion protection efficiency when immersed in an aqueous saline solution of 3% NaCl. FTIR measurements and electrochemical impedance spectroscopy (EIS) experiments revealed that thin SiOx-like coating layers (20 nm thick) do not prevent the carbon steel from corrosion, while thicker silica layers (d ≥ 100 nm) protect efficiently carbon steel interfaces in highly saline media with a protection efficiency of about 96% for a 200 nm thick coating.  相似文献   

11.
Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H) composite films, which possess n-type conduction with enhanced electrical conductivities, were prepared by pulsed laser deposition and they were structurally studied by Fourier transform infrared (FTIR) spectroscopy. The film with a nitrogen content of 7.9 at.% possessed n-type condition with an electrical conductivity of 18 S/cm at 300 K. The FTIR spectra revealed peaks due to nitrogen impurities, C = N, C-N, and CHn (n = 1, 2, 3) bands. The sp2-CHn/(sp2-CHn + sp3-CHn), estimated from the area-integration of decomposed peaks, were 24.5 and 19.4% for undoped and 7.9 at.% doped films, respectively. The nitrogen-doping not only form the chemical bonds between carbon and nitrogen atoms such as C = N and C-N bonds but also facilitate the formation of both sp2 and sp3 bonds, in particular, the sp3-CHn bond is preferentially formed. From the analysis of the FTIR spectra, it was found that the hydrogen content in the film is increased with an increase in the nitrogen content. The increased hydrogen content might be owing to the enhanced volume of grain boundaries (GBs) between UNCD grains, and those between UNCD grains and an a-C:H matrix, which is caused by a reduction in the UNCD grain size. The CHn peaks predominantly come from an a-C:H matrix and GBs. Since the nitrogen-doping for a-C:H has been known to be hardly effective, the n-type conduction with the enhanced electrical conductivities might be attributed to the sp2-CHn formation at the GBs.  相似文献   

12.
The adsorption kinetics and thermodynamics for the formation of redox active self-assembled monolayer (SAM) of 2-(n-mercaptoalkyl)hydroquinone (abbreviated as H2Q(CH2)nSH, where n = 4, 6, 8, 10, and 12) on gold electrode has been investigated by cyclic voltammetry to study the effects of concentration and alkyl chain length. The time dependence of surface coverage, differential capacitance, and formal potential of electroactive hydroquinone(H2Q) moiety supports that the adsorption of H2Q(CH2)nSH molecules typically processes with a two-step adsorption consisted of a fast initial adsorption and a slowly following reorganization. The adsorption processes can be satisfactorily described by simple Langmuir adsorption kinetics, irrespective of concentration and alkyl chain length of adsorbate molecule. Based on Langmuir kinetics, the adsorption rate constant was determined at the initial step for the formation of all H2Q(CH2)nSH-SAMs studied in this work. The rate constant value was found to be decreased with increasing alkyl chain length and decreasing bulk solution concentration (≤10 μM). The dependence of a surface coverage (Γe) at adsorption equilibrium on the bulk concentration is accurately described by the Langmuir isotherm at several concentrations ranging from 8 × 10−6 to 1 × 10−5 M for all H2Q(CH2)nSH molecules. Parameters characterizing the adsorption thermodynamics, such as Γs, adsorption coefficient (β), and adsorption free energy (ΔGads) were determined from this isotherm.  相似文献   

13.
The combination of sonolysis and photolysis in the presence of hydrogen peroxide (H2O2) in a 7-L external-loop airlift sonophotoreactor was used to treat the aqueous solution of p-aminophenol. The central composite design (CCD) and response surface methodology (RSM) were employed to evaluate the interaction effects of the initial H2O2 concentration (x1 = 100–900 mg/L), the ultrasonic power (x2 = 25–65 W), the air flow rate (x3 = 1–5 L/min), and the initial concentration of p-aminophenol (x4 = 10–50 mg/L) on the p-aminophenol degradation and total organic carbon (TOC) reduction efficiencies as well as to optimize operating conditions. The coefficients of determination (R2) and adjusted-R2 obtained from the analysis of variance (ANOVA) were 0.9900 and 0.9812 for the p-aminophenol degradation; and 0.9742 and 0.9516 for the TOC removal, respectively, ensuring a satisfactory adjustment of the quadratic regression model with experimental results. The linear, square, and interaction effects of x1, x2, x3, and x4 were also calculated. Genetic algorithm optimization was employed to maximize the mineralization efficiency. 79% TOC reduction efficiency after 90 min and 86.5% p-aminophenol removal efficiency after 30 min were achieved under recirculating batch mode at operating conditions of x1 = 740 mg/L, x2 = 65 W, x3 = 5 L/min, and x4 = 24 mg/L.  相似文献   

14.
This work shows a comparative study of the incineration of 2-mM p-cresol and o-cresol in 1 M-H2SO4 in aqueous media. Microelectrolysis studies indicated that both the p-cresol and o-cresol oxidation were carried out via hydroxyl radicals (OH) formed by water oxidation in the boron-doped diamonds (BDD)-H2O-H2SO4-p-cresol and o-cresol interface. In both cases, the potential and current density ranges, where great amounts of OH are formed, were between 2.3 V ≤ E ≤ 2.75 V versus SHE and J = 10 mA cm−2. Electrolyses in an undivided FM01-LC reactor were performed at different Reynolds values 27,129 ≤ Re ≤ 42,631, and at J = 10 mA cm−2. For p-cresol and o-cresol, the rate of degradation was slow, however it increases slightly as a function of the Re, indicating that the oxidation involves a complex pathway; current efficiency also rises as a function of the Re. For p-cresol, the mineralization at Re = 42,631 reached 90%, with 71% current efficiency and an energy consumption of 7.84 kWh m−3; whereas o-cresol was mineralized to 84%, with 67% current efficiency and an energy consumption of 6.56 kWh m−3. The results obtained in this work demonstrated that o-cresol is more recalcitrant than p-cresol.  相似文献   

15.
Ionically conducting materials based on a poly(?-caprolactone) (PCL)/siloxane organic/inorganic host framework doped with magnesium triflate (Mg(CF3SO3)2) were synthesized by the sol-gel process. In this matrix short PCL chains are covalently bonded to the siliceous network via urethane linkages. In this study the salt content of samples was identified using the conventional notation n, where n indicates the number of (C(O)(CH2)5O) PCL repeat units per Mg2+ ion. Xerogels with compositions ranging from n = ∞ to 1 were prepared. The only composition studied that was not entirely amorphous was that prepared with n = 1. Xerogels with n ≥ 7 are thermally stable up to at least 200 °C. The composition with the highest conductivity of the series is that with n = 34 (5.9 × 10−9 and 9.8 × 10−7 S cm−1 at 24 and 104 °C, respectively).  相似文献   

16.
The effect of the alkyl side group on the synthesis and the electrochemical properties of N-alkyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1ATFSI) ionic liquids (ILs) is reported. The investigation was focused on the PYR1ATFSI ionic liquid family because of the interesting electrochemical properties of the members with propyl and butyl side chains. Side alkyl groups (A = CnH2n+1 with n ranging from 1 to 10) of different length and structure were used for the synthesis of PYR1ATFSI materials. NMR and DSC have shown that the ionic liquids were correctly synthesized with the exception of the compounds with tertiary side chains. Most of the materials exhibited a conductivity higher than 10−3 S cm−1 already at 12 °C. In the molten state a moderate conductivity decrease was observed with increasing the length and the branching of the side chain (C2H2n+1) group according with the change of viscosity of the ionic liquids. Most of the PYR1ATFSI samples exhibited an electrochemical stability window exceeding 5 V.  相似文献   

17.
Water-soluble amino acid derivatives of gadolinium (Gd) endohedral metallofullerenes (AAD-EMFs), Gd@C82Om(OH)n(NHCH2CH2COOH)l (m ≈ 6, n ≈ 16 and l ≈ 8) are synthesized by a direct reaction of the pure endohedral metallofullerene Gd@C82 with an excess of alkaline solution of β-alanine. The structure of the AAD-EMFs is characterized by FTIR, XPS and laser-desorption time-of-flight (LD-TOF) mass spectrometries. Water proton relaxivity analysis indicates that the longitudinal relaxivity R1 (the effect on 1/T1, 9.1 mM−1 s−1) of AAD-EMFs is higher than that of the commercial MRI contrast agent, Magnevist (gadolinium-diethylenetriaminepentaacetic acid, Gd-DTPA, 5.6 mM−1 s−1). The MRI phantom studies are performed to confirm the high efficiency of this sample as MRI contrast agents.  相似文献   

18.
The low temperature FTIR spectrum of long chain n-alkanes has been investigated in the region between the C-C stretching and CH2 twisting fundamentals (1050-1133 cm−1). With successive annealing and cooling stages, extended chain crystals of n-C198H398 show an improvement in the regularity of the progression bands observed. This is related to a ‘perfecting’ of the crystals. A once-folded sample of the same alkane shows additional features between 1050 and 1100 cm−1, attributed to resonance modes from a tight (110) fold. These disappear on transformation to the extended form, to be replaced by progression bands. Assignment of the individual bands enables the length of the all-trans chain to be estimated and this method is used to show that centre-branched long chain n-alkanes have a folded conformation. It is also shown that the chain length derived from such FTIR data for a 1:1 molar mixture of n-C162H326 and n-C246H494 is consistent with a triple layer superlattice structure.  相似文献   

19.
A general method has been developed for accumulation of a dinuclear ruthenium complex [Ru2(dhpta)(μ-O2CCH3)2] (H5dhpta = 1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetraacetic acid) on a gold surface. The accumulation using a ligand substitution reaction of bridging acetate in the complex by terminal benzoic acid in a self-assembled monolayer (SAM) with ω-mercaptoalkoxy benzoic acid (HOOC-C6H4-O-(CH2)n-SH) (n = 4, 6, 12) is undergone. The methyl benzoate-containing alkyl disulfides capable to form SAMs on gold electrode have been synthesized utilizing reductive dimerization of the corresponding alkyl thiocyanates with tetraphenylphosphonium tetrathiomolybdate. The methyl benzoate group in the SAM was converted into benzoic acid group by base hydrolysis, which was confirmed by surface-enhanced Raman scattering measurements for silver electrode. After the ligand substitution reactions to accumulate the complex on the gold electrode surface, in the case of n = 6 and n = 12, voltammetric waves for surface confined redox process, which corresponds to RuIIIRuIII/RuIIIRuII redox couple are observed, respectively, and these surfaces of gold electrodes are covered with the complex completely. The present ligand substitution reaction should be widely applicable for the accumulation of other complexes and useful for designing of functional electrodes.  相似文献   

20.
A modified technique of rapid expansion of supercritical solutions (RESS) was applied to incorporate essential oil extracted from Atractylodes macrocephala Koidz into liposomes. In the modified RESS process, both the liposomal materials and the essential oil were dissolved in the mixture of supercritical carbon dioxide (SC-CO2)/ethanol and then the solution was sprayed into an aqueous medium through a coaxial nozzle to form liposomes suspension. The encapsulation performance of liposomes could be controlled by changing expansion processing conditions such as pressure, temperature of SC-CO2 and the amount of ethanol. The entrapment efficiency, drug loading and average particle size of liposomes were found to be 82.18%, 5.18% and 173 nm, respectively, under the optimum conditions of at a pressure of 30 MPa, a temperature of 338 K and a ethanol mole fraction in SC-CO2 [(x(CH3CH2OH)] of 15%. The formed liposomes appeared as double-layered colloidal spheres with a uniform and narrow particle size distribution. The physicochemical properties of liposomes including entrapment efficiency, dissolution rate and stability were complied with the provisions of Chinese pharmacopoeia. All these results indicate that the modified RESS technique is an innovative way for self-assembly of liposomes incorporation of multi-components extracted from Chinese traditional medicines in the SC-CO2.  相似文献   

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