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1.
Electrically facilitated molecular transport in an ion-exchange membrane (Nafion, 1100 equiv wt) has been studied using a scanning electrochemical microscope. The transport rates of ferrocenylmethyltrimethylammonium (a cation), acetaminophen (a neutral molecule), and ascorbate (an anion) through approximately 120-micron-thick membranes were measured as a function of the iontophoretic current passed across the membrane (-1.0 to +1.0 A/cm2). Transport rates were analyzed by employing the Nernst-Planck equation, modified to account for electric field-driven convective transport. Excellent agreement between experimental and theoretical values of the molecular flux was obtained using a single fitting parameter for each molecule (electroosmotic drag coefficient). The electroosmotic velocity of the neutral molecule, acetaminophen, was shown to be a factor of approximately 500 larger than that of the cation ferrocenylmethyltrimethylammonium, a consequence of the electrostatic interaction of the cation with the negatively charged pore walls of the ion-exchange membrane. Electroosmotic transport of ascorbate occurred at a negligible rate due to repulsion of the anion by the cation-selective membrane. These results suggest that electroosmotic velocities of solute molecules are determined by specific chemical interactions of the permeant and membrane and may be very different from the average solution velocity. The efficiency of electroosmotic transport was also shown to be a function of the membrane thickness, in addition to membrane/solute interactions. 相似文献
2.
The density of Nafion membranes wetted in water and acetonitrile and the solubility of Nafion in a 50:50 ethanol/water mixture are reported. Commercially available membranes, solution recast membranes, and recast membranes thermally processed for varying lengths of time were examined. Unheated recast membranes were found to be ~20% less dense in water than both commercial membranes and recast membranes heated at 140 °C for 40, 50, and 60 min. For heating times of ≥40 min, the density of recast membranes in water was invariant and equal to the density of commercial films. Similarly, in acetonitrile, commercial membranes and films heated for 1 h had the same density; unheated recast films were ~25% less dense. Nafion density in acetonitrile was ~15% less than that in water. Acid pretreatment reduced Nafion film density by ~15%. Unheated recast films were 22-100% soluble in a sonicated ethanol/water mixture. Commercial membranes and recast films heated for as little as 10 min were insoluble under the same conditions. 相似文献
3.
Electrokinetic flow provides a mechanism for a variety of fluid pumping schemes. The design and characterization of an electrochemically driven pump that utilizes porous carbon electrodes, iodide/triiodide redox electrolytes, and Nafion membranes is described. Fluid pumping by the cell is reversible and controlled by the cell current. Chronopotentiometry experiments indicate that the total available fluid that can be pumped in a single electrolysis without gas evolution is determined solely by the initial concentration of electrolyte and the applied current. The magnitude of the fluid flow at a given current is determined by the nature of the cation in the electrolyte and by the water absorption properties of the Nafion membrane. For 1 M aqueous electrolytes, pumping rates ranging from 1 to 14 microL/min were obtained for current densities of 10-30 mA/cm2 of membrane area. Molar volume changes for the I3-/I- redox couple and for the alkali cation migration contribute little to the observed volumetric flow rates; the magnitude of the flow is dominated by the migration-induced flow of water. 相似文献
4.
In this study, carbon nanofiber (CNF) was used as a support in which 47.5 wt% Pt/CNFs catalyst was prepared by a modified polyol method. The platinum particle size and dispersion on the CNFs are approximately 2-4 nm as determined by X-ray diffractometry and transmission electron microscopy. The specific surface area was approximated as 55.90 m2/g by BET analysis. Electrodes were prepared by the spray method and have a size of 5 cm2. A commercial catalyst (TKK, 46 wt% Pt/C) was used as the anode and the cathode was Pt/CNFs. Different amounts of Nafion ionomer (Aldrich, 5 wt% solution, in the range of 0-20 wt%) were coated on a membrane (Dupont, Nafion 212) with 0.4 mg/cm2 of Pt catalyst at the cathode side. The resulting polarization, ohmic and mass transfer resistances changed significantly based on the Nafion ionomer content. Optimum Nafion ionomer content in the 47.5 wt% Pt/CNFs was 5 wt%. The well-dispersed Nafion ionomer was observed on the catalyst surface area using SEM-EDAX analysis. A sufficient triple-phase boundary was formed by a small amount of Nation ionomer due to the BET surface area of the Pt/CNFs. 相似文献
5.
Transmission infrared spectroscopy was applied to investigate properties of the perfluorosulfonated polymer Nafion. Measurements were made on thin films formed by casting the polymer from solution onto ZnSe windows. Effects of water vapor permeation were studied. A complex band structure between 1350 and 1100 cm(-1) was analyzed qualitatively by fitting the region to Gaussian functions. Features associated with vibrational modes of -CF(2) and -SO(3)(-) groups were identified and observed to be sensitive to film hydration. The intensities of bands for the -SO(3)(-) modes increased with film hydration, while bands assignable to -CF(2) modes decreased. The results were applied to interpret infrared difference spectra of Nafion and shed light on the complicated features that appear. Vibrational bands for water were also examined. In partially hydrated films, the stretching mode of the free -OH group for interfacial water present in pores and channels of the polymer and bands for hydrated proton clusters were detected. 相似文献
6.
以磺化杂萘联苯聚醚酮(SPPEK)为基体,采用共混法制备了SPPEK/PWA复合质子交换膜。采用红外光谱、热分析与交流阻抗等方法对复合膜的结构和性能进行了研究,并与Nafion117膜进行了比较。结果表明,磷钨酸(PWA)的掺杂使得复合膜的吸水率和溶胀度增大,同时热稳定性能得到提高。复合膜在20℃时的质子电导率为0.67×10-2S/cm,接近Nafion117膜的质子电导率(1.08×10-2S/cm)。且随着温度的升高,电导率逐渐增大,最高可达1.18×10-2S/cm。此外,对复合膜不同方向上的电导率进行了测试,表明膜平面方向上的电导率(8.10×10-2S/cm)高于厚度方向上电导率(7.50×10-3S/cm)约一个数量级。 相似文献
7.
Demers LM Mirkin CA Mucic RC Reynolds RA Letsinger RL Elghanian R Viswanadham G 《Analytical chemistry》2000,72(22):5535-5541
Using a fluorescence-based method, we have determined the number of thiol-derivatized single-stranded oligonucleotides bound to gold nanoparticles and their extent of hybridization with complementary oligonucleotides in solution. Oligonucleotide surface coverages of hexanethiol 12-mer oligonucleotides on gold nanoparticles (34 +/- 1 pmol/cm2) were significantly higher than on planar gold thin films (18 +/- 3 pmol/cm2), while the percentage of hybridizable strands on the gold nanoparticles (1.3 +/- 0.3 pmol/cm2, 4%) was lower than for gold thin films (6 +/- 2 pmol/cm2, 33%). A gradual increase in electrolyte concentration over the course of oligonucleotide deposition significantly increases surface coverage and consequently particle stability. In addition, oligonucleotide spacer sequences improve the hybridization efficiency of oligonucleotide-modified nanoparticles from approximately 4 to 44%. The surface coverage of recognition strands can be tailored using coadsorbed diluent oligonucleotides. This provides a means of indirectly controlling the average number of hybridized strands per nanoparticle. The work presented here has important implications with regard to understanding interactions between modified oligonucleotides and metal nanoparticles, as well as optimizing the sensitivity of gold nanoparticle-based oligonucleotide detection methods. 相似文献
8.
Evanescent wave cavity ring-down absorption spectroscopy is applied to measure the thermodynamic properties of the surface adsorption for neutral trans-4-[4-(dibutylamino)styryl]-1-(3-sulfopropyl) pyridinium (DP) and charged trans-4-[4-(dibutylamino)styryl]-1-methylpyridinium iodide (DMP+ I-) at the silica/CH3CN interface, where the interfacial density is determined by measurement of absorbance. The bulk concentration dependence of the surface density may be characterized with a Langmuir isotherm model, which yields saturated surface density, equilibrium constant, and free energy of adsorption of (7.0 +/- 0.3) x 10(13) cm(-2), (1.3 +/- 0.2) x 10(4) M(-1), and -23.5 +/- 0.4 kJ/mol for DP and (8.9 +/- 0.3) x 10(12) cm(-2), (2.6 +/- 0.7) x 10(4) M(-1), and -25.2 +/- 0.6 kJ/mol for DMP+ I-, respectively. The surface density of the isolated silanol groups may then be estimated in terms of the molecular probe results. The absorption contribution from the bulk solution is a factor of approximately 10(1)-10(2) smaller than the total absorbance measured such that subtraction of the bulk contribution leads to negligible change of the thermodynamic properties. The DP is adsorbed to the SiOH sites by forming hydrogen bonds, while the DMP+ cation is bound to the SiO- sites by electrostatic attraction. Surface forces are also probed by addition of triethylamine (TEA), which is competitive with DP for the silanol sites. When the TEA concentration is increased, the DP surface density is found to decrease, whereas the DMP+ surface density increases. The obtained thermodynamic properties are generally consistent with those measured by second harmonic generation spectroscopy. However, when a tetramethylammonium ((CH3)4N+ Cl-) salt is added, the DMP+ cation behaves differently between these two methods. Formation of an electrical double layer may account for the difference. 相似文献
9.
Microfabrication techniques common in commercial semiconductor manufacturing were used to produce carbon/nitroazobenzene/Cu/Au molecular junctions with a range of areas from 3×3 to 400×400 μm, starting with 100-mm-diameter silicon wafers. The approach exhibited high yield (90-100%) and excellent reproducibility of the current density (relative standard deviation of typically 15%) and 32 devices on a chip. Electron-beam-deposited carbon films are introduced as substrates and may be applied at the full wafer level before dicing and electrochemical deposition of the molecular layer. The current scaled with the device area over a factor of >600, and the current density was quantitatively consistent with structurally similar molecular junctions made by other techniques. The current densities were weakly dependent on temperature over the range of 100-390 K, and maximum current densities above 400 A/cm2 were observed without breakdown. To simulate processing and operation conditions, the junction stability was tested at elevated temperatures. The JV curves of microfabricated junctions were unchanged after 22 h at 100 °C. A ~50% increase in the current density was observed after 20 h at 150 °C but then remained constant for an additional 24 h. Parallel fabrication, thermal stability, and high yield are required for practical applications of molecular electronics, and the reported results provide important steps toward integration of molecular electronic devices with commercial processes and devices. 相似文献
10.
Granger MC Witek M Xu J Wang J Hupert M Hanks A Koppang MD Butler JE Lucazeau G Mermoux M Strojek JW Swain GM 《Analytical chemistry》2000,72(16):3793-3804
Standard electrochemical data for high-quality, boron-doped diamond thin-film electrodes are presented. Films from two different sources were compared (NRL and USU) and both were highly conductive, hydrogen-terminated, and polycrystalline. The films are acid washed and hydrogen plasma treated prior to use to remove nondiamond carbon impurity phases and to hydrogen terminate the surface. The boron-doping level of the NRL film was estimated to be in the mid 1019 B/cm3 range, and the boron-doping level of the USU films was approximately 5 x 10(20) B/cm(-3) based on boron nuclear reaction analysis. The electrochemical response was evaluated using Fe-(CN)6(3-/4-), Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, dopamine, ascorbic acid, Fe(3+/2+), and chlorpromazine. Comparisons are made between the apparent heterogeneous electron-transfer rate constants, k0(app), observed at these high-quality diamond films and the rate constants reported in the literature for freshly activated glassy carbon. Ru(NH3)6(3+/2+), IrCl6(2-/3-), methyl viologen, and chlorpromazine all involve electron transfer that is insensitive to the diamond surface microstructure and chemistry with k0(app) in the 10(-2)-10(-1) cm/s range. The rate constants are mainly influenced by the electronic properites of the films. Fe(CN)6(3-/4-) undergoes electron transfer that is extremely sensitive to the surface chemistry with k0(app) in the range of 10(-2)-10(-1) cm/s at the hydrogen-terminated surface. An oxygen surface termination severely inhibits the rate of electron transfer. Fe(3+/2+) undergoes slow electron transfer at the hydrogen-terminated surface with k0(app) near 10(-5) cm/s. The rate of electron transfer at sp2 carbon electrodes is known to be mediated by surface carbonyl functionalities; however, this inner-sphere, catalytic pathway is absent on diamond due to the hydrogen termination. Dopamine, like other catechol and catecholamines, undergoes sluggish electron transfer with k0(app) between 10(-4) and 10(-5) cm/s. Converting the surface to an oxygen termination has little effect on k0(app). The slow kinetics may be related to weak adsorption of these analytes on the diamond surface. Ascorbic acid oxidation is very sensitive to the surface termination with the most negative Ep(ox) observed at the hydrogen-terminated surface. An oxygen surface termination shifts Ep(ox) positive by some 250 mV or more. An interfacial energy diagram is proposed to explain the electron transfer whereby the midgap density of states results primarily from the boron doping level and the lattice hydrogen. The films were additionally characterized by scanning electron microscopy and micro-Raman imaging spectroscopy. The cyclic voltammetric and kinetic data presented can serve as a benchmark for research groups evaluating the electrochemical properties of semimetallic (i.e., conductive), hydrogen-terminated, polycrystalline diamond. 相似文献
11.
聚甲基丙烯酸酰亚胺(PMI)泡沫因其性能优越,在航空航天领域广泛应用。本文主要针队PMI泡沫在弹筒适配器领域的功能特性开展研究,主要研究了其在常温条件下的压缩蠕变特性。依据使用工况及高分子材料的蠕变特性,采用“时间强化”模型设计实验,分别对密度为0.075 g/cm3和0.110 g/cm3的PMI泡沫进行了为期180天的常温压缩蠕变实验。通过对实验数据分析、拟合,预测了两种不同密度的PMI泡沫常温、1 250 N条件下的压缩蠕变寿命,密度0.075 g/cm3 PMI泡沫压缩蠕变失效寿命约为11年;而密度0.110 g/cm3PMI泡沫约为53年,同时对模型的可靠性进行了验证分析。 相似文献
12.
A simple procedure to incorporate tris(2-2'-bipyridyl)ruthenium(II), [Ru(bpy)3]2+, into Nafion Langmuir-Schaefer (LS) films is described. Nafion LS films (tens of nanometers thick) were formed on quartz glass and indium tin oxide (ITO) directly from Nafion-[Ru(bpy)3]2+ Langmuir films assembled at the water-air interface. This procedure allowed the direct incorporation of [Ru(bpy)3]2+ into Nafion films without the need for subsequent loading. UV-vis spectroscopy confirmed the successful incorporation of [Ru(bpy)3]2+ within the LS films and showed that the amount of [Ru(bpy)3]2+ immobilized in this way scaled with film thickness. Voltammetric studies on ITO-modified electrodes confirmed the successful incorporation of [Ru(bpy)3]2+ and demonstrated that [Ru(bpy)3]2+ was retained within the ultrathin films over a long time scale. These electrodes were tested for the electrocatalytic reduction of tripropylamine. Significant catalysis was observed due to the rapid turnover of [Ru(bpy)3]2+/3+ between the electrode surface and outer boundary of the film, as a direct consequence of the ultrathin film dimensions. Concomitant electrochemiluminescence (ECL) was demonstrated highlighting the potential of this material for sensing applications. 相似文献
13.
14.
Nafion 117和PE-01阳离子交换膜均可作为全钒液流氧化还原电池的隔膜用材料,PE-01在机械性能和化学稳定性方面优于Nafion 117.探讨PE-01作为钒电池隔膜材料的优势和劣势,测定PE-01膜和Nafion 117的离子交换容量、4价钒离子在其中的扩散能力以及膜面电阻.实验表明,Nafion 117具有导电性能优良、较大的离子交换容量以及较小的面电阻;PE-01具有很好的物理性能和阻钒离子渗透能力. 相似文献
15.
The purpose was to investigate the effectiveness of an ethylcellulose (EC) bead matrix and different film-coating polymers in delaying drug release from compacted multiparticulate systems. Formulations containing theophylline or cimetidine granulated with Eudragit RS 30D were developed and beads were produced by extrusion-spheronization. Drug beads were coated using 15% wt/wt Surelease or Eudragit NE 30D and were evaluated for true density, particle size, and sphericity. Lipid-based placebo beads and drug beads were blended together and compacted on an instrumented Stokes B2 rotary tablet press. Although placebo beads were significantly less spherical, their true density of 1.21 g/cm(3) and size of 855 mum were quite close to Surelease-coated drug beads. Curing improved the crushing strength and friability values for theophylline tablets containing Surelease-coated beads; 5.7 +/- 1.0 kP and 0.26 +/- 0.07%, respectively. Dissolution profiles showed that the EC matrix only provided 3 h of drug release. Although tablets containing Surelease-coated theophylline beads released drug fastest overall (t(44.2%) = 8 h), profiles showed that coating damage was still minimal. Size and density differences indicated a minimal segregation potential during tableting for blends containing Surelease-coated drug beads. Although modified release profiles >8 h were achievable in tablets for both drugs using either coating polymer, Surelease-coated theophylline beads released drug fastest overall. This is likely because of the increased solubility of theophylline and the intrinsic properties of the Surelease films. Furthermore, the lipid-based placebos served as effective cushioning agents by protecting coating integrity of drug beads under a number of different conditions while tableting. 相似文献
16.
A new film-forming solution was developed for the efficient immobilization of enzymes on solid substrates. The solution consisted of a biopolymer, chitosan (CHIT), that was chemically modified with a permeability-controlling agent, Acetyl Yellow 9 (AY9), using glutaric dialdehyde (GDI) as a molecular tether. A model enzyme, glucose oxidase (GOx), was mixed with the CHIT-GDI-AY9 solution and cast on the surface of platinum electrodes to form robust CHIT-GDI-AY9-GOx films for glucose biosensing. UV-visible and infrared spectroscopies were used to determine the composition of the films. The optimized films contained on average 1 molecule of AY9/3 glucosamine units of chitosan and 25 free GDI tethers/1 molecule of GOx. The electrochemical assays of the films indicated both a very high efficiency of enzyme immobilization (approximately 99%) and large enzyme activity (60 units cm(-2)). The latter translated into a high sensitivity (42 mA M(-1) cm(-2)) of the Pt/CHIT-GDI-AY9-GOx biosensor toward glucose. The biosensor operated at 0.450 V, had a fast response time (t90% < or = 3 s), and was free of typical interferences, and its dynamic range covered 3 orders of magnitude of glucose concentrations. The lowest actually detectable concentration was 10 microM glucose. In addition, the biosensor displayed a practical shelf life and excellent operational stability, e.g. its response was stable during 24-h testing under continuous polarization and continuous flow of 5.0 mM glucose solution. The proposed approach to enzyme immobilization is simple, efficient, and cost-effective and should be of importance in the development of biosensors based on other enzymes that are more expensive than glucose oxidase. 相似文献
17.
Humidity detection has been widely used in a variety of fields. A humidity sensor with high sensitivity is reported in this paper. A surface acoustic wave resonator (SAWR) with high resonance frequency was fabricated as a basic sensitive component. Various nanotechnologies were used to improve the sensor's performance. A multi-walled carbon nanotube/Nafion (MWCNT/Nafion) composite material was prepared as humidity-sensitive films, deposited on the surface of an SAWR by the electrospinning method. The electrospun MWCNT/Nafion nanofiber films showed a three-dimensional (3D) porous structure, which was profitable for improving the sensor's performance. The new nano-water-channel model of Nafion was also applied in the humidity sensing process. Compared to other research, the present sensor showed excellent sensitivity (above 400 kHz/% relative humidity (RH) in the range from 10% RH to 80% RH), good linearity (R(2) > 0.98) and a short response time (~3 s@63%). 相似文献
18.
There is an active demand for the commercial indium tin oxide (ITO) target with density above 99% of the theoretical density (TD). Some works found the increase of the target density could lead to a slight decrease of the resistivity of the direct current (DC) sputtered ITO films, however, the possible effect of target density on the radio frequency (RF) sputtered ITO films is not clear. In this paper, ITO targets with different densities are successfully prepared. The structural, electrical and optical properties of the thin films deposited from these targets are studied at the substrate temperature of 750 °C. It is found that the target density has no effect on the above properties and the deposition rate of the RF sputtered ITO thin films, different from the DC sputtered films. So for the RF sputtered process, the target needs not high density so that the used target can be just compacted from the powders without sintering. All the as-prepared ITO films with different densities have a resistivity of 1.56 × 10−4 Ω cm and a transmittance of ∼87%, which are lower than the ITO films prepared at temperatures lower than 400 °C. 相似文献
19.
We investigated the applicability of Raman microprobe spectroscopy for determining the density of CO2 in fluid inclusions in minerals of mantle-derived xenolith samples. A separation (delta) between two Raman bands of CO2 due to Fermi resonance can be a reliable densimeter for CO2 fluid. The relationship between the density of CO2 (g/cm3) and delta (cm-1) can be expressed as: d = -0.03238697 delta 3 + 10.08428 delta 2 - 1046.189 delta + 36163.67. This equation was obtained from the Raman data on CO2 fluid with densities from 0.1 to 1.21 g/cm3, including super critical fluids at 58-59 degrees C. The delta value was constant with increasing temperature from room temperature to 200 degrees C. This indicates that the Raman densimeter is not affected by a possible rise in temperature, an artifact induced by the high flux of the incident laser. The minimum size of measurable inclusions is 1 micron, and the precision in the determination of delta is 0.1 cm-1, corresponding to 0.02 g/cm3 for inclusions of 1 micron in size. The precision can be better for larger inclusions. The micro-Raman densimeter can determine the density of CO2 fluid inclusions over a wide range. In particular, densities of gas and mixtures of gas and liquid phases, which cannot be measured by microthermometry, can be determined. 相似文献
20.
Indium tin oxide (ITO) films are representative transparent conducting oxide media for organic light-emitting diodes, liquid crystal displays, and solar cell applications. Extending the utility of ITO films from passive electrodes to active channel layers in transparent field-effect transistors (FETs), however, has been largely limited because of the materials' high carrier density (>1 × 10(20) cm(-3)), wide band gap, and polycrystalline structure. Here, we demonstrate that control over the cation composition in ITO-based oxide films via solid doping of titanium (Ti) can optimize the carrier concentration and suppress film crystallization. On 120 nm thick SiO(2)/Mo (200 nm)/glass substrates, transparent n-type FETs prepared with 4 at % Ti-doped ITO films and fabricated via the cosputtering of ITO and TiO(2) exhibited high electron mobilities of 13.4 cm(2) V(-1) s(-1), a low subthreshold gate swing of 0.25 V decade(-1), and a high I(on/)I(off) ratio of >1 × 10(8). 相似文献