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1.
Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η5-C5H5)Fe2+(η5-C5H4)-CH2-CH2-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe3+ at the expenses of Fe2+ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO− groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe3+ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing. 相似文献
2.
3.
Jin-Mok Hur Chung-Seok Seo Sun-Seok Hong Dae-Seung Kang Seong-Won Park 《Reaction Kinetics and Catalysis Letters》2003,80(2):217-222
The concept of a novel electrochemical reduction process for the treatment of spent nuclear fuels in Li2O-LiCl molten salt was proposed and fresh tests using U3O8 powder were carried out to elucidate the reaction mechanism and verify the feasibility of the process. Electrolysis of Li2O and reduction of U3O8 powder took place simultaneously at the cathode part of the electrolysis cell via a catalytic EC mechanism and the conversion of U3O8 to U metal was more than 99%.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
4.
Applied Biochemistry and Biotechnology - 相似文献
5.
In the present investigation, holographic interferometry was utilized for the first time to determine the rate change of the number of the fringe evolutions during the corrosion test of a carbon steel in blank seawater and seawater with different concentrations of a corrosion inhibitor. In other words, the anodic dissolution behaviors (corrosion) of the carbon steel were determined simultaneously by holographic interferometry, as an electromagnetic method, and by the electrochemical impedance (EI) spectroscopy, as an electronic method. So, the abrupt rate change of the number of the fringe evolutions during corrosion tests, EI spectroscopy, of the carbon steel is called electrochemical emission spectroscopy. The corrosion process of the steel samples was carried out in blank seawater and seawater with different concentrations, 5–20 ppm, of TROS C-70 corrosion inhibitor using the EI spectroscopy method, at room temperature. The electrochemical-emission spectra of the carbon steel in different solutions represent a detailed picture of the rate change of the anodic dissolution of the steel throughout the corrosion processes. Furthermore, the optical interferometry data of the carbon steel were compared to the data, which was obtained from the EI. spectroscopy. Consequently, holographic interferometry is found very useful for monitoring the anodic dissolution behaviors of metals, in which the number of the fringe evolutions of the steel samples can be determined in situ. 相似文献
6.
Materials from the Mn(0.5−x)CaxTi2(PO4)3 (0≤x≤0.50) solid solution were obtained by solid-state reaction in air at 1000 °C. Selected compositions were investigated by powder X-ray diffraction analysis, 31P nuclear magnetic resonance (NMR) spectroscopy and electrochemical lithium intercalation. The structure of all samples determined by Rietveld analysis is of the Nasicon type with the R
space group. Mn2+/Ca2+ ions occupy only the M1 sites in the Ti2(PO4)3 framework. The divalent cations are ordered in one of two M1 sites, except for the Mn0.50Ti2(PO4)3 phase, where a small departure from the ideal order is observed by XRD and 31P MAS NMR. The electrochemical behaviour of Mn0.50Ti2(PO4)3 and Mn(0.5−x)CaxTi2(PO4)3 phases was characterised in Li cells. Two Li ions can be inserted without altering the Ti2(PO4)3 framework. In the 0≤y≤2 range, the OCV curves of Li//LiyMn0.50Ti2(PO4)3 cells show two main potential plateaus at 2.90 and 2.50–2.30 V. Comparison between the OCV curves of Li//Li(1+y)Ti2(PO4)3 and Li//LiyMn0.50Ti2(PO4)3 shows that the intercalation occurs first in the unoccupied M1 site of Mn0.50Ti2(PO4)3 at 2.90 V and then, for compositions y>0.50, at the M2 site (2.50–2.30 V voltage range). The effect of calcium substitution in Mn0.50Ti2(PO4)3 on the lithium intercalation is also discussed from a structural and kinetic viewpoint. In all systems, the lithium intercalation is associated with a redistribution of the divalent cation over all M1 sites. In the case of Mn0.50Ti2(PO4)3, the stability of Mn2+ either in an octahedral or tetrahedral environment facilitates cationic migration. 相似文献
7.
控温相变免疫分析测定雌酮 总被引:4,自引:0,他引:4
通过热引发聚合与氧化还原引发聚合,合成水凝胶,作为雌酮全抗原(E1— BSA)载体;以异硫氰基灾光素标记雌酮的单克隆抗体(McAb)作为示踪剂,建立了控温相变竞争免疫分析测定雌酮(EI)的方法并应用于分析血清样品。实验表明:以热引发聚合合成的水凝胶为载体的荧光免疫分析方法具有更高的灵敏度,它的线性范围为10-700μg/L,检出限为1μg/L(n=10,3倍空白)。经水凝胶性质的比较(包括LCST、非特异性吸附、抗原与抗体反应时间及固定化抗原活性),证明了热引发聚合的水凝胶较氧化还原引发聚合的水凝胶更适合于作为免疫分析的载体。 相似文献
8.
Kai Kamada Shintaro Udo Shuichi Yamashita Yuko Tsutsumi Yasumichi Matsumoto 《Solid State Ionics》2003,160(3-4):389-394
Quantitative analysis of metal cation doping by solid oxide electrochemical doping (SOED) has been performed under galvanostatic doping conditions. A M–β″-Al2O3 (M=Ag, Na) microelectrode (contact radius: about 10 μm) was used as cation source to attain a homogeneous solid–solid contact between the β″-Al2O3 and doping target. In Ag doping into alkali borate glass, the measured dopant amount closely matched the theoretical value. High Faraday efficiencies of above 90% were obtained. This suggests that the dopant amount can be precisely controlled on a micromole scale by the electric charge during electrolysis. On the other hand, current efficiencies of Na doping into Bi2Sr2CaCu2Oy (BSCCO) ceramics depended on the applied constant current. Efficiencies of above 80% were achieved at a constant current of 10 μA (1.6 A cm−2). The relatively low efficiencies were explained by the saturation of BSCCO grain boundaries with Na. By contrast, excess Na was detected on the anodic surface of ceramics at a constant current of 100 μA (16 A cm−2). In the present study, we demonstrate that SOED enables micromole-scale control over dopant amount. 相似文献
9.
Yaping Guo 《European Polymer Journal》2007,43(6):2292-2297
Polyaniline (PANI) nanofibers with interconnected network-like structures were electropolymerized on stainless steel substrates by galvanostatic electrolysis. The samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV-visible spectroscopy (UV-vis) and Fourier transform infrared spectroscopy (FTIR). The results show that PANI and gels (mixtures of oligomer, dopant and aniline) form simultaneously during the electrochemical deposition. The gels play an important role in the formation of PANI nanofibers. The PANI formed in the early stage of polymerization is subject to secondary growth along one dimension, since the nucleation sites are suppressed by the wrapped gels. The dendritic degree of PANI nanofibers is related to dopants, and the order is as follows: PANI-H3PO4 > PANI-H2SO4 > PANI-HNO3. No nanofibers are obtained using CH3COOH as dopants due to the high solubility of PANI-CH3COOH. 相似文献
10.
Doubly tunable sum frequency generation (SFG) spectra demonstrate that the water molecules at gold/electrolyte interface change their orientation with applied potential. At negative potentials, water molecules in the double layer align with their oxygen atom pointing to the solution. As potential became positive to be close to the potential of zero charge (PZC), the SFG signal decreased, suggesting the OH groups of the water molecule are either in random orientation or parallel to the electrode. As potential became more positive than the PZC, the SFG signal increased again with the oxygen-up orientation as same as in the negative potential region, indicating that water molecules interact with the adsorbed sulfate anions. The peak position of the SFG spectra indicates a relatively disordered state of water molecules at the gold electrode surface, in contrast to the previously observed ice-like structure of water at electrolyte/oxide interfaces. 相似文献