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31.
以电化学和现场紫外-可见-近红外及现场FTIR光谱电化学方法对Dawson结构杂多阴离子[HAS2Mo18O62]5-在非质子介质(CH3CN)中的电还原过程进行了研究.结果表明,该杂多阴离子在非质子介质中经历4步单电子还原反应,所产生的杂多蓝阴离子在近红外区出现宽广的价间电荷转移吸收带,而红外区Mo=O端键及Mo—O—Mo桥键的特征吸收峰在还原后均有不同程度的红移. 相似文献
32.
Shaofeng Zhang Yong-Seung Shin Richard Mayer Franco Basile 《Journal of Analytical and Applied Pyrolysis》2007,80(2):353-359
An on-probe pyrolyzer has been constructed and interfaced with desorption electrospray ionization (DESI) mass spectrometry (MS) for the rapid analysis of non-volatile pyrolysis products. The detection and analysis of non-volatile pyrolysis products of peptides, proteins and the synthetic polymer poly(ethylene glycol) were demonstrated with this instrument. The on-probe pyrolyzer can be operated off-line or on-line with the DESI source and was interfaced with a tandem MS (MS/MS) instrument, which allowed for structure characterization of the non-volatile pyrolytic products. Advantages of this system are its simplicity and speed of analysis since the pyrolysis is performed in situ on the DESI source probe and hence, it avoids extraction steps and/or the use of matrices (e.g., as in MALDI–MS analyses). 相似文献
33.
S. Cattarin M.M. Musiani U. Casellato P. Guerriero R. Bertoncello 《Journal of Electroanalytical Chemistry》1995,380(1-2)
In+As+Sb alloys have been deposited onto Ni and Ti cathodes from tartaric acid solutions at pH 2. Homogeneous deposits of composition suitable for achieving InAsxSb1−x can be obtained from this medium. The As-to-Sb ratio can be controlled by properly selecting solution composition and deposition potential.X-ray photoelectron spectroscopy and X-ray diffraction analyses show that formation of III–V compounds occurs at room temperature. In reacts preferentially with As rather than with Sb, but crystalline phases formed at room temperature are Sb-rich. After annealing the In+As+Sb alloys at 250°C, the composition calculated from cell parameters appears similar to that measured by energy-dispersive X-ray analysis, suggesting that the entire deposit has been converted into the InAsxSb1−x crystalline phase. 相似文献
34.
Zhonghua Ji Jingjian Li Gu Yuan Shengmin Cai Jia Liu Chang Liu 《Journal of Electroanalytical Chemistry》2004,570(2):265-273
Polyamides containing N-methyl pyrroles and N-methyl imidazoles are a type of small molecule that can bind and recognize the bases of DNA with high affinity and specificity. Five polyamides were studied at glassy carbon electrode in acetate buffer by cyclic and differential pulse voltammetry to clarify their redox pathways. The polyamide electrochemical responses are compared by peak currents and peak potentials. The slopes of the three anodic Ep vs. pH plots of a typical polyamide are linear and show 0.059, 0.057, 0.056 V per pH in acid media, respectively, which correspond to a mechanism involving the equal number of electrons and protons. A possible mechanism for the redox pathway of various polyamides is proposed: the oxidation product of imidazole ring is acylamide and the results of in situ UV–Vis spectroscopy at Pt web electrode support the proposed mechanism. electrospray ionization mass spectroscopy (ESI-MS) indicates that one or two oxygen atoms are added into polyamide molecule after electrochemical oxidation. 相似文献
35.
A. Krause M. Uhlemann A. Gebert L. Schultz 《Journal of Solid State Electrochemistry》2007,11(6):679-685
The present work demonstrates the possibilities and the limits of the in situ electrochemical scanning tunneling microscopy
for investigation of nucleation processes in magnetic fields on the examples of Cu and Co electrodeposition onto Au(111) electrodes
from sulfate electrolytes with pH 3. Cyclic voltammograms of Cu in the underpotential range (UPD) exhibit no significant change
in the cathodic and anodic peaks recorded in magnetic fields parallel to the surface. In magnetic fields of a permanent magnet,
the reconstruction of Au has been annihilated during UPD of Cu. In the overpotential range, the dissolution of Cu is inhibited.
This triggers the formation of a Cu–Au surface alloy. The UPD deposition of Co onto Au(111) could be proven without magnetic
field, which leads to the formation of two monolayers. The nucleation in an applied field could not be observed due to higher
induced fluctuations and microconvective effects.
Contribution to special issue “Magnetic field effects in Electrochemistry”. 相似文献
36.
WANG Xiu-li BI Yan-feng LIN Hong-yan LIU Guo-cheng 《高等学校化学研究》2007,23(3):50-253
Hydrothermal treatment of MCl2(M=Co or Cu), NH4VO3, and 1,10-phenanthroline-5,6-dione(pdon) resulted in the formation of a duplex coordination polymer [Co(bpdc)(H2O)3]·H2O(bpdc=2,2′-bipyridine-3,3′-dicarboxylate) and a chain-like coordination polymer [Cu(bpy)V2O6](bpy=2,2′-bipyridine). X-ray single-crystal structural analysis shows that under hydrothermal conditions and in the presence of different transition metals, the organic reagent pdon was transformed in situ into bpdc and bpy, respectively. Mechanism of the in situ ligand synthesis reaction has been discussed. 相似文献
37.
The cerium‐containing MCM‐41 (Ce‐MCM‐41) has been synthesized by direct hydrothermal method. The low‐angle XRD patterns revealed the typical five major peaks of MCM‐41 type hexagonal structures. The interplanar spacing d100 = 38.4 Å was obtained that can be indexed on a hexagonal unit cell parameter with ao = 44.3 Å which was larger than that of pure siliceous MCM‐41 (Si‐MCM‐41). Transmission electron micrograph shows the regular hexagonal array of uniform channel characteristics of MCM‐41. The BET surface area of Ce‐MCM‐41 was 840 m2/g, which is much reduced as compared to that of Si‐MCM‐41, with the pore size of 26.9 Å and mesopore volume of 0.78 cm3/g were measured by nitrogen adsorption‐desorption isotherm at 77 K. Along with the results, the synthesized Ce‐MCM‐41 exhibited a well‐ordered MCM‐41‐type mesoporous structure with the incorporation of cerium. Using Ce‐MCM‐41 as a support, the Rh (0.5 wt%) catalyst exhibited very high activity for the NO/CO reactions. 相似文献
38.
原位合成分子筛膜毛细管色谱柱的研制 总被引:1,自引:0,他引:1
吸附型多孔层毛细管柱既耐高温又对气体及烃类异构体有选择性,同时又具有毛细管色谱快速、高效等优点,是解决难分离组分的重要柱型.常用作气一固吸附色谱固定相的有强极性的硅、中极性的氧化铝、非极性的碳质及特殊吸附作用的分子筛.其中分子筛以其独特的吸附作用,在永久性气体和烃类碳数族组成分析中有重要地位.Pruecell和Soulages[1,2]等制备了涂渍型5A和13X型分子筛的毛细管柱,对低碳烃类化合物显示了良好的分离能力,分析柱温较填充柱降低约100℃.邹乃忠等[3~5]也先后制备了分子筛层的毛细管柱用来作直馏汽油的分析.由于通… 相似文献
39.
We have evaluated the potential of near-infrared spectroscopy (NIRS) as a technique for rapid analysis of lactate in whole blood. To test the NIRS technique, a comparison was made with a standard clinical method using whole blood samples taken from five exercising human subjects at three different stage of exercise. To expand lactate concentration within the physiological range, standard additions method was used to generate 45 unique data points. Spectra were collected over the 2050-2400 nm spectral range with a 1 mm optical path length quartz cell. Reference lactate concentrations in the samples were determined by enzymatic measurements. Estimates and calibration of the lactate concentration with NIRS was made using partial least squares (PLS) regression analysis and leave-N-out cross validation on second derivative spectra. Separate calibrations were determined from each of the subject samples and cumulative PRESS was used to determine the number of PLS factors in the final model. The results from the PLS model presented are generated from the five individual calibration coefficient vectors and provided a correlation coefficient of 0.978 and a standard error of cross validation of 0.65 mmol l−1 between the enzymatic assay and the NIRS technique. To study the parameters that impact the spectra baseline and the correlation between the calculated model and the data, referenced measurements of lactate against baseline spectrum were made for each individual. A correlation coefficient of 0.992 and a standard error of cross validation of 0.21 mmol l−1 were found. The results suggest that NIRS may provide a valuable tool to assess physiological status for both research and clinical needs. 相似文献
40.
制备了对丙烯直接气相环氧化具有较好催化性能的Ag-MoO3催化剂, 采用原位FT-IR技术研究了丙烯、环氧丙烷及丙烯+氧气的混合气在Ag和Ag-MoO3催化剂表面上的吸附及反应行为. 研究表明, 丙烯在Ag和Ag-MoO3催化剂表面上吸附后, 均不发生化学反应, 而环氧丙烷吸附后在较高温度下则发生开环和聚合反应直至产生积炭. 与Ag催化剂相比, 在Ag-MoO3催化剂上, MoO3的加入在降低催化剂活性的同时, 在一定程度上抑制了产物环氧丙烷的开环及深度反应, 使环氧丙烷的选择性提高. 另外, 在较低的反应温度和较短的滞留时间下, 环氧丙烷发生深度反应的程度明显降低. 相似文献