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101.
Shape-controlled synthesis of metal nanostructures: the case of silver 总被引:19,自引:0,他引:19
The concept of shape-controlled synthesis is discussed by investigating the growth mechanisms for silver nanocubes, nanowires, and nanospheres produced through a polymer-mediated polyol process. Experimental parameters, such as the concentration of AgNO(3) (the precursor to silver), the molar ratio between poly(vinylpyrrolidone) (PVP, the capping agent) and AgNO(3), and the strength of chemical interaction between PVP and various crystallographic planes of silver, were found to determine the crystallinity of seeds (e.g., single crystal versus decahedral multiply twinned particles). In turn, the crystallinity of a seed and the extent of the PVP coverage on the seed were both instrumental in controlling the morphology of final product. The ability to generate silver nanostructures with well-defined morphologies provides a great opportunity to experimentally and systematically study the relationship between their properties and geometric shapes. 相似文献
102.
用超高真空程序升温反应谱和瞬时应答方法研究了乙二醇在电解银表面的氧化,实验表明,室温下乙二醇吸附在电解银表面,并在343K分解给出一组产物群,预吸附氧与乙二醇反应时,在343K,433K和612K处给出三组产物群,它们分别对应于不同的表面反应,并给出了电解银催化乙二醇制乙二醛的活性结果。 相似文献
103.
《Electroanalysis》2006,18(3):259-266
In this paper, a new strategy for constructing a mediator‐type amperometric hydrogen peroxide (H2O2) microbiosensor was described. An electropolymerized thionine film (PTH) was deposited directly onto a gold electrode surface. The resulting redox film was extremely thin, adhered well onto a substrate (electrode), and had a highly cross‐linked network structure. Consequently, horseradish peroxidase (HRP) was successfully immobilized on nanometer‐sized Au colloids, which were supported by thiol‐tailed groups of 11‐mercaptoundecanoic acid (11‐MUA) monolayer covalently bound onto PTH film. With the aid of the PTH mediator, HRP‐labeled Au colloids microbiosensor displayed excellent electrocatalytical response to the reduction of H2O2. This matrix showed a biocompatible microenvironment for retaining the native activity of the covalent HRP and a very low mass transport barrier to the substrate, which provided a fast amperometric response to H2O2. The proposed H2O2 microbiosensor exhibited linear range of 3.5 μM–0.7 mM with a detection limit of 0.05 μM (S/N=3). The response showed a Michaelis‐Menten behavior at larger H2O2 concentrations. The KMapp value for the biosensors based on 24 nm Au colloids was found to be 47 μM, which demonstrated that HRP immobilized on Au colloids exhibited a high affinity to H2O2 with no loss of enzymatic activity. This microbiosensor possessed good analytical performance and storage stability. 相似文献
104.
Jason R McCarthyPatricia J Melfi Steven H CapettaChristian Brückner 《Tetrahedron》2003,59(46):9137-9146
The use of AgII as a removable template in synthetic porphyrin chemistry is described. Mild procedures for the insertion of AgII into chlorins and the demetallation of the [chlorinato]AgII complexes are delineated. The UV-vis spectra of the novel [chlorinato]AgII complexes are discussed. The diol cleavage products of [meso-tetraphenyl-2,3-diolchlorinato]silver(II) under a number of conditions are characterized and compared to those resulting from the cleavage of the corresponding free base diol chlorin or its NiII complex, highlighting the unique templating effect of AgII. The scopes and limits of electrospray ionization mass spectrometry (ESI-MS) for the analysis of AgII chlorins is described. The use of AgII as a templating metal is superior over NiII or ZnII for the preparation of free base pyrrole-modified porphyrins along metal templated pathways. 相似文献
105.
Rui M. Almeida Ana C. Marques Maurizio Ferrari 《Journal of Sol-Gel Science and Technology》2003,26(1-3):891-896
The present paper is focused on multilayer Er3+-doped silica-titania planar waveguides, co-doped with silver, which were prepared by spin-coating on silica glass, or buffered single crystal silicon substrates. The single layer thickness (0.4 m) and refractive index (1.60–1.63) were measured by spectroscopic ellipsometry at 715 nm. The thickness of the waveguides (measured by mechanical profilometry) was 1 m and their optical propagation losses were measured at different laser wavelengths (488 nm, 514 nm and 633 nm), exhibiting an approximately Rayleigh-like behavior. The thermal precipitation of silver nanocrystallites was achieved, both in air and under a controlled atmosphere (dry nitrogen) and these were characterized by visible absorption spectroscopy, which clearly showed the development of a plasmon absorption band near 415 nm, by X-ray diffraction (XRD) and Transmission Electron Microscopy (TEM). The Er3+ metastable level lifetimes for the emission at ca. 1.54 m were found to be ca. 4–6 ms, for Er3+ concentrations varying between 0.2–2.0 mol% (or (0.4–4.4) × 1020 ions/cm3), but no significant variation was observed with the Ag concentration added (up to 2.5 mol%). 相似文献
106.
Maksymilian Ignaczak Andrzej Grzejdziak Barbara Olejniczak 《Monatshefte für Chemie / Chemical Monthly》1989,120(6-7):515-527
Summary The conditional protonation constants (=0.1) for 2,2:6,2-terpyridine, logK
1=4.93, logK
2=3.69, were determined by thepH-metric method. The compositions of complexes of Ag2+ and Ag+ ions with 2,2:6,2-terpyridine (tp) were studied and equilibria of the complex formation process were described. The values of conditional complex formation constants are as follows: for Ag(tp)
2
+
:log01=5.79, log02=9.68, for Ag(tp)
2
2+
:log02=25.31, while the conditional constant of the Ag(tp)NO3 precipitate formation is:K
SO=2.45·104. Using coulometric and chronovoltamperometric measurements, the redox systems being formed in the complex solutions of Ag(II) and Ag(I) were determined and described including their formal potentials.
Komplexibildungsgleichgewichte und Redoxpotentiale des Systems Ag(II)/Ag(I) in Gegenwart von 2,2:6,2-Terpyridin in Wasser
Zusammenfassung Mit Hilfe derpH-metrischen Methode wurden die konditionalen Protonationskonstanten (=0.1) von 2,2:6,2-Terpyridin bestimmt: logK 1=4.93, logK 2=3.69. Es wurde auch die Zusammensetzung der Komplexe von Ag(II) und Ag(I) mit 2,2:6,2-Terpyridin(tp) bestimmt sowie die Gleichgewichte der komplexbildung beschrieben. Die Werte der Konditionalkomplexbildungskonstanten sind: für Ag(tp) 2 + :log01=5.79, log02=9.68, für Ag(tp) 2 2+ :log02=25.31 und für das Löslichkeitsprodukt Ag(tp)NO3:K SO –1 =4.08·10–5. Die in Komplexlösungen von Ag(II) und Ag(I) vorliegenden Redoxsysteme wurden mittels cyclischer Voltametrie und Coulometrie untersucht und die Formalpotentialwerte dieser Systeme in Wasser bestimmt.相似文献
107.
108.
Organometallic rhodium complexes are described which are highly efficient initiators for the ring-opening polymerization of expoxides and other heterocyclic compounds. A cocatalyst, consisting of a compound or polymer containing silicon–hydrogen bonds must also be present. These same catalyst–cocatalyst mixtures are also highly active for hydrosilylation reactions. Other complexes bearing phosphine ligands have been discovered, which while active for hydrosilylation, are not catalysts for epoxide polymerizations. Polymer supported rhodium catalysts are also described which permit the synthesis of epoxy-functional silanes in high yields without competing ring-opening polymerization. 相似文献
109.
《Surface and interface analysis : SIA》2003,35(2):174-178
Effective energy‐loss functions for Al, Cu, Ag and Au were derived from the reflection electron energy‐loss spectroscopy (REELS) spectra for 1 keV electrons using extended Landau theory. Features of the obtained effective energy‐loss functions are close to those of optical surface energy‐loss functions, revealing the significant contribution of the low energy loss below a few tens of electron‐volts in the REELS spectrum for Cu, Ag and Au. The REELS spectra were reproduced using the newly derived effective energy‐loss functions, leading to the confirmation that this type of database of the effective energy‐loss function is very useful not only for more comprehensive understanding of the measured spectrum of surface electron spectroscopies but also for practical background subtraction in surface electron spectroscopy. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
110.
F. H. B. Lima M. L. Calegaro E. A. Ticianelli 《Russian Journal of Electrochemistry》2006,42(12):1283-1290
This work reviews the studies conducted in this laboratory of the oxygen reduction reaction (ORR) on electrocatalysts formed
by Pt-M/C (M = V, Cr, Co) and Ag-Pt/C alloys and on different Mn oxides (MnO/C, Mn3O4/C, MnO2/C) in KOH electrolyte. The physical and electronic properties of the materials are investigated by in situ XAS (x-ray absorption
spectroscopy) in the XANES (x-ray absorption near edge structure) region. The electrocatalytic activity for the ORR on the
different catalysts is compared through mass-transport-corrected Tafel plots. The XANES results for the Pt-M/C and Ag-Pt/C
composites at high electrode potentials show lower vacancy of the Pt 5d band compared to pure Pt/C, while for the results indicate a chance of the Mn oxidation state as a function of the electrode
potential. The electrochemical measurements evidence increased electrocatalytic activity of the Pt alloys compared to pure
Pt and this is attributed to a lowering of the adsorption strength of adsorbed oxygen species caused by the reduced Pt reactivity.
An activity enhancement of the Ag atoms on the Ag-Pt/C alloys compared to pure Ag is ascribed to an electronic effect induced
by the presence of Pt, increasing the Ag-O adsorption strength. In the case of the MnyOx/C materials, the electrochemical results show low activity for MnO/C and higher activity for MnO2/C and Mn3O4/C. This is explained based on the activation for the ORR, which is higher for the material with higher MnO2 contents and the occurrence of a mediation processes involving the reduction of Mn(IV) to Mn(III), followed by the electron
transfer of Mn(III) to oxygen.
Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 12, pp. 1417–1426.
Based on the report delivered at the 8th International Frumkin Symposium “Kinetics of the Electrode Processes,” October 18–22,
2005, Moscow.
The text was submitted by the authors in English. 相似文献