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71.
A comparative investigation of electrocatalytic and adsorption properties of platinum microparticles electrodeposited onto a glassy carbon surface (Pt/GC) and within a thin Nafion® film formed on a GC electrode (Pt/Nf/GC) is described. As test reaction the methanol oxidation in sulfuric acid solutions is used. Dependences of the steady-state specific reaction rates upon potential and methanol concentration were established, as well as those of the platinum surface coverage with methanol chemisorption products upon concentration. It was shown that at higher platinum loadings (above 60 μg cm−2) the specific activities of Pt/GC and Pt/Nf/GC are nearly the same and close to that of smooth platinum. At such loadings the surface coverage of the platinum deposit surface with organic particles does not differ from that of smooth platinum. At very low platinum loadings in the polymeric matrix (10–30 μg cm−2) a considerable decrease in the adsorption of strongly chemisorbed methanol particles is observed. These deposits are characterized by a low specific activity, which may be caused by the decrease of the platinum particle’s size, leading to a decrease in the amount of weakly bound methanol particles participating in the limiting reaction step. 相似文献
72.
Metal segregation in bimetallic clusters and its possible role in synergism and bifunctional catalysis 总被引:1,自引:0,他引:1
Aspects of the reactivity of segregated bimetallic compounds and their unusual catalytic properties are reviewed with an emphasis on the author's own studies of platinum—ruthenium mixed-metal cluster complexes and their ability to produce hydrogenation and hydrosilylation of alkynes, catalytically. 相似文献
73.
74.
Takako Toda Hiroshi Igarashi Masahiro Watanabe 《Journal of Electroanalytical Chemistry》1999,460(1-2)
The design of high performance cathode electrocatalysts is essential for polymer–electrolyte fuel cells, which are now attracting enormous interest as a primary power source for zero-emission electric vehicles. We have discovered a significant enhancement of electrocatalytic activity of Pt by alloying with Fe, and found a maximum activity at ca. 50% Fe content, which results in 25 times higher activity than pure Pt activity. It was confirmed experimentally at Pt–Fe bulk alloys that the alloy catalyst surface consists of a pure Pt skin-layer (<1 nm in thickness) that is modified in the electronic structure by that of the bulk alloy. The enhancement could be well explained by the 5d-vacancy of the surface, but not by Pt interatomic distance or roughening of the surfaces. 相似文献
75.
The preparation of various (hex-5-ynyl)silanes was achieved following two different synthetic approaches from readily available materials such as 4-bromobutene, 6-iodohexyne and chlorosilanes. Different reaction conditions for intramolecular hydrosilylation were tested to prepare the corresponding 2-methylidene-1-silacyclohexanes. Notably, the use of Speier’s catalyst allowed the regioselective formation of the desired products in moderate yields. 相似文献
76.
M. Manolova V. Ivanova D.M. Kolb H.-G. Boyen P. Ziemann M. Büttner A. Romanyuk P. Oelhafen 《Surface science》2005,590(2-3):146-153
In this study we describe details of a new technique that allows to deposit metal on top of a self-assembled monolayer (SAM). Monoatomic high platinum islands were formed on a 4-mercaptopyridine SAM on Au(1 1 1) by first immersing the SAM-covered gold electrode in an aqueous solution of K2PtCl4 without potential control to allow Pt(II) ions to form a complex with the pyridine nitrogen. The complexed Pt(II) ions were then reduced electrochemically to Pt(0) after transferring the electrode to a Pt(II) ion-free solution. Upon reduction, monoatomic high Pt islands were observed in STM, the total coverage depending on the time for complexation. Ex situ angle-resolved XPS studies reveal that the Pt islands indeed reside on top of the SAM. 相似文献
77.
Density Functional Theory has been used to determine the energetically preferred structures of submonolayer, monolayer, and multilayer Pt films on both ideal terminations of SrTiO3(1 0 0), SrTiO3(1 1 1), and SrTiO3(1 1 0). The strength of the resulting metal/metal oxide interfaces was characterized by the adsorption energy of the film and the film’s work of separation. The two polar surfaces, SrTiO3(1 1 1) and SrTiO3(1 1 0), form significantly stronger interfaces than the non-polar SrTiO3(1 0 0) surface. Approximate criteria were applied to predict the growth mode of Pt on each surface. 相似文献
78.
The time dependence of the concentration of CO2 in an electrochemical thin layer cavity is studied with Fourier transform infrared spectroscopy (FTIR) in order to evaluate
the extent to which the thin layer cavity is diffusionally decoupled from the surrounding bulk electrolyte. For the model
system of CO on Pt(111) in 0.1 M HClO4, it is found that the concentration of CO2, formed by electro-oxidation of CO, equilibrates rapidly with the surrounding bulk electrolyte. This rapid equilibration
indicates that there is diffusion out of the thin layer, even on the short time scales of typical infrared experiments (1–3 min).
However, since the measured CO2 absorbance intensity as a function of time is reproducible to within 10%, a new time-dependent method for surface coverage
calibration using solution-phase species is proposed.
Dedicated to Prof. Dr. Teresa Iwasita on the occasion of her 65th birthday in recognition of her numerous contributions to
interfacial electrochemistry. 相似文献
79.
The high economic value of catalysts containing the platinum group elements platinum, rhodium and palladium as active components causes the need to be able to measure the precious metal loading with small uncertainty and to have suitable certified reference materials fulfilling high demands on the quality of the certified values. In European Reference Material ERM®-EB504, a used cordierite-based car catalyst material, mass fractions of platinum, palladium and rhodium were certified. The raw material was milled, homogenised and annealed before analysis. Seventeen laboratories experienced in precious metals analysis participated in the certification interlaboratory comparison, most of them analysing with inductively coupled plasma optical emission spectrometry using different sample pretreatment techniques. Homogeneity testing was carried out using X-ray fluorescence spectrometry. The certified mass fractions of Pt, Pd and Rh and their expanded uncertainties (k = 2) in ERM®-EB504 are (1777 ± 15), (279 ± 6) and (338 ± 4) mg/kg respectively. 相似文献
80.
Burkhard Butschke Maria Schlangen Detlef Schröder Helmut Schwarz 《Helvetica chimica acta》2008,91(10):1902-1915
Mechanistic details for the formation of methane from the title compound as well as the combined elimination of (CH3)2S/CH4 are derived from various mass‐spectrometric experiments including deuterium‐labeling studies and DFT calculations. For the first process, i.e., methane formation, we have identified three competing pathways in which the intact, Pt‐bonded methyl group combines with a H‐atom that originates from a phenyl substituent (ca. 7%), the dimethyl sulfide ligand (ca. 41%), and a methyl group of the diazabutadiene backbone (ca. 52%). In contrast, in the combined (CH3)2S/CH4 elimination, the methane is specifically formed from the Pt‐bound CH3 group and a H‐atom provided by one of the phenyl groups (‘cyclometalation’). 相似文献