排序方式: 共有31条查询结果,搜索用时 37 毫秒
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Price SW Speed JD Kannan P Russell AE 《Journal of the American Chemical Society》2011,133(48):19448-19458
The underpotential deposition (upd) of a Cu shell on a non-Pt nanoparticle core followed by galvanic displacement of the Cu template shell to form core-shell electrocatalyst materials is one means by which the Pt-based mass activity targets required for commercialization of PEM fuel cells may be reached. In situ EXAFS measurements were conducted at both the Au L(3) and the Cu K absorption edges during deposition of Cu onto a carbon-supported Au electrocatalyst to study the initial stages of formation of such a core-shell electrocatalyst. The Au L(3) EXAFS data obtained in 0.5 mol dm(-3) H(2)SO(4) show that the shape of the Au core is potential dependent, from a flattened to a round spherical shape as the Cu upd potential is approached. Following the addition of 2 mmol dm(-3) Cu, the structure was also measured as a function of the applied potential. At +0.2 V vs Hg/Hg(2)SO(4), the Cu(2+) species was found to be a hydrated octahedron. As the potential was made more negative, single-crystal studies predict an ordered bilayer of sulfate anions and partially discharged Cu ions, followed by a complete/uniform layer of Cu atoms. In contrast, the model obtained by fitting the Au L(3) and Cu K EXAFS data corresponds first to partially discharged Cu ions deposited at the defect sites in the outer shell of the Au nanoparticles at -0.42 V, followed by the growth of clusters of Cu atoms at -0.51 V. The absence of a uniform/complete Cu shell, even at the most negative potentials investigated, has implications for the structure, and the activity and/or stability, of the core-shell catalyst that would be subsequently formed following galvanic displacement of the Cu shell. 相似文献
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The following modification of a general state space discrete-time Markov chain is considered: certain transitions are supposed “forbidden” and the chain evolves until there is such a transition. At this instant the value of the chain is “replaced” according to a given rule, and, starting from the new value, the chain evolves normally until there is a forbidden transition again; the cycle is then repeated. The relationship of this modified process to the original one is studied in general terms, with particular emphasis being given to invariant measures. Examples are given which illustrate the results obtained. 相似文献
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Jonathan Guild Michael J. Morris Craig C. Robertson Alexander W.H. Speed 《Tetrahedron letters》2019,60(39):151079
The reaction of phenyl acetylide anion with aryl isocyanates followed by quenching with water is shown to produce pyrrolopyrrole (iso-DPP) derivatives in addition to the isomeric cyclopentadienone imines previously reported. If the reaction is quenched with dilute HCl, 5-ylidenepyrrol-2(5H)-ones, formed by a Meyer-Schuster rearrangement, can be isolated instead. A possible mechanism for this reaction is suggested. 相似文献
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Speed S Vicente R Aravena D Ruiz E Roubeau O Teat SJ El Fallah MS 《Inorganic chemistry》2012,51(12):6842-6850
The syntheses, structural characterization, and magnetic behavior of two new hexanuclear copper(II) complexes derived from R-phosphonic acids and 1,3-bis(dimethylamino)-2-propanol (Hbdmap) with formulas [Cu(6)(μ-bdmap)(3)(μ(3)-Ph-PO(3))(2)(μ(3)-O···H···μ(3)-O)(ClO(4))(2)(H(2)O)]·5H(2)O (1) and [Cu(6)(μ-bdmap)(3)(μ(3)-t-Bu-PO(3))(2)(μ(3)-O···H···μ(3)-O)(μ(1,3)-dca)(dca)(H(2)O)]·6H(2)O (2) (Ph-H(2)PO(3) = phenylphosphonic acid, t-Bu-H(2)PO(3) = tert-butylphosphonic acid, dca = dicyanamide) are reported. Compounds 1 and 2 are hexanuclear 3.111 R-phosphonate(2-)/1,3-bis(dimethylamino)-2-propanolato(1-) cages including in the center the [μ(3)-O···H···μ(3)-O](3-) unit. The temperature dependence of the magnetic properties of 1 and 2 clearly indicates an overall strong antiferromagnetic coupling confirmed by DFT calculations. 相似文献
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AW Hilkert CB Douthitt HJ Schlüter WA Brand 《Rapid communications in mass spectrometry : RCM》1999,13(13):1226-1230
Of all the elements, hydrogen has the largest naturally occurring variations in the ratio of its stable isotopes (D/H). It is for this reason that there has been a strong desire to add hydrogen to the list of elements amenable to isotope ratio monitoring gas chromatography/mass spectrometry (irm-GC/MS). In irm-GC/MS the sample is entrained in helium as the carrier gas, which is also ionized and separated in the isotope ratio mass spectrometer (IRMS). Because of the low abundance of deuterium in nature, precise and accurate on-line monitoring of D/H ratios with an IRMS requires that low energy helium ions be kept out of the m/z 3 collector, which requires the use of an energy filter. A clean mass 3 (HD(+.)) signal which is independent of a large helium load in the electron impact ion source is essential in order to reach the sensitivity required for D/H analysis of capillary GC peaks. A new IRMS system, the DELTA(plus)XL(trade mark), has been designed for high precision, high accuracy measurements of transient signals of hydrogen gas. It incorporates a retardation lens integrated into the m/z 3 Faraday cup collector. Following GC separation, the hydrogen bound in organic compounds must be quantitatively converted into H(2) gas prior to analysis in the IRMS. Quantitative conversion is achieved by high temperature conversion (TC) at temperatures >1400 degrees C. Measurements of D/H ratios of individual organic compounds in complicated natural mixtures can now be made to a precision of 2 per thousand (delta notation) or, better, with typical sample amounts of approximately 200 ng per compound. Initial applications have focused on compounds of interest to petroleum research (biomarkers and natural gas components), food and flavor control (vanillin and ethanol), and metabolic studies (fatty acids and steroids). Copyright 1999 John Wiley & Sons, Ltd. 相似文献
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William Speed Jeffrey M. Long Roger J. Simmonds Trevor A. Enos 《Rapid communications in mass spectrometry : RCM》1995,9(14):1452-1456
A method is described for the determination of fenticonazole in human female plasma. The method utilizes high performance liquid chromatography coupled to atmospheric pressure positive-ion chemical ionization triple quadrupole mass spectrometry. Multiple reaction monitoring is employed for selectivity and sensitivity which enables quantification over the range 0.5–20 ng mL−1 with acceptable precision and accuracy. A comparison is made with an existing HPLC-UV assay and the utility of the technology of combined liquid chromatography and tandem mass spectrometry for subnanogram per mL assays is discussed. 相似文献