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71.
72.
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
73.
A method for calculating the various components of the magnetically induced current-density tensor using gauge-including atomic orbitals is described. The method is formulated in the framework of analytical derivative theory, thus enabling implementation at the Hartree-Fock self-consistent-field (HF-SCF) as well as at electron-correlated levels. First-order induced current densities have been computed up to the coupled-cluster singles and doubles level (CCSD) augmented by a perturbative treatment of triple excitations [CCSD(T)] for carbon dioxide and benzene and up to the full coupled-cluster singles, doubles, and triples (CCSDT) level in the case of ozone. The applicability of the gauge including magnetically induced current method to larger molecules is demonstrated by computing first-order current densities for porphin and hexabenzocoronene at the HF-SCF and density-functional theory level. Furthermore, a scheme for obtaining quantitative values for the induced currents in a molecule via numerical integration over the current flow is presented. For benzene, a perpendicular magnetic field induces a (field dependent) ring current of 12.8 nA T(-1) at the HF-SCF level using a triple-zeta basis set augmented with polarization functions (TZP). At the CCSD(T)/TZP level the induced current was found to be 11.4 nA T(-1). Gauge invariance and its relation to charge-current conservation is discussed. 相似文献
74.
Flow injection system with gas diffusion for the sequential determination of total nitrogen and phosphorus in vegetables 总被引:1,自引:0,他引:1
Jose´ L. F. C. Lima Antoacutenio O. S. S. Rangel M. Renata S. Souto 《Analytical and bioanalytical chemistry》1997,358(5):657-662
A flow injection system was developed for the sequential determination of total nitrogen and phosphorus in digests of vegetables
using potentiometric and spectrophotometric detection systems, respectively. A tubular ammonium selective electrode with a
sensor system composed of nonactin/monactin in tris(2-ethylhexyl) phosphate was used. The selectivity limitations of this
electrode were overcome by the inclusion of a gas-diffusion unit in the system that separated ammonium from the rest of the
sample matrix and allowed the determination of total nitrogen and phosphorus by the partition of the sample plug between two
streams.
The results obtained with the developed FIA system were in good agreement with those of the reference methods. Sampling rates
from 40 to 60 samples per hour and relative standard deviations below 3.5% were achieved.
Received: 17 October 1996/Revised: 21 November 1996/Accepted: 27 November 1996 相似文献
75.
The use of a laboratory-made iodide ion-selective electrode with tubular configuration and based on a crystalline membrane (AgI/Ag2S) as the detector for ion chromatographic determination of iodide in urine and serum is described. A CIS reversed-phase column was coated withN-cetylpyridinium chloride to prepare a low-exchange-capacity analytical column and with hexadecyltrimethylammonium bromide to prepare a concentrator pre-column. A 2.0 ml min–1 flow rate of deionized water and 0.1 mol 1–1 KNO3 solution was used for the pre-concentration and for the chromatographic separation, respectively. For optimum performance of the detector a background level of iodide was added into the column effluent. A linear relationship (r = 0.9997) between tubular electrode potential (as peak height) and iodide concentration in the range 5–400 g 1–1 and a detection limit of 1.47 g 1–1 were obtained. The method shows good reproducibility for both peak height (2.2% RSD) and retention time (1.3% RSD). Recoveries on its application to the samples were 93.0–100.9% for urine and 91.4–106.0% for serum. 相似文献
76.
Lamellar crystalline calcium phenylphosphonate, as anhydrous Ca(HO3PC6H5)2 and hydrated Ca(HO3PC6H5)2·2H2O compounds, were used as hosts for intercalation of polar n-alkylmonoamine molecules of the general formula CH3(CH2)nNH2 (n=0–4, 7) in water or 1,2-dichloroethane. An increase in the interlayer distance was observed. The exothermic enthalpic values for intercalation increased with the number of carbon atoms and with increasing concentration of the amines. The intercalation followed by a titration procedure in the solid/liquid interface with Ca(HO3PC6H5)2·2H2O and Ca(HO3PC6H5)2 gave the enthalpy/number of carbons correlations: ΔintH=−(1.74±0.43)–(1.30±0.13)nc and ΔintH=−(4.15±0.15)–(1.07±0.03)nc, for water and 1,2-dichloroethane, respectively. A similar correlation ΔintH=−(4.27±0.80)–(1.85±0.21)nc was obtained in water by using the ampoule breaking procedure for Ca(HO3PC6H5)2·2H2O. The increase in exothermic enthalpic values with the increase in n-aliphatic carbon atoms is more pronounced for the anhydrous compound and also when using the ampoule breaking procedure. The Gibbs free energies are negative. Positive entropic values favor intercalation in these systems. 相似文献
77.
78.
Anjos JC Appel JA Bean A Bediaga I Bracker SB Browder TE Cremaldi LM Duboscq JE Elliot JR Escobar CO Gibney MC Hartner GF Karchin PE Kumar BR Lima JG Losty MJ Luste GJ Mantsch PM Martin JF McHugh S Menary SR Morrison RJ Nash T Pinfold J Punkar G Purohit MV Ross WR Santoro AF Sliwa K Sokoloff MD Souza MH Spalding WJ Streetman ME Stundzia AB Witherell MS 《Physical review letters》1992,69(20):2892-2895
79.
The isolation and structure determination of (2S,5S)-2,5-dibenzyl-1,4-dimethylpiperazine (), a new alkaloid biogenetically related to L-phenylalanine diketopiperazine, is described. 相似文献
80.
Xu Y Eilers G Borgström M Pan J Abrahamsson M Magnuson A Lomoth R Bergquist J Polívka T Sun L Sundström V Styring S Hammarström L Akermark B 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(24):7305-7314
To mimic the electron-donor side of photosystem II (PSII), three trinuclear ruthenium complexes (2, 2a, 2b) were synthesized. In these complexes, a mixed-valent dinuclear Ru2(II,III) moiety with one phenoxy and two acetato bridges is covalently linked to a Ru(II) tris-bipyridine photosensitizer. The properties and photoinduced electron/energy transfer of these complexes were studied. The results show that the Ru2(II,III) moieties in the complexes readily undergo reversible one-electron reduction and one-electron oxidation to give the Ru2(II,III) and Ru2(III,III) states, respectively. This could allow for photooxidation of the sensitizer part with an external acceptor and subsequent electron transfer from the dinuclear ruthenium moiety to regenerate the sensitizer. However, all trinuclear ruthenium complexes have a very short excited-state lifetime, in the range of a few nanoseconds to less than 100 ps. Studies by femtosecond time-resolved techniques suggest that a mixture of intramolecular energy and electron transfer between the dinuclear ruthenium moiety and the excited [Ru(bpy)3]2+ photosensitizer is responsible for the short lifetimes. This problem is overcome by anchoring the complexes with ester- or carboxyl-substituted bipyridine ligands (2a, 2b) to nanocrystalline TiO2, and the desired electron transfer from the excited state of the [Ru(bpy)3]2+ moiety to the conduction band of TiO2 followed by intramolecular electron transfer from the dinuclear Ru2(II,III) moiety to photogenerated Ru(III) was observed. The resulting long-lived Ru2(III,III) state decays on the millisecond timescale. 相似文献