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991.
992.
Kostelansky CN Pietron JJ Chen MS Dressick WJ Swider-Lyons KE Ramaker DE Stroud RM Klug CA Zelakiewicz BS Schull TL 《The journal of physical chemistry. B》2006,110(43):21487-21496
Ligand-stabilized platinum nanoparticles (Pt NPs) can be used to build well-defined three-dimensional (3-D) nanostructured electrodes for better control of the catalyst architecture in proton exchange membrane fuel cells (PEMFCs). Platinum NPs of 1.7 +/- 0.5 nm diameter stabilized by the water-soluble phosphine ligand, tris(4-phosphonatophenyl)phosphine (TPPTP, P(4-C6H4PO3H2)3), were prepared by ethylene glycol reduction of chloroplatinic acid and subsequent treatment of the isolated nanoparticles with TPPTP. The isolated TPPTP-stabilized Pt NPs were characterized by multinuclear magnetic resonance spectroscopy (31P and 195Pt NMR), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS). The negatively charged TPPTP-Pt NPs were electrostatically deposited onto a glassy carbon electrode (GCE) modified with protonated 4-aminophenyl functional groups (APh). Multilayers were assembled via electrostatic layer-by-layer deposition with cationic poly(allylamine HCl) (PAH). These multilayer films are active for the key hydrogen fuel cell reactions, hydrogen oxidation (anode) and oxygen reduction (cathode). Using a rotating disk electrode configuration, fully mass-transport limited kinetics for hydrogen oxidation was obtained after 3 layers of TPPTP-Pt NPs with a total Pt loading of 4.2 microg/cm2. Complete reduction of oxygen by four electrons was achieved with 4 layers of TPPTP-Pt NPs and a total Pt loading of 5.6 microg/cm2. A maximum current density for oxygen reduction was reached with these films after 5 layers resulting in a mass-specific activity, i(m), of 0.11 A/mg(Pt) at 0.9 V. These films feature a high electrocatalytic activity and can be used to create systematic changes in the catalyst chemistry and architecture to provide insight for building better electrocatalysts. 相似文献
993.
Shumate WJ Mattern DL Jaiswal A Dixon DA White TR Burgess J Honciuc A Metzger RM 《The journal of physical chemistry. B》2006,110(23):11146-11159
We report spectroscopic characterization and unimolecular rectification (asymmetric electrical conduction) measurements of three donor-sigma-acceptor (D-sigma-A) compounds N-(10-nonadecyl)-N-(1-pyrenylmethyl)perylene-3,4,9,10-bis(dicarboximide) (1), N-(10-nonadecyl)-N-(4-[1-pyrenyl]butyl)perylene-3,4,9,10-bis(dicarboximide) (2), and N-(10-nonadecyl)-N-(2-ferrocenylethyl)perylene-3,4,9,10-bis(dicarboximide) (3). These molecules were arranged as one-molecule thick Langmuir-Blodgett monolayers between Au electrodes. In such an "Au | D-sigma-A | Au" sandwich, molecule 1 is a unimolecular rectifier, with rather small rectification ratios (between 2 and 3 at +/-1 V) that decrease upon cycling. Molecule 2 does not rectify. Molecule 3 rectifies, with a rectification ratio of between 14 and 28 at +/-1 V; the through-film rectification and currents persist, even with scans of +/-2 V, for up to 40 cycles of measurement. Qualitative arguments, based on a two-level rectification mechanism, are consistent with the current asymmetries observed in the monolayers of 1 and 3. 相似文献
994.
We study the photoreduction of adsorbed copper ions onto Au nanoparticles, on an indium tin oxide (ITO) electrode in an aqueous electrochemical cell, as a function of applied voltage and laser intensity. The photocurrent is a nonlinear function of laser intensity and increases sharply with cathodic voltage in the underpotential deposition region. The photoreduction is attributed to laser heating of the Au nanoparticles rather than "hot electron" processes. Numerical simulation of the Butler-Volmer kinetic equation using experimental parameters predicts a several orders of magnitude increase in current for a temperature rise of a few Kelvin. 相似文献
995.
996.
2H/1H isotope ratios of polyhalogenated compounds were determined by elemental analysis and isotope ratio mass spectrometry (EA-IRMS).
Initial measurements with standard EA-IRMS equipment, which used high-temperature pyrolysis to convert the organic compounds
into hydrogen, did not achieve significant signals for polychlorinated pesticides and related compounds, presumably due to
the formation of HCl instead of hydrogen. To reverse this problematic reaction, a chromium reactor was incorporated into the
element analyzer system, which scavenged Cl, forming chromium chloride and releasing hydrogen again in the form of H2. The optimized system therefore allowed the δ2H values of polyhalogenated compounds to be determined. A quality assurance program was developed based on several parameters.
(i) Each compound was analyzed using a sequence of five injections, where the first measurement was discarded. (ii) Recovery
of H (when calculated relative to acetanilide) had to be >90% for all replicates in a sequence. (iii) All δ-values within
a sequence had to vary by less than 10‰. (iv) Results had to be reproducible on another day with a different sample scheme.
Once this reproducibility had been established, variabilities in the δ2H values of organohalogen standards were investigated using the technique. The highest δ2H value of +75‰ was found for o,p′-DDD, whereas the strongest depletion in deuterium was found for Melipax (–181‰). The most important results for comparable
compounds were as follows. DDT-related compounds gave δ2H values of between +59 and +75‰ (technical DDT, o,p′- and p,p′-DDD) or in the range of approximately −1‰, indicative of the different sources/methods of producing this compound. Four
HCH isomers from the same supplier showed relatively similar hydrogen isotope distributions, whereas two lindane (γ–HCH) standards
from other sources had 39‰ less deuterium. This difference is likely due to different purification steps during the isolation
of pure lindane from the technical HCH mixture. An even greater difference was observed between the δ2H values of Toxaphene (US product dating from 1978) and Melipax (product from the former East Germany, dating from 1979),
which gave δ2H values of –101‰ and –181‰, respectively, meaning that both products were easily distinguished via δ2H-IRMS. Fractioning of hydrogen isotopes in the atmospheric water cycle was suggested as one reason for the different values.
In this theory, the water (which had different δ2H values depending on where it was taken from) was incorporated during the biosynthesis of camphene, which is the natural
product used to produce both products. These results indicate that hydrogen isotope-specific analysis can be a valuable tool
for tracing the origins of a compound in certain cases. 相似文献
997.
Claude Bardos Uriel Frisch Walter Pauls Samriddhi Sankar Ray Edriss S. Titi 《Communications in Mathematical Physics》2010,293(2):519-543
We consider a modification of the three-dimensional Navier–Stokes equations and other hydrodynamical evolution equations with
space-periodic initial conditions in which the usual Laplacian of the dissipation operator is replaced by an operator whose
Fourier symbol grows exponentially as e|k|/kd{{{\rm e}^{|k|/k_{\rm d}}}} at high wavenumbers |k|. Using estimates in suitable classes of analytic functions, we show that the solutions with initially finite energy become
immediately entire in the space variables and that the Fourier coefficients decay faster than e-C(k/kd) ln(|k|/kd){{{\rm e}^{-C(k/k_{\rm d})\,{\rm ln}(|k|/k_{\rm d})}}} for any C < 1/(2 ln 2). The same result holds for the one-dimensional Burgers equation with exponential dissipation but can be improved:
heuristic arguments and very precise simulations, analyzed by the method of asymptotic extrapolation of van der Hoeven, indicate
that the leading-order asymptotics is precisely of the above form with C = C
* = 1/ ln 2. The same behavior with a universal constant C
* is conjectured for the Navier–Stokes equations with exponential dissipation in any space dimension. This universality prevents
the strong growth of intermittency in the far dissipation range which is obtained for ordinary Navier–Stokes turbulence. Possible
applications to improved spectral simulations are briefly discussed. 相似文献
998.
Walter F. Wreszinski 《Journal of statistical physics》2010,138(4-5):567-578
We consider random generalizations of a quantum model of infinite range introduced by Emch and Radin. The generalizations allow a neat extension from the class l 1 of absolutely summable lattice potentials to the optimal class l 2 of square summable potentials first considered by Khanin and Sinai and generalised by van Enter and van Hemmen. The approach to equilibrium in the case of a Gaussian distribution is proved to be faster than for a Bernoulli distribution for both short-range and long-range lattice potentials. While exponential decay to equilibrium is excluded in the nonrandom l 1 case, it is proved to occur for both short and long range potentials for Gaussian distributions, and for potentials of class l 2 in the Bernoulli case. Open problems are discussed. 相似文献
999.
Steady-state turbulence is generated in a tank of water and the trajectories of particles forming a compressible system on the surface are tracked in time. The initial uniformly distributed floating particles coagulate and form a fractal structure, a rare manifestation of a strange attractor observable in real space. The surface pattern reaches a steady state in approximately 1 s. Measurements are made of the fractal dimensions Dq(t) (q=1 to 6) of the floating particles starting with the uniform distribution Dq(0)=2 for Taylor Microscale Reynolds number Reλ?160. Focus is on the time evolution of the correlation dimension D2(t) as the steady state is approached. This steady state is reached in several large eddy turnover times and does so at an exponential rate. 相似文献
1000.