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1.
Braunstein P Kormann HP Meyer-Zaika W Pugin R Schmid G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(24):4637-4646
Two complementary strategies are presented for the anchoring of molecular palladium complexes, of cobalt or platinum clusters or of gold colloids inside the nanopores of alumina membranes. The first consists in the one step condensation of an alkoxysilyl functional group carried by the metal complex with the hydroxy groups covering the surface of the membrane pores. Thus, using the short-bite alkoxysilyl-functionalized diphosphane ligands (Ph2P)2N(CH2)3Si(OMe)3 (1) and (Ph2P)2N(CH2)4SiMe2(OMe)] (2) derived from (Ph2P)2NH (dppa) (dppa bis(diphenylphosphanyl)amine), the palladium complexes [Pd(dmba)(kappa2-P,P-(Ph2P)2N(CH2)3Si(OMe)3)] Cl (3) and [Pd(dmba)[kappa2-P,P-(Ph2P)2N(CH2)4SiMe2(OMe)]]Cl (4) (dmba-H = dimethylbenzylamine). respectively, were tethered to the pore walls. After controlled thermal treatment. confined and highly dispersed palladium nanoparticles were formed and characterized by transmission electron microscopy (TEM). This method could not be applied to the cobalt cluster [Co4(CO)8(mu-dppa)[mu-P,P-(Ph2P)2N(CH2)4SiMe2(OMe)]] (7) owing to its too limited solubility. However, its anchoring was achieved by using the second method which consisted of first derivatizing the pore walls with 1 or 2. The covalent attachment of the diphosphane ligands provides a molecular anchor that allows subsequent reaction with the cluster [Co4(CO)10(mu-dppa)] 6 to generate anchored 7 and this step was monitored by UV/Vis spectroscopy. In addition, the presence of carbonyl ligands in the cluster provides for the first time a very sensitive spectroscopic probe in the IR region which confirms both cluster incorporation and the retaining of its molecular nature inside the membrane. The presence of the bridging dppa ligand in 6 provides additional stabilization and accounts for the selectivity of the procedure. Using this method, platinum clusters (diameter ca. 2 nm) and gold colloids (diameter ca. 13 nm) were immobilized after passing their solution through the functionalized membrane pores. The resulting membranes were characterized by TEM which demonstrated the efficiency of the complexation and showed the high dispersion of the metal loading. The successful application of these methods has demonstrated that nanoporous alumina membranes are not only unique supports to incorporate metal complexes, clusters, or colloids but can also be regarded as functional matrices or microreactors, thus opening new fields for applications. 相似文献
2.
Hans‐Peter Kormann Günter Schmid Katrin Pelzer K. Philippot Bruno Chaudret 《无机化学与普通化学杂志》2004,630(12):1913-1918
Nanoporous alumina membranes, loaded with palladium and ruthenium nanoparticles of various size, were used for gas phase hydrogenation of 1, 3‐butadiene and for oxidation of carbon monoxide, respectively. Those membranes contain 109 ‐ 1011 pores per cm2, all running perpendicular to the surface. Membrane discs of 20 mm in diameter and only 60 μm thick, incorporated in a reactor in which the reactants can be pumped in a closed circuit through the pores, turned out to very actively catalyze hydrogenation of butadiene (Pd) and oxidation of CO (Ru). The activity of the Pd catalysts depends characteristically on the particles size, the gas flow, and of the educts ratio. As could be expected, larger particles are less active than smaller ones, whereas increasing gas flows in case of hydrogenation accelerates the reactions. Excessive hydrogen reduces selectivity with respect to the various butenes, but favours formation of butane. 相似文献
3.
G. Doucas M. F. Kimmitt Th. Kormann G. Korschinek C. Wallner 《International Journal of Infrared and Millimeter Waves》2003,24(6):829-845
Spontaneous Smith-Purcell radiation at wavelengths of 100 and 220m has been observed. The angles of observation were 17° and 28° and the electron beam energies 1.9 and 1.56MeV, respectively. The radiated power was about 320nW at 17° and 92nW at 28°. These values are in reasonable agreement with what is theoretically expected if the emission process is due to the acceleration of image charges induced on the grating surface by the electrons of the beam. 相似文献
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5.
T. N. Mamedov D. G. Andrianov D. Herlach V. N. Gorelkin K. I. Gritsai V. N. Duginov O. Kormann J. Major A. V. Stoikov U. Zimmermann 《JETP Letters》2001,73(12):674-677
Results of studying the temperature dependence of the residual polarization of negative muons in crystalline silicon with germanium (9×10 19 cm ?3 ) and boron (4.1×10 18 , 1.34×10 19 , and 4.9×10 19 cm ?3 ) impurities are presented. It is found that, similarly to n-and p-type silicon samples with impurity concentrations up to ~10 17 cm ?3 , the relaxation rate ν of the magnetic moment of a μ Al acceptor in silicon with a high impurity concentration of germanium (9×10 19 cm ?3 ) depends on temperature as ν~T q , q≈3 at T=(5–30) K. An increase in the absolute value of the relaxation rate and a weakening of its temperature dependence are observed in samples of degenerate silicon in the given temperature range. Based on the experimental data obtained, the conclusion is made that the spin-exchange scattering of free charge carriers makes a significant contribution to the magnetic moment relaxation of a shallow acceptor center in degenerate silicon at T?30 K. Estimates are obtained for the effective cross section of the spin-exchange scattering of holes (σ h ) and electrons (σ e ) from an Al acceptor center in Si: σ h ~10?13 cm2 and σ e ~8×10?15 cm2 at the acceptor (donor) impurity concentration n a (n d )~4×1018 cm?3. 相似文献
6.
T. N. Mamedov D. Herlach K. I. Gritsaj O. Kormann J. Major A. V. Stoikov U. Zimmermann 《Journal of Experimental and Theoretical Physics》2001,93(5):941-947
The magnetic moment of the negative muon in the 1s state was measured in carbon, oxygen, magnesium, silicon, sulfur, and zinc. The attained precision of measurements allowed the dependence of the relativistic correction to the magnetic moment of the bound muon on the charge of the nucleus to be verified. 相似文献
7.
Near- and mid-infrared laser-optical sensors for gas analysis 总被引:3,自引:0,他引:3
Peter Werle Franz Slemr Karl Maurer Robert Kormann Robert Mücke Bernd Jnker 《Optics and Lasers in Engineering》2002,37(2-3)
Semiconductor diode lasers were first developed in the mid-1960s and found immediate application as much needed tunable sources for high-resolution laser spectroscopy commonly referred to as tunable diode laser absorption spectroscopy (TDLAS). In this paper, currently available semiconductor lasers for spectroscopy in the near- and mid-infrared spectral region based upon gallium arsenide, indium phosphite, antimonides and lead-salt containing compounds will be reviewed together with the main features of TDLAS. Room-temperature measurements of atmospheric carbon dioxide near 2 μm will be discussed and recent results obtained with a fast chemical sensor for methane flux measurements based on lead-salt diode lasers operating near 7.8 μm will be presented. 相似文献
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9.
S. Lederer H. Winter HP. Winter F. Aumayr 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2007,41(3):505-511
The energy loss of hydrogen atoms with energies of 400
eV and 1 keV is studied in coincidence with the number of emitted
electrons during grazing scattering from atomically clean and flat
KI(001) and LiF(001) surfaces. The energy loss spectra for
specific numbers of emitted electrons are analyzed in terms of a
binary interaction model based on the formation of transient
negative ions via local capture of valence band electrons from
anion sites. Based on computer simulations we derive for this
interaction scenario probabilities for the production of surface
excitons, for electron loss to the conduction band of KI, for
emission of electrons, and for formation of negative hydrogen
ions. The pronounced differences of data obtained for the two
surfaces are attributed to the different electronic structures of
KI and LiF. 相似文献
10.
A compact 14.5GHz electron cyclotron resonance (ECR) ion source for the production of slow, multiply charged ions has been constructed,with the plasma-confining magnetic field produced exclusively by permanent magnets.Microwave power of up to 175W in the frequency range from 12.75 to 14.SGHz is transmitted from ground potential via a PTFE window into the water-cooled plasma chamber which can be equipped with an aluminum liner.The waveguide coupling system serves also as biased electrode,and two remotely-controlled gas inlet valves connected via an insulating break permit plasma operation in the gas- mixing mode.A triode extraction system sustains ion acceleration voltages between 1kV and 10kV.The ECR ion source is fully computer-controlled and can be remotely operated from any desired location via Ethernet. 相似文献