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91.
We have performed calculations on the fullerene cage and stacked structures of neutral and ionic Si50 cluster by full-potential linear-muffin-tin-orbital molecular-dynamics (FP-LMTO-MD) method. It is found that the neutral and charged fullerene cages relax into distorted structures resembling puckered balls. Their electronic structures are remarkably similar besides their geometrical structures. However, the relaxed cages are still not so stable as the stacked structure built from tricapped trigonal prism. By comparison, for the fullerene cages and stacked structures of neutral and ionic Si60 cluster, similar characteristics are found. 相似文献
92.
溶剂化金属原子浸渍法制备Pd-Cu/γ-Al2O3低温CO氧化催化剂 总被引:5,自引:0,他引:5
Nano-particle Pd/γ-Al2O3 monometallic and Pd-Cu/γ-Al2O3 bimetallic catalysts were prepared by solvated metal atom impregnation (SMAI) method. The results of XRD measurement indicated that Pd- Cu alloy was formed in the bimetallic catalysts and the crystalline particle size of the alloy increased as Cu contents increased with av-erage diameters < 6.0nm for all the samples. XPS and Auger spectra showed that Pd was in zero- valent state, Cu existed mainly in zero- valent state and partially in monovalent state Cu+. The Pd/γ-Al2O3 and Pd-Cu/γ-Al2O3 catalysts exhibited higher activity for CO oxidation at low temperature. The activity of Pd-Cu/γ-Al2O3 bimetallic catalyst was higher than that of Pd/γ-Al2O3 monometallic catalyst. The Pd-Cu/γ-Al2O3 catalyst with Pd/Cu atomic ratio of 1∶1 showed the highest activity. 相似文献
93.
Hans Bock 《Angewandte Chemie (International ed. in English)》1989,28(12):1627-1650
Silicon and its compounds have made possible the design of new materials, which, from computers to space travel, have helped to shape the technology of our 20th century. Conversely, the demands of new technology have stimulated the fast development of silicon chemistry as part of the “renaissance” of inorganic chemistry. This article uses selected examples of predominantly organosilicon compounds to discuss in simplified terms the measurement and assignment of suitable spectroscopic “molecular fingerprints” as well as the resulting benefit for the preparative chemist. The comparison of “equivalent” states of “chemically related” molecules is emphasized, based on perturbation arguments and supporting quantum-chemical models. Special attention is given to the relation between structure and energy, which allows us to understand and to predict the connectivity between and the spatial arrangement of silicon “building blocks”, the energy-dependent electron distribution over the effective nuclear potentials of a molecular framework, and, especially, the partly considerable effects of “silicon substituents” on molecular properties. Future-directed extensions and applications include polysilane band structures, Rydberg states of chromophores containing silicon centers, redox reactions and ion-pair formation of silicon-substituted π systems, and molecular dynamic phenomena in solution or on thermal fragmentation in the gas phase. The main objective is a set of clear and practical rules for interpreting measurements and planning experiments. 相似文献
94.
Selective hydrogenation of α,β‐unsaturated carbonyls into saturated carbonyls is important to obtain remunerative products. However, it is still a challenge to achieve high activity and selectivity under mild conditions. Herein, Pd, Ir and bimetallic Pd‐Ir nanoparticles were uniformly deposited with high dispersity on the surface of SiC by a facile impregnation method, respectively. The as‐prepared Pd/SiC catalysts efficiently hydrogenate cinnamaldehyde to hydrocinnamaldehyde at room temperature and atmospheric pressure, and the activity of Pd/SiC is observed further enhanced by adding Ir component (conversion of 100%). In addition, the dependence of Pd‐Ir catalyst activity on Pd/Ir molar ratio confirms a synergistic effect between Ir and Pd, which originates from the electron transfer between Pd and Ir. 相似文献
95.
It was demonstrated that adsorbed CO is obtained from the reduction of NaHCO3 solution when Pt(100), Pt(110), disordered Pt(111) and polycrystalline electrodes are employed. Reduction of CO2 coming from the dissociation of the hydrogencarbonate anion is proposed as the reaction that produces CO. By using Fourier transform infrared spectroscopy, linear and multi-bonded CO were detected on polycrystalline platinum electrodes. The shape of the band associated with linearly adsorbed CO is monopolar as a consequence of the partial overlapping, at lower wavenumbers, of the absolute bands at both potentials (0.05 and 0.35 V). 相似文献
96.
Rong-Li Jia Zhong-Long Ma Cheng-Yang Wang Su-Mei Wang 《Reaction Kinetics and Catalysis Letters》2005,85(1):73-78
Summary Novel amorphous Ni-La-B/-Al2O3 catalysts have been developed for the production of hydrogen peroxide from carbon monoxide, water and oxygen. The experimental investigation confirmed that the catalyst dried at 120ºC in air shows the best initial activity. The deactivation of amorphous Ni-La-B/-Al2O3 catalysts was also studied. 相似文献
97.
98.
Tetraallylsilane was functionalised using (chloromethyl)dimethylsilane to give the first generation chloromethyl terminated dendrimer 1. The resulting dendrimer was successfully reacted with K[CpM(CO)2] (Cp=η5-C5H5; M=Fe, Ru) to give Si[(CH2)3SiMe2CH2MCp(CO)2]4 functionalised dendrimers in satisfactory yield. Reaction of dendrimer 1 with NaI in acetone gave the -SiMe2CH2I functionalised dendrimer, while reactions of 1 with K[CpM(CO)3] (M=Mo, W, Re), Li[C5Me4H], Na[C5Me4H], the cobaloxime nucleophile or tert-BuLi were not successful. 相似文献
99.
M. A. Desando Y. P. Handa R. E. Hawkins C. I. Ratcliffe J. A. Ripmeester 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(1-2):3-16
The structure I clathrate hydrate of carbon monoxide has been studied using dielectric measurements and13C NMR spectroscopy. Broad, weak dielectric absorption curves with maxima at 2.2–3.8 K yieldE
a
= 0.14 kJ mol–1 for the average Arrhenius activation energy associated with the reorientation of the low polarity guest. Except for H2S this represents the fastest reorienting polar guest known among the clathrate hydrates. The low temperature dielectric absorption curves can best be fitted with a Cole-Davidson asymmetric distribution of relaxation times and activation energies (with = 0.06 at 4 × 106 Hz), which at 107 Hz has been resolved into a double symmetric distribution of discrete relaxation times for CO in the small and large cages. The cross-polarization magic angle spinning13C NMR spectra indicate identical chemical shifts for CO in the small and large cages, in contrast to other hydrates. The static spectra show that the CO molecules undergo anisotropic reorientation in the large cages and that there is still considerable mobility at 77 K. One possible model for the anisotropic motion has the CO rapidly moving among sites over each of the 14 faces of the cage with the CO axis orientated towards the cage centre. The cage occupancy ratio at 220 K,
s/
L = 1.11, indicates slightly greater preference of CO for the small cage.Dedicated to Dr D. W. Davidson in honor of his great contributions to the sciences of inclusion phenomena. 相似文献
100.
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