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Self-sensitisation of photo-oxygen evolution occurs in aqueous dispersions of silver zeolites. In presence of Cl?, chlorine is the photoproduct in acidic medium, and the same type of self-sensitisation occurs. Self-sensitisation means that systems which are first insensitive to light of a certain wavelength become photo-active after they have been illuminated by light of higher energy. For a better understanding of silver zeolites, we have carried out EH-MO calculations on the 6–6 subunit (SBU) of a zeolite, on the 6–6 SBU with an Ag-atom in the center, on the 6–6 SBU with one Ag-atom in the center and one outside on top of the hexagon, and finally on another with one Ag-atom in the center and two Ag-atoms outside, each on top of a hexagon. The Ag0 in the cage of the 6–6 SBU is significantly polarized by the 6–6 SBU environment. The energy barrier to escape the 6–6 SBU is 0.8 eV for Ag0 and 0.5 eV for Ag+. The HOMO of the Ag(6–6 SBU) is a totally symmetric 5s* orbital and the LUMO is a 5pz* type. 5pz*←5s* electronic excitation reduces the energy barrier and allows an (Ag0)* to exit the 6–6 SBU, provided the excited-state lifetime is long enough. The MO picture predicts low-energy charge-transfer transitions from the zeolite framework to the 5s* orbital. The highest occupied orbitals of the zeolite framework are localized on the O-atoms. Interactions between an Ag-atom in the 6–6 SBU and one or two external Ag-atoms are discussed. 相似文献
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Ovshinsky SR Young RT Allred DD DeMaggio G Van der Leeden GA 《Physical review letters》1987,58(24):2579-2581
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Synthesis of 4-Trichlorosilylmethylbenzonitrile and 4-(2-Trichlorosilylethyl)pyridine for Surface Modification of Tin Dioxide We describe the synthesis of 4-(trichlorosilylmethyl)benzonitrile and 4-(2-trichlorosilylethyl)pyridine, starting from 4-(bromomethyl)benzonitrile and trichlorosilane or vinylpyridine and trichlorosilane. Trimethoxysilanes are obtained by reaction of the trichlorosilyl compounds with methyl orthoformate. 4-(Trichlorosilylmethyl)benzonitrile and 4-(2-trichlorosilylethyl)pyridine are used to modify the surface of tin dioxide. 相似文献
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种植沙生植物--沙棘改善内蒙古地区生态环境 总被引:2,自引:0,他引:2
结合内蒙古地区现状,对沙棘的生物学和生态学特性、沙棘属植物化学成分和微量元素及种植沙生植物——沙棘的重要性和必要性进行了详细的研究和探讨。研究表明,沙棘属植物具有极强的生态适应性并富含多种营养成分和生物活性物质,并以耐干旱、耐瘠薄、萌蘖及固氮能力强等特点被称为治理非宜林地水土流失、改善生态环境的先锋树种。种植沙棘是治理内蒙古脆弱生态环境最经济、最有效的措施,是贫瘠的不毛之地发展经济、增加收入的经济树种。另外.种植沙棘的技术简便,容易掌握,投资少,见效快。 相似文献
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The electronic structures of the 4-4 SBU, the β-cage, and the β-cage with two 4-4 SBU's attached to it have been studied by means of EH-MO calculations. No indication of the formation of a band structure has been found. The HOMO region consists of many closely spaced, localized states, 98.6% of them concentrated on the O-atoms. Reversible color changes of Cu+1 and Ag+1 zeolites observed upon hydration-dehydration experiments can be understood as charge-transfer transitions from the HOMO concentrated on the zeolite O-atoms to the metal cations. As soon as the Cu+1 or Ag+1 are partially hydrated, the ns* and np* states are shifted to higher energies. The luminescence observed with dehydrated Cu+1-zeolites X is caused by a 4p*←HOMO absorption, followed by spontaneous 4s*←4p* emission. After a detailed study of a Cu+1 in the 6-6 SBU, we discuss the electronic structure of a β-cage filled with 1,2,4,8, and 9 Cu+1. In each case, the β-cage is found to be too small to allow the formation of a band structure. The levels caused by the added copper are distinctly quantized. Calculations on [Ag3(H2O)3]3+ in a β-cage are reported. The direct interaction between the Ag-atoms is significant. As a consequence, the states formed by Ag 5s and 5p atomic orbitals are delocalized over the three Ag-centers. In both the Cu+1 and the Ag+1 zeolites, the ligand-field picture is found to be insufficient to explain the electronic structure, when the metal is coordinated to the zeolite oxygen framework. 相似文献
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Host-guest antenna materials 总被引:2,自引:0,他引:2
Calzaferri G Huber S Maas H Minkowski C 《Angewandte Chemie (International ed. in English)》2003,42(32):3732-3758
The focus of this review is on host-guest composites with photonic antenna properties. The material generally consists of cylindrical zeolite L crystals the channels of which are filled with dye molecules. The synthesis is based on the fact that molecules can diffuse into individual channels. This means that, under the appropriate conditions, they can also leave the zeolite by the same way. In some cases, however, it is desirable to block their way out by adding a closure molecule. Functionalization of the closure molecules allows tuning of, for example, wettability, refractive index, and chemical reactivity. The supramolecular organization of the dyes inside the channels is a first stage of organization. It allows light harvesting within a certain volume of a dye-loaded nanocrystalline zeolite and radiationless transport to both ends of the cylinder or from the ends to the center. The second stage of organization is the coupling to an external acceptor or donor stopcock fluorophore at the ends of the channels, which can trap or inject electronic excitation energy. The third stage of organization is the coupling to an external device through a stopcock molecule. The wide-ranging tunability of these highly organized materials offers fascinating new possibilities for exploring excitation-energy-transfer phenomena, and challenges for developing new photonic devices. 相似文献