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51.
《Journal of Chemical Sciences》2005,117(5):525-531
The silicon atom may increase its coordination number to values greater than four, to form pentacoordinated compounds. It
has been observed experimentally that, in general, pentacoordinated compounds show greater reactivity than tetracoordinated
compounds. In this work, density functional theory is used to calculate the global softness and the condensed softness of
the silicon atom for SiH
n
F4−n
and SiH
n
F
5−n
1−
. The values obtained show that the global and condensed softness are greater in the pentacoordinated compounds than in the
tetracoordinated compounds, a result that explains the enhanced reactivity. If the results are analysed through a local version
of the hard and soft acids and bases principle, it is possible to suggest that in nucleophilic substitution reactions, soft
nucleophiles preferably react with SiH
n
F
5−n
1−
, and hard nucleophiles with SiH
n
F4−n
. 相似文献
52.
Quantitative H–Al distances in acid sites of two zeolites with MFI and IFR framework topology were obtained by numerical simulation of 1H{27Al} rotational echo adiabatic passage double resonance (REAPDOR) experiments. A 27Al offset-dependent data set yields for each resolved 1H NMR line a corresponding nuclear electric quadrupole coupling constant of the neighboring 27Al site. This information is used for analyzing a second data set for on-resonance irradiation, where the dipolar evolution time (number of rotor cycles) was varied, to yield the 1H–27Al dipolar coupling constant. Numerical simulations indicate that the REAPDOR method does not depend significantly on the polar angles, defining the orientation of the electric field gradient tensor of 27Al with respect to the Al–H dipolar vector. In contrast, the transfer of populations in double resonance sequence is sensitive to these angles, and it can be thus used to measure them. 相似文献
53.
用过氧聚钨酸(PPTA)水溶液,通过离心涂膜法在显微镜载玻片上制备了具有光滑表面且厚度为100nm的PPTA薄膜,利用PPTA薄膜在紫外光照下可研制光栅以及其它光学元件的薄膜材料,具有很高的利用价值。 相似文献
54.
Methods to synthesize magnetic Fe3O4 nanoparticles and to modify the surface of particles are presented in the present investigation. Fe3O4 magnetic nanoparticles were prepared by the co-precipitation of Fe3+ and Fe2+, NH3·H2O was used as the precipitating agent to adjust the pH value, and the aging of Fe3O4 magnetic nanoparticles was accelerated by microwave (MW) irradiation. The obtained Fe3O4 magnetic nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), X-ray powder diffraction (XRD) and vibrating sample magnetometer (VSM). The average size of Fe3O4 crystallites was found to be around 8–9 nm. Thereafter, the surface of Fe3O4 magnetic nanoparticles was modified by stearic acid. The resultant sample was characterized by FT-IR, scanning electron microscopy (SEM), XRD, lipophilic degree (LD) and sedimentation test. The FT-IR results indicated that a covalent bond was formed by chemical reaction between the hydroxyl groups on the surface of Fe3O4 nanoparticles and carboxyl groups of stearic acid, which changed the polarity of Fe3O4 nanoparticles. The dispersion of Fe3O4 in organic solvent was greatly improved. Effects of reaction time, reaction temperature and concentration of stearic acid on particle surface modification were investigated. In addition, Fe3O4/polystyrene (PS) nanocomposite was synthesized by adding surface modified Fe3O4 magnetic nanoparticles into styrene monomer, followed by the radical polymerization. The obtained nanocomposite was tested by thermogravimetry (TG), differential scanning calorimetry (DSC) and XRD. Results revealed that the thermal stability of PS was not significantly changed after adding Fe3O4 nanoparticles. The Fe3O4 magnetic fluid was characterized using UV–vis spectrophotometer, Gouy magnetic balance and laser particle-size analyzer. The testing results showed that the magnetic fluid had excellent stability, and had susceptibility of 4.46×10−8 and saturated magnetization of 6.56 emu/g. In addition, the mean size d (0.99) of magnetic Fe3O4 nanoparticles in the fluid was 36.19 nm. 相似文献
55.
X. Yang 《Applied Surface Science》2006,252(10):3647-3657
The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K. 相似文献
56.
功能性丙烯酸/MBAM体系共聚产物的研制 总被引:2,自引:0,他引:2
以丙烯酸和MBAM为主要原料,经聚合,合成了一种高性能的具有良好保水性能的聚合产物,其保水量达到750~1000倍.50℃以下有良好的保水性能,28℃以下有极好的保水性能,并研究了工艺条件对该产品性能的影响因素. 相似文献
57.
Wei Jun Liao Xianfeng Chen Fucheng Chen Yuping Chen Yuxing Xia Yingli Chen 《Optics & Laser Technology》2004,36(8):603-606
In this paper, we first report that a new proton source, glutaric acid, has been used to fabricate optical waveguides in Z-cut lithium niobate crystals. The relationship was experimentally established between proton-exchanged (PE) waveguide parameters and fabrication conditions. It is shown that this new organic acid can be used to obtain deep PE waveguides in fast diffusion speed (0.275 μm2/h at 221°C) and with low loss (0.2 dB/cm). It provides an alternative approach for fabricating PE waveguides in lithium niobate substrate. 相似文献
58.
用溶胶 凝胶法以磷钼酸 (MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2 催化剂 .使用ICP、XRD、TG DTA、IR、TPD MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能 .杂多钼酸盐与TiO2 通过O2 -在TiO2 表面发生了键合 .在 6 2 3K下 ,杂多阴离子仍保持原有的Keggin结构 .CO2 在Lewis酸位Ni(Ⅱ )和Lewis碱位Ni-O -Mo的桥氧协同作用下生成CO2 卧式吸附态Ni(Ⅱ )←O - (CO)← (O--Ni) .丙烯有多种吸附态在催化剂上吸附 .在 5 6 3K、1MPa和空速 15 0 0h-1的反应条件下 ,丙烯的摩尔转化率为 3.2 % ,产物MAA选择性为 95 % . 相似文献
59.
E. E. Ergozhin N. A. Bektenov A. K. Mekebaeva N. N. Chopabaeva 《Chemistry of Natural Compounds》2003,39(3):299-302
Phosphorus-containing cellulose cation exchangers were synthesized by reaction of wood cellulose with orthophosphoric acid and the ternary polymer from glycidylmethacrylate, styrene, and maleic anhydride. The effects of the ratio of reactants, temperature, and duration of the reaction on the phosphorylation and exchange capacity of the modified cellulose material were studied. 相似文献
60.
Xuyuan GuScott Cowell Jinfa YingXuejun Tang Victor J. Hruby 《Tetrahedron letters》2003,44(31):5863-5866
(2S,3S)- and (2R,3R)-2-amino-3-phenyl-5-hexenoic acids have been synthesized in large scale by using Ni(II)-complexes as a template. The amino acids were used in the synthesis of [4,3,0]-bicyclic β-turn mimetics by a convergent methodology. The unique advantage of this strategy is the convenience of introducing side chain groups with predetermined chiralities on both the five- and six-membered heterocyclic rings. 相似文献