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191.
ZhenshanPeng ChanglinYu TiejunCai QianDeng 《天然气化学杂志》2004,13(3):172-176
Mixed oxide catalyst Cs0.1Fe2Co6BiMnMo12Ox was prepared by the coprecipitation method.Selective oxidation of isobutene was carried out in a fixed-bed reactor over Cs0.1Fe2Co6BiMnMo12Ox.The results showed that the catalyst had high catalytic activity. Under the optimum reaction conditions(n(i-C4):n(O2)=1:2-1:4, space velocity=180 h^-1, T=360℃), the yields of methacrolein and methacrylic acid can reach 80% and 8%, respectively. The total yield of liquid products (methacrolein, methacrylic acid and acetic acid) can reach about 90%. 相似文献
192.
The first implementation of the intrinsic reaction coordinate (IRC ) method within the density functional theory (DFT ) framework is presented. The implementation has been applied to four different types of chemical reactions represented by the isomerization process, HCN ? HNC (A); the SN2 process, H? + CH4 ? CH4 + H? (B); the exchange process, H˙ + HX ? HX + H˙ (X ? F,Cl) (C); and the elimination process, C2H5Cl ? C2H4 + HCl (D). The present study presents for each process optimized structures and calculated harmonic vibrational frequencies for the reactant(s), the transition state, and the product(s) along with the IRC path connecting the stationary points. The calculations were carried out within the local density approximation (LDA ) as well as the LDA/NL scheme where the LDA energy expression is augmented by Perdew's and Becke's nonlocal (NL ) corrections. The LDA and LDA/NL results are compared with each other as well as the best available ab initio calculations and experimental data. For reaction (D), ab initio calculations based on MP 2 geometries and MP 4SDTQ energies have been added due to the lack of accurate published post-HF calculations on this process. A detailed discussion is provided on the efficiency of the IRC algorithms, the relative accuracy of the DFT and ab initio schemes, as well as the reaction mechanisms of the four reactions. It is concluded that the LDA/NL scheme affords the same accuracy as does the MP 4 method. The post-HF methods seem to overestimate activation energies, whereas the corresponding LDA/NL estimates are too low. The LDA activation energies are even lower than the LDA/NL counterparts. The incorporation of the IRC method into the DFT framework provides a promising and reliable tool for probing the chemical reaction path on the potential energy surfaces, even for large-size systems. IRC calculations by ab initio methods of an accuracy similar to the LDA/NL scheme, such as the MP 4 scheme, are not feasible. © John Wiley & Sons, Inc. 相似文献
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通过分子设计,合成了一种新颖的双β-二酮有机配体9-乙基-3,6-二(乙酰基-3-苯甲酰基)咔唑(H2L)及其铕配合物,红外光谱和电子光谱表明Eu^3+与H2L发生配位。配合物的溶液荧光光谱不仅有613 nm处的中心离子Eu^3+的特征红光,属^5D0→^7F2跃迁带,还有445nm处配体的宽带蓝色发光,属H2L^*→H2L跃迁带,而配合物的光致发光光谱只有611 nm处为中心离子Eu^3+的特征红光,属^5D0→^7F2跃迁带,峰形尖锐,半峰宽仅7 nm,单色性好,表明该固体铕双β-二酮配合物是一种潜在的红色发光材料。 相似文献
198.
Using ClO2 as chemiluminescence (CL) oxidant, a novel homogeneous CL system in neutral and near neutral aqueous solution is proposed in this paper. ClO2 could oxidize sulfite in pH 5.0–8.5 acetate buffer to produce CL emission, and pipemidic acid could sensitize the CL system. The ClO2–SO32−–pipemidic acid reaction was used as a model CL system and explored the possibility of highly active and eco-friendly ClO2 being used as CL oxidant in neutral and near neutral aqueous solution. Combined with flow-injection analysis, the proposed CL system was applied to the automated dissolution testing of pipemidic acid tablet. Compared with the common strong acidic or strong basic CL system, this proposed CL owns its advantages. 相似文献
199.
Reaction solutions of selectfluor (1) with triphenylethylene (4a) and tetraphenylethylene (4b) were monitored by ESI-MS and ESI-MS/MS. Detection and characterization of the key radical cationic intermediates 5a.+ and 5b.+) fully supports the SET mechanism in electrophilic fluorination as depicted above. [reaction: see text] 相似文献
200.
[structure: see text] Remarkable UV OLED devices using novel spiro-configured bifluorenes as UV emitters have been successfully achieved with external quantum efficiencies up to 2.6-3.1% and emission wavelengths as short as 370 nm. In addition, these large-gap materials have been shown to be effective hosts for red phosphorescent emitters in phosphorescent OLEDs. This result represents the first example that pure hydrocarbon molecules can serve as an efficient host for red electrophosphorescence devices. 相似文献