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51.
(100-x) mole% SiO2-x mole% P2O5-glasses withx=1–9 have been prepared by the sol-gel process using tetraethylorthosilicate and triethylphosphate as precursors. The gels
were fired at various temperatures up to 950°C and then exposed to γ-ray irradiation to induce paramagnetic centers. CW-EPR
and FT-EPR Spectroscopies were employed at temperatures between 4 and 300 K in order to determine the resulting structures.
The dried gels exhibited four types of O
2
−
-ions trapped in pores of different sizes. The gels fired atT=670°C exhibited theE’
1-center and non-bridging oxygen as a results of the fracture of the Si-O-Si bonds. At higher temperatures, the spectra of
the POHC, POHC
b
,E’, and CH
3
−
-centers have been detected that are a function ofx andT. 相似文献
52.
53.
常压气相氧化羰基化合成碳酸二乙酯 总被引:3,自引:0,他引:3
碳酸二乙酯是一种重要的有机化工原料,可广泛用于合成农药如脱叶灵,医药如喹啉酮衍生物,中间体3-氧硫代羧酸酯,还可用于电子管阴极的镀层[1-3]。生产碳酸二乙酯的传统方法为:无水乙醇与光气反应生成氯甲酸乙酯,氯甲酸乙酯继续与乙醇反应生成碳酸二乙酯后经水洗蒸馏制成。使用光气为原料对设备的要求较高。我们在常压下气相羰基化合成碳酸二乙酯[4]:2NO+C2H5OH+0.5O2→2C2H5ONO+H2O(1)CO+2C2H5ONO→(C2H5O)2CO+2NO(2)产生的一氧化氮可与氧气和乙醇进行反应再生为亚硝酸乙酯,符合原子经济反应且几乎不放出对… 相似文献
54.
研究了H4SiW12O40.24H2O(SiW12)在水,乙醇,乙酸,乙酸丁酯中在活性炭上的吸附得出,活性炭微孔结构对SiW12在其表面的吸附起着分子筛作用,水溶剂化的SiW12分子可顺利进行活性1.7nm左右的微孔,而其它溶剂化的SiW12分子,则需较大的孔径,提出了SiW12在活性炭表面吸附的微孔中孔扩散模型。 相似文献
55.
Stephen P. Walch 《中国化学会会志》1995,42(2):221-231
Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NOx and soot formation in hydrocarbon combustion are discussed. 相似文献
56.
The diffusion length of charge carriers in the active layer of a perovskite solar cell (PSC) of the structure Glass/PEDOT: PSS/CH3NH3PbI3/PC60BM/Al is modelled. It is found that the diffusion length depends on the position x in the active layer measured from the PEDOT: PSS interface, Urbach energy and temperature. By varying the voltage in the range from zero to , it is shown that the dependence of diffusion length on the position x in the active layer reduces at higher voltage. The combined influence of applied voltage and temperature on the diffusion length of charge carriers is investigated and it is found that in the low voltage range the diffusion length is temperature independent, but it becomes significantly temperature dependent at higher voltages. Also, it is found that the diffusion length decreases as the applied voltage increases and this reduction becomes much more significant at higher voltage and temperatures. The combined influence of applied voltage and Urbach energy on diffusion length of charge carriers reveals that the diffusion length decreases when both the applied voltage and Urbach energy increase. However, the reduction in the diffusion length due to the increase in Urbach energy becomes less significant at higher voltage. 相似文献
57.
Gert Brandl Fritz Kastner Rainer Fritsch Herbert Zinner Albrecht Mannschreck 《Monatshefte für Chemie / Chemical Monthly》1992,123(11):1059-1069
Summary A procedure is described which serves to measure circular dichrograms () on line during stops of flow in liquid chromatography. Since the concentration of substrate in the spectrometer cell during the stop is not known, the differential absorption coefficients are calculated from the experimental differential absorbances A by means of UV absorption (i. e. photomultiplier voltage) data. Verifications of the procedure are obtained by its application to three substrates (Table 1), the () spectra of which were known. The present on-line technique is compared with a corresponding off-line method.The N,N-dimethylthiobenzamides1 and2 as well as the 9,10-phenanthrenequinone7 consist of interconvertible enantiomers because their planar states are destabilized by steric overcrowding of groups. The unknown dichrograms () of1, 2 and7 are obtained (Figs. 2 and 4) and discussed with reference to the helicities of these molecules.In memory of the late Professor Dr. Dr. h. c. Günther Snatzke. 相似文献
58.
The semilocalized approach to chemical reactivity (J. Mol. Struct. (Theochem) 588 (2002) 99; Int. J. Quant. Chem. 94 (2003) 302) is applied to study the addition reaction of an electrophile or nucleophile to the butadiene molecule. In accordance with the classical concept of the reaction center and its neighborhood (substituent), only one of the two H2C=CH-fragments of butadiene is supposed to be under a direct attack of the reagent, whereas the remaining H2C=CH-group is assumed to play the role of the substituent and thereby to participate in the process indirectly by exerting certain electron-donating or accepting effect upon the former group and/or the reagent. The main aim of the study consists in revealing the role of the H2C=CH-substituent in the formation of the known higher reactivity of the terminal carbon atom of the attacked C=C-bond (as compared to the internal atom) irrespective of the nature of the reagent. To this end, we seek to obtain an explicit algebraic representation of the interdependence between the direction and the extent of the total influence of the H2C=CH-substituent, on the one hand, and the nature of the reagent, on the other hand. The expressions for electron density and bond order redistributions among separate fragments of contacting molecules derived previously in the form of power series are shown to yield the above-anticipated representation. On this basis, it is demonstrated that the electron-donating effect of the initially occupied (bonding) orbital of the substituent and the electron-accepting effect of its initially vacant (antibonding) orbital upon the remaining fragments of the whole reacting system may be considered independently whatever the nature of the reagent. However, a strong interdependence is established between the actual relative extents of these two components of the total effect of the H2C=CH-group and the electron-donating (accepting) properties of the reagent. Moreover, this group of atoms is shown to manifest itself as an electron-donating (accepting) substituent under influence of an electrophilic (nucleophilic) attack. Using this principal result of the paper, the actual reactivity of butadiene with respect to electrophile (nucleophile) is interpreted by invoking a model system of a substituted ethene containing a simple (one-orbital) electron-donating (accepting) substituent, and a terminal addition easily follows for both types of the reagent. 相似文献
59.
YAN Zi-Feng 《天然气化学杂志》1996,5(2):116-125
1yttroductionIMcthancactivationisoncofthemostintriguingsubjectsinheterogencouscatal}'sisbccauscmcthancisathcrmod}namicall}'stabIccompoundt`ithanoblcgas-likeconfiguration.0fintcrcstsisthcrcccntt"orkreportcdb}'KocrtsIll,BeIguedl21.andYanl3ltthosucccssfull}'convcrtnaturalgasintohighcrh}.drocarbonsb}'thctt"o-stcproutcinwhichnaturalgasisfirstthcrmall}'activatcdonthctransitionmctalcatal}.stsatmoderatctemperature.Toasccrtainthcnaturcofrcactionsofmcthane.thcactivationofmcthaneisextensivel)'invcstiga… 相似文献
60.
乙醇羰化反应负载型催化剂的研究 总被引:9,自引:0,他引:9
本文由七种负载型催化剂中选出两种比较好的乙醇羰化催化剂,研究了影响反应转化率和选择性的因素,考察了活性组份的价态和载体的酸性。此外,还对催化剂进行了能量色散X射线分析。从其结果看,谱图上只有活性中心铑的谱峰而没有氯的谱峰,说明铑是以离子形式进入载体,而不是以化合物形式被吸附于载体上。 相似文献