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911.
Charles Allgood Yi Lin Yee-Chung Ma Burnaby Munson 《Journal of mass spectrometry : JMS》1990,25(10):497-502
Dilute mixtures of C6H6 or C6D6 in He provide abundant [C6H6]+· or [C6D6]+· ions and small amounts of [C6H7]+ or [C6D7]+ ions as chemical ionization (CI) reagent ions. The C6H6 or C6D6 CI spectra of alkylbenzenes and alkylanilines contain predominantly M+· ions from reactions of [C6H6]+· or [C6D6]+· and small amounts of MH+ or MD+ ions from reactions of [C6H7]+ or [C6D7]+. Benzene CI spectra of aliphatic amines contain M+·, fragment ions and sample-size-dependent MH+ ions from sample ion-sample molecules reactions. The C6D6 CI spectra of substituted pyridines contain M+· and MD+ ions in different ratios depending on the substituent (which alters the ionization energy of the substituted pyridine), as well as sample-size-dependent MH+ ions from sample ion-sample molecule reactions. Two mechanisms are observed for the formation of MD+ ions: proton transfer from [C6D6]+· or charge transfer from [C6D6]+· to give M+·, followed by deuteron transfer from C6D6 to M+·. The mechanisms of reactions were established by ion cyclotron resonance (ICR) experiments. Proton transfer from [C6H6]+· or [C6D6]+· is rapid only for compounds for which proton transfer is exothermic and charge transfer is endothermic. For compounds for which both charge transfer and proton transfer are exothermic, charge transfer is the almost exclusive reaction. 相似文献
912.
XRD and XPS are used to study the dispersion state of CuO on ceria surface. The dispersion capacity values of CuO measured
by the two methods are consistent, which are of 1.20 mmol CuO/100 m2 CeO2. In addition, the results reveal that highly dispersed Cu2+ ions are formed at low CuO loadings and that increasing the CuO content to a value higher than its dispersion capacity produces
crystalline CuO after the surface vacant sites on CeO2 are filled. The atomic composition of the outermost layer of the CuO/CeO2 samples has been probed by using static secondary ion mass spectroscopy (SSIMS), and the ratim of Cu/Ce are found to be 0.93
and 0.46 for the 1.22 and 0.61 mmol CuO/CeO2 samples respectively. Temperature-programmed reduction (TPR) profile with two reduction peaks at 156 and 165°C suggests that
the reduction of highly dispersed Cu2+ ions consists of two steps and is easier than that of CuO crystallites, in which the TPR profile has only one reduction peak
at about 249°C. The above experimental results are in good agreement with the prediction of the incorporation model.
Project supported by the National Natural Science Foundation of China. 相似文献
913.
Two crystalline compounds from the bark of Taiwania cryptomerioides Hayata were isolated. One of them was identified as 6,7-dehydroroyleanone and the other was shown to be a new derivative of royleanone having a structure of 6β-acetoxy-7α-hydroxyroyleanone. 相似文献
914.
Effects of Calcination Temperature on the Acidity and Catalytic Performances of HZSM-5 Zeolite Catalysts for the Catalytic Cracking of n-Butane
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The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature (excluding 800 ℃). The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature.The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking. 相似文献
915.
This article reports the results of a computational and experimental study on the reaction of hydrazoic acid, HN3, adsorbed on 15-20 nm TiO2 particle films. Experimentally, FTIR spectra of HN3(a) have been measured by varying HN3 dosage, UV irradiation time and surface annealing temperature. Three sharp peaks, related to v(a)(NNN) of HN3(a) and N3(a) with different configurations in the 2000-2200 cm(-1) region, and a broad band absorption, related to associated and isolated HN(a) and HO(a) adsorptions in the 3000-3800 cm(-1) region, have been detected. Computationally, molecular structures, vibrational frequencies and adsorption energies of possible adsorbates including HN3 and its derivatives, N3, N2, NH, and H, have been predicted by first-principles calculations based on the density functional theory (DFT) and the pseudopotential method. On the basis of the experimental and computational results, the peak appeared at 2075 cm(-1), which increases at a faster rate with HN3 exposure time, is attributed to a stable adsorbate, N3-Ti(a), with the predicted adsorption energy, E(ads) = 13 kcal/mol. The peak at 2118 cm(-1), which survives at the highest surface temperature in the heating experiment, is attributable to the most stable adsorbate, Ti-N2N(H)-O(a) with E(ads) = 36 kcal/mol. The peak at 2170 cm(-1), which vanishes most readily in all of the aforementioned experiments, is related to less stable molecular adsorbates, end-on HN3-Ti(a) with E(ads) = 5 kcal/mol and side-on HN(N2)-Ti(a) with E(ads) = 8 kcal/mol. A potential energy diagram for the formation of various absorbates with their transition states has been established for the HN3/TiO2 system. On the basis of the predicted desorption energies, the four most stable products of the HN3 reaction on TiO2 are H-O(a), 118 kcal/mol; HN-O(a), 85 kcal/mol; Ti-N2N(H)-O(a), 36 kcal/mol; and N3-O(a), 19 kcal/mol. 相似文献
916.
The vibrationally resolved mass analyzed threshold ionization (MATI) spectra of jet-cooled 7-azaindole have been recorded by ionizing via four different intermediate levels. The adiabatic ionization energy of this molecule is determined to be 65 462±5 cm−1, which is greater than that of indole by 2871 cm−1. The vibrational spectra of 7-azaindole in the S1 and D0 states have been successfully assigned by comparing the measured frequencies with those of indole as well as the predicted values from the ab initio calculations. Detailed analysis on the MATI spectra shows that the structure of the cation is somewhat different from that of this species in the neutral S1 state. 相似文献
917.
The equation of state (EOS) of Duh and Mier-y-Terán for one Yukawa potential is expanded to two Yukawa potentials to describe the nonidealities of the charged lysozyme and alpha-chymotrypsin solutions. Instead of the classical DLVO theory, the attractive dispersion and double-layer repulsion interactions are represented by two Yukawa potentials, respectively. For the aqueous lysozyme solutions, the only adjustable dispersion energy parameter epsilon/k is regressed and the average deviation is 1.76%. For the aqueous alpha-chymotrypsin solutions, two adjustable parameters (the molecular weight and dispersion energy parameter) are regressed and the average deviation is 7.62%. Some correlation and prediction results are discussed. 相似文献
918.
A novel immune algorithm for resolution and quantitative determination of the components in overlapping chromatograms was proposed by imitating biological immune systems. The algorithm takes an overlapping chromatogram as its input and subtracts the chromatograms of standard samples from the input by iteration of a network. When the residual does not change, the network will converge and chromatographic information of the components in overlapping chromatogram will be obtained. Both simulated and experimental data sets were investigated by the method. Results showed that both resolved results and recoveries of quantitative determination are satisfactory. Comparing with conventional least-square method, the immune algorithm is fast in calculation. 相似文献
919.
920.
Yuan Zhihao Wang Yuhong Sun Yongchang Wang Jing Bie Lijian Duan Yueqing 《中国科学B辑(英文版)》2006,49(1):67-74
A nanocomposite photocatalyst composed of AlFeO3 and TiO2 is prepared, and characterized through X-ray diffraction. Application of the nanocomposite for the photodegradations of eosin
dye and methyl orange gives an improved photoactivity compared with TiO2-only nanomaterials. The optimal concentration of AlFeO3 in the composite is about 1.0 wt% under UV excitation, and 9.0 wt% under sunlight excitation for the improved photoactivity.
Furthermore, this nanocomposite is more active for eosin photodegradation if natural sunlight rather than UV is used. This
may be due to the reason that adding AlFeO3 nanoparticles into TiO2 matrix can promote the separation of photogener-ated charge carriers, and extend the photoresponse of TiO2 toward visible region, which results in an increase in the solar energy utilization efficiency. 相似文献