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51.
The rhodium-phosphine complex catalyst Rh(CO)(acac)(PPh3)(Ⅰ) for 1-hexene hydroformylation was studied under the following reaction conditions: CO/H2=1(mole rate), pressure 1.0 MPa, temperature 25-120℃, by using the pressurized in-situ 1H NMR technique. Experimental results indicated that the formation of a rhodium hydride complex from (Ⅰ) began at room temperature and its amount increased with increasing of reaction temperature. This intermediate complex began to decompose at 100℃ and disapeared completely at 120℃. The intensity change of the proton signal was parallel to catalytical activity in hydroformylation of olefins. Under pure CO pressure the proton signal of Ph-H bond was not observed. There was a 0.2 ppm difference in proton chemical shifts of Rh-H bond under pure H2 pressure and under H2+CO pressure. The results showed that the rhodium-hydride carbonyl complex is the active intermediate in the industrial hydroformylation process. 相似文献
52.
茶汤及河水中铁的形态分析 总被引:11,自引:0,他引:11
本文采用阳离子交换、活性炭分离-光度法研究了铁的形态分离及测定条件,建立了铁的形态分析方法。应用此法测定了茶汤及河水中铁的总量、悬浮态、溶解态、无机态、有机态、Fe(Ⅲ)和Fe(Ⅱ)等形态,结果令人满意。 相似文献
53.
Employing hot tungsten filament to thermal dissociate molecular hydrogen,we generated gas phase atomic hydrogen under ultra-high vacuum(UHV)conditions and investigated its interaction with Pt(111) surface.Thermal desorption spectroscopy(TDS)results demonstrate that adsorption of molecular hy- drogen on Pt(111)forms surface Had species whereas adsorption of atomic hydrogen forms not only surface Had species but also bulk Had species.Bulk Had species is more thermal-unstable than surface Had species on Pt(111),suggesting that bulk Had species is more energetic.This kind of weakly- adsorbed bulk Had species might be the active hydrogen species in the Pt-catalyzed hydrogenation reactions. 相似文献
54.
Mao-Peng Lin Haeng-Boo Kim Tomiki Ikeda Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》1992,30(11):2365-2369
Benzyl cation was detected by transient absorption spectroscopy with a spectroscopic multichannel analyzer on pulse excitation (fourth harmonic of Nd:YAG laser, 266 nm; 10 ns fwhm) of benzyl(4-hydroxyphenyl) methylsulfonium hexafluoroantimonate(BSS) in 1,2-dichloroethane (EDC). The benzyl cation was long-lived (lifetime, 59 ms) at room temperature and quenched by a vinyl ether compound. The formation of the benzyl cation as active species on photolysis of BSS is in contrast to the formation of Brønsted acids in other sulfonium salts so far reported. © 1992 John Wiley & Sons, Inc. 相似文献
55.
56.
NH_3-TPD技术表征固体催化剂的酸性似乎已很成熟,其实不然。如该技术表征HZSM-5沸石时,有作者观察到773K左右的高温脱氨峰,而有些作者则检测不到。诚然,各作者间所用试样及预处理条件等存在差异,但实验装置和实验操作条件不同带来的影响也不可忽视。此外,该技术在用于表征一些新的较复杂的催化剂时,其程脱谱也会呈现出新现象,这些现象有时是不能通过酸性来解释的,这是因为NH_3作为探针分子不仅具有碱性,同时还有还原性和配位性。本文对载镍沸石上NH_3-TPD谱图中出现的某些新峰进行了剖析和归属。 相似文献
57.
YUAN Song-Yue ZHAO ZhenChangchun Institute of Applied Chemistry. Academia Sinica Changchun Jilin CYU Zuo-LongChengdu Institute of Organic Chemistry. Academia Sinica Chengdu. Sichuan To whom correspondence should be addressed 《天然气化学杂志》1995,(3)
The surface basicity of Ti-La-Li multicoinponent oxides has been investigated by means of CO2-TPD. The experiment results show that C2 (C2H6 C2H4) selectivity is related to surface basic strength. The surface active oxygen species have also been characterized by means of XPS, O2-TPD and so on. It has been indicated that C2 selectivity and CH4 conversion are correlated with lattice oxygen and the adsorbed oxygen on the surface of the catalyst respectively In the O2-TPD experiments, it has also been found that there are three kinds of oxygen species on the surface of the series catalvsts, which are a (100℃ 750℃) Among them α-oxvgen causes deep oxidation whileβand γ oxygen species are related to oxidalive coupling of methane (OCM). 相似文献
58.
Summary Two epimers of the mycotoxin chlamydosporol were separated by HPLC on an RP-18 column using a quaternary mobile phase consisting of water (79.1%), methanol (10.0%), acetonitrile (10.4%) and tetrahydrofuran (0.5%), with a flow rate of 1 ml min–1. This optimal composition of mobile phase, with which the resolution value for the two epimers (1 and2) was 2.73 with retention times of 5.88 and 7.12 min, respectively, was achieved by the application of Philips Solvent Optimisation Software PU 6100. The presence of free silanols on the stationary phase was shown to be an essential requirement for the separation of the chlamydosporol epimers. 相似文献
59.
A new direct procedure for the determination of inorganic arsenic species was developed by electrochemical hydride generation atomic absorption spectrometry (EcHG-AAS) with selective electrochemical reduction. The determination of inorganic arsenic species is based on the fact that As(Ⅲ) shows significantly higher absorbance at low electrolytic currents than As(Ⅴ) in 0.3 mol·L^-1 H2SO4. The electrolytic current used for the determination of As(Ⅲ) without considerable interferences of As(Ⅴ) was 0.4 A, whereas the current for the determination of As(Ⅲ) and As(Ⅴ) was 1.2 A. For equal concentrations of As(Ⅲ) and As(Ⅴ) in a sample, the interferences of As(Ⅴ) during the As(Ⅲ) determination were smaller than 5%. The absorbance for As(Ⅴ) could be calculated by subtracting that for As(Ⅲ) measured at 0.4 A from the total absorbance for As(Ⅲ) and As(Ⅴ) measured at 1.2 A, and then the concentration of As(Ⅴ) can be obtained by its calibration curve at 1.2 A. The methodology developed provided the detection limits of 0.3 and 0.6 ng·mL^-1 for As(Ⅲ) and As(Ⅴ), respectively. The relative standard deviations were of 3.5% for 20 ng·mL^-1 As(Ⅲ) and 3.2% for 20 ng·mL^-1 As(Ⅴ). The method was successfully applied to determination of soluble inorganic arsenic species in Chinese medicine. 相似文献
60.
In the presence of CuCN, reaction of γ,γ-dialkoxyallylic zirconium species 1 with imines proceeded at the γ-position of 1 to give gem-dialkoxyhomoallylic amines 3 in high yield. In this reaction, γ,γ-dialkoxyallylic zirconium species 1 acts as an α,β-unsaturated acyl anion equivalent. 相似文献