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991.
Hydroxyl (OH) is identified and characterized on the Ni(111) surface by high‐resolution electron energy loss spectroscopy. We find clear evidence of stretching, bending, and translational modes that differ significantly from modes observed for H2O and O on Ni(111). Hydroxyl may be produced from water by two different methods. Annealing of water co‐adsorbed with atomic oxygen at 85 K to above 170 K leads to the formation of OH with simultaneous desorption of excess water. Pure water layers treated in the same fashion show no dissociation. However, the exposure of pure water to 20 eV electrons at temperatures below 120 K produces OH in the presence of adsorbed H2O. In combination with temperature‐programmed desorption studies, we show that the OH groups recombine between 180 and 240 K to form O and immediately desorbing H2O. The lack of influence of co‐adsorbed H2O at 85 K on the O? H stretching mode indicates that OH does not participate in a hydrogen‐bonding network. 相似文献
992.
Gabriela Smeureanu Dr. Amit Aggarwal Clifford E. Soll Dr. Julius Arijeloye Erik Malave Charles Michael Drain Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):12133-12140
The catalytic oxidation of alkenes by most iron porphyrins using a variety of oxygen sources, but generally not dioxygen, yields the epoxide with minor quantities of other products. The turnover numbers for these catalysts are modest, ranging from a few hundred to a few thousand depending on the porphyrin structure, axial ligands, and other reaction conditions. Halogenation of substituents increases the activity of the metalloporphyrin catalyst and/or makes it more robust to oxidative degradation. Oxidation of cyclohexene by 5,10,15,20‐tetrakis‐(2,3,4,5,6‐pentafluorophenyl)porphyrinato iron(III), ([FeIII(tppf20)]) and H2O2 is typical of the latter: the epoxide is 99 % of the product and turnover numbers are about 350. 1 – 4 Herein, we report that dynamic organic nanoparticles (ONPs) of [FeIII(tppf20)] with a diameter of 10 nm, formed by host–guest solvent methods, catalytically oxidize cyclohexene with O2 to yield only 2‐cyclohexene‐1‐one and 2‐cyclohexene‐1‐ol with approximately 10‐fold greater turnover numbers compared to the non‐aggregated metalloporphyrin in acetonitrile/methanol. These ONPs facilitate a greener reaction because the reaction solvent is 89 % water and O2 is the oxidant in place of synthetic oxygen sources. This reactivity is unexpected because the metalloporphyrins are in close proximity and oxidative degradation of the catalyst should be enhanced, thus causing a significant decrease in catalytic turnovers. The allylic products suggest a different oxidative mechanism compared to that of the solvated metalloporphyrins. These results illustrate the unique properties of some ONPs relative to the component molecules or those attached to supports. 相似文献
993.
Blue emission of oxygen‐doped tertiary amine (triethylamine), a key unit of fluorescent poly(amido amine) dendrimer, was demonstrated. It was found that the fluorescence intensity could be further enhanced if the tertiary amines locate densely in the dendrimer interior as the branching sites. Moreover, a solvatochromic phenol blue, instead of oxygen, is able to induce the blue fluorescence of the tertiary amino‐branching sites based on a guaranteed host‐guest complexation of phenol blue molecules and dendrimer interior.
994.
Polymerizable vinylimidazolium ionic liquids (ILs) that contain mesogenic coumarin and biphenyl units, respectively, have been synthesized. The N‐alkylation of N‐vinylimidazole with bromoalkylated mesogenic units 7‐(6‐bromohexyloxy)coumarin ( 1 ) and 4,4′‐bis(6‐bromohexyloxy)biphenyl ( 2 ) was then carried out. The thermal behavior of the obtained ILs 3 and 4 was investigated by differential scanning calorimetry and polarizing optical microscopy. These measurements showed that the attached mesogenic units induce the self‐assembly of ILs and, therefore, the occurrence of liquid crystalline phases. Subsequently, the ionic liquid crystals (ILCs) 3 and 4 were polymerized by a free‐radical mechanism.
995.
Bagiyan G. A. Koroleva I. K. Soroka N. V. Ufimtsev A. V. 《Russian Chemical Bulletin》2003,52(5):1135-1141
Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity. 相似文献
996.
SrTi0.9M0.1O3-δ钙钛矿型氧化物催化剂甲烷氧化偶联反应性能的研究 总被引:2,自引:0,他引:2
The structure and catalytic properties of SrTi0.9M0.1O3-δ (M=Mg,Al, Zr) perovskite-type catalysts for ox-idative coupling of methane (OCM) have been studied by using X-ray diffraction (XRD),X-ray photoelectron spectroscopy (XPS) and temperature-programmed desorption of oxygen(O2-TPD) methods. It has been shown that doping the cations of lower valence (e.g. Mg2+, Al3+) to the B site of SrTi0.9M0.1O3-δ perovskite-type catalysts results in the higher content of adsorbed oxygen species on the surface of catalysts and thus higher C2-selectivity for OCM reaction. It is suggested that the oxygen vacancies of SrTi0.9M0.1O3-δ (M=Mg, Al, Zr) perovskite-type catalysts are the sites responsible for oxygen activation, and the adsorbed oxygen species on the surface of SrTi0.9M0.1O3-δ catalysts are the main active species for OCM reaction. 相似文献
997.
纳秒强激光场中苯电离产生高价离子的研究 总被引:2,自引:0,他引:2
用25 ns脉冲Nd-YAG 532 nm的激光,在1010~1011 W•cm-2的光场强度下,利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时,除观察到C2+、C2H2+、C3H3+、C6H6+离子外,还观察到很强的Cq+(q=1~3)高价离子.这些离子都有很高的平动能, C2+的最可几平动能为12.9 eV, C3+为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验,可以认为这些高价离子来源于含苯团簇的库仑爆炸过程. 相似文献
998.
Electrophoretic mobilities of hexadecane/water emulsions containing dimyristoyl-phosphatidylcholine (DMPC) or egg yolk lecithin
(EYL) monolayers at the interface and those of liposomes prepared from the same lipids were measured as functions of the concentrations
of Ca2+, Mn2+, Cu2+, and Ni2+ cations in the aqueous phase. The surface potentials, surface charge densities (σ), and the Langmuir adsorption isotherms
for various distances from the charged surface to the slip plane (d) were calculated on the basis of the Gouy-Chapman theory for 1∶2 electrolytes and the values of ζ-potentials. The binding
constants (K) and parametersd were determined under the assumption that the maximum σ values correspond to one ion per phospholipid molecule at the interface.
In the case of DMPC, the ion binding constants (L mol−1) at 25°C are 230 and 87 for Ca2+, 31.5 and 21 for Mn2+, 11 and 6 for Cu2+, and 7.5 and 5.3 for Ni2+ in liposomes and emulsions, respectively. The affinities of Cu2+ and Ni2+ ions for EYL monolayers and bilayers are lower than those for DMPC mono- and bilayers. Thed parameters for all ions are smaller than the radii of the hydrated ions. In the case of Ca2+, Cu2+, and Ni2+, thed values for mono- and bilayers are different. The differences in K values between monolayers and bilayers as well as those
between DMPC and EYL mono- and bilayers can be attributed to the differences in the local environment and orientation of the
interfacial phosphate groups in these systems.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2490–2495, December, 1998. 相似文献
999.
1000.
用CuO/γ-Al2O3催化剂同时脱除烟气中的SO2和NO 总被引:13,自引:1,他引:13
研究了用CuO/γ-Al2O3催化剂同时脱除烟气中的SO2和NO,并在固定床反应器中考察了反应条件对其催化活性的影响.结果表明,温度和SO2对CuO/γ-Al2O3的催化活性均具有双重影响.新鲜催化剂和硫化催化剂上最适宜的脱硝温度分别为250~300℃和300~450℃,最适宜的n(NH3)/n(NO)约为1.2.烟气中的氧可大大提高CuO/γ-Al2O3的脱硫脱硝活性.综合考虑吸附硫容和NO脱除率,CuO/γ-Al2O3同时脱硫脱硝的最适宜温度为350~450℃.温度和SO2在高温区对CuO/γ-Al2O3活性的影响源于两者对NH3氧化活性的改变,高温下CuO/γ-Al2O3的活性下降是因为NH3氧化加剧;SO2通过使催化剂硫化生成硫酸盐来抑制NH3氧化,从而提高CuO/γ-Al2O3的活性.吸硫饱和的催化剂可于5%NH3中还原再生,再生后其硫容较初始时降低,但其活性大幅度提高. 相似文献