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11.
Ceria-supported copper-palladium catalysts have been tested in the hydrogenation of 1,3-butadiene. The SMSI behavior of the bimetallic catalysts depended on the temperature of reduction. They were analyzed by H2 chemisorption and XPS. 相似文献
12.
Kim HG Lee CW Yun S Hong BH Kim YO Kim D Ihm H Lee JW Lee EC Tarakeshwar P Park SM Kim KS 《Organic letters》2002,4(22):3971-3974
[formula: see text] A new molecular system, 2,11-dithio[4,4]metametaquinocyclophane containing a quinone moiety, was designed and synthesized. As the quinone moiety can readily be converted into an aromatic pi-system (hydroquinone) upon reduction, the nanomechanical molecular cyclophane system exhibits a large flapping motion like a molecular flipper from the electrochemical redox process. The conformational changes upon reduction and oxidation are caused by changes of nonbonding interaction forces (devoid of bond formation/breaking) from the edge-to-face to face-to-face aromatic interactions and vice versa, respectively. 相似文献
13.
The near-diffusion-controlled reactions of hydroxyl radical, hydrated electron, and hydrogen atom with platinum macrocyclic complex ions in aqueous media have been studied using pulse radiolysis in conjunction with UV-visible absorption and conductivity detection. The hydrated electron and hydrogen atom react with trans-[Pt(cyclam)(Cl)(2)](2+) where cyclam is 1,4,8,11-tetraazacyclotetradecane to yield platinum(III) transients that exhibit intense absorption peaks in the 280-300 nm region; however in the case of the H-atom, the reaction involves a competition between chloride abstraction and a minor process, suggested to be attack on the organic ligand. The platinum(III) products are kinetically labile toward loss of chloro ligands, but these reactions are reversible in the presence of added KCl. The reactions of hydroxyl radical with [Pt(cyclam)](2+) and with [Pt(tmc)](2+), where tmc is 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, lead to platinum(III) intermediates absorbing in the 250-300 nm region. Depending on the presence or absence of added KCl and on the pH, the platinum(III) cyclam systems can react to form a product(s) exhibiting absorption peaks near 330 and 455 nm, and this species is proposed to be a long-lived amidoplatinum(III) complex. In support of this proposal is the observation that the tmc system does not give rise to a similar visible-absorbing product. The interrelations of the cyclam-based transients through acid-base, chloro-substitution and water-elimination processes are discussed. 相似文献
14.
Hyoung Sik Kim Min Kang Min Woo Song Jin Won Park Byoung Ryul Min 《Reaction Kinetics and Catalysis Letters》2004,81(2):251-257
Pt-Pd bimetallic catalysts were prepared in order to develop and investigate catalysts having excellent activity and stability
for benzene destruction. The effect of Pt addition to Pd catalysts is studied by XPS analysis.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
15.
Young-Gu Cho Dae-Kwang Park Dae-Won Park Hee-Chul Woo Jong-Shik Chung 《Research on Chemical Intermediates》2002,28(5):419-431
The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over vanadium-bismuth mixed oxide catalysts. The investigation was focused on understanding the complex reaction steps and the roles of each metal oxide. Therefore, supported V2O5/TiO2, V-Bi-O/TiO2 catalysts and a mechanical mixture of V2O5 + Bi2O3 were tested in the reaction. Ammonia reacted either with H2S or SO2, produced from the oxidation of H2S. Water vapor promoted the reaction of ammonia and SO2. Strong synergistic phenomena in catalytic activity were observed for the mechanically mixed catalyst of V2O5 and Bi2O3. V-Bi-O/TiO2 catalyst showed very high H2S conversion without any considerable emission of SO2. Temperature-programmed studies (TPR and TPO), XRD and Raman analyses revealed that the high catalytic performance of V-BiO/TiO2 catalyst originated from the high redox capacity of the bismuth vanadate phase. 相似文献
16.
We have measured the rate of carbon dioxide evolution in the aniline catalyzed decomposition of acetone dicarboxylic acid in a mixture of isobutyric acid + water near its consolute point. Within a temperature interval of 1 degrees C, which included the critical solution temperature, the first-order rate constant oscillated in magnitude by about 10% as it passed through three complete cycles of slowing down followed by speeding up. Whereas we can find no ready explanation for the speeding up, we suggest that, because the mixture contained no inert components, the slowing down should belong to the Griffiths-Wheeler class of strong critical effects [Phys. Rev. A 1970, 2, 1047]. As a check on this conclusion, we have measured the rate of the SN1 decomposition of benzene diazonium tetrafluoroborate in 2-butoxyethanol + water near the lower critical solution temperature and also the rate of the acid-catalyzed decomposition of ethyl diazoacetate in isobutyric acid + water near the upper critical solution temperature. Both of these reactions evolve nitrogen. In the first reaction, 2-butoxyethanol is inert, whereas in the second, isobutyric acid is inert. In both cases, because there was one inert component, we regarded the response of the rate constant to temperature in the critical region to be representative of the Griffiths-Wheeler class of weak critical effects. Within our accuracy of measurement of about 2% in the rate constant and about 1 mK in the temperature, we could detect no effect of the critical point on the rates of either of these reactions, suggesting that a weak effect may be too small to be seen with our experimental apparatus. The successful observation of a critical effect in the rate of decomposition of acetone dicarboxylic acid proves, however, that kinetic critical phenomena are observable in heterogeneous reactions. 相似文献
17.
Sung Woo Moon Gun-Dae Lee Seong Soo Park Seong-Soo Hong 《Reaction Kinetics and Catalysis Letters》2004,82(2):303-310
Catalytic combustion of chlorobenzene over supported vanadium oxides has been investigated. TiO2 was prepared by the sol-gel method from titanium isopropoxide. The supported vanadium oxide catalysts have been prepared
by precipitation-deposition and impregnation method and characterized by XRD, FT-Raman and TPR. In the VOx/TiO2catalysts prepared using the impregnation method, when vanadium loading reaches 3 wt.%, the activity shows a maximum. However,
in the VOx/TiO2catalysts prepared by precipitation-deposition, when vanadium loading reaches 7 wt.%, the activity shows a maximum. This result
suggests that the precipitation-deposition can yield a higher metal loading on the support and a high dispersion compared
to the impregnation method.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
18.
For any -complexes and , we show that . We use this fact to compute generalized evaluation subgroups of generalized tori relative to a sphere.
19.
The organic basic solution, 1 M tetramethylammonium hydroxide (TMAH) in methanol, was employed for the hydrolysis of extremely small amounts of lipids compared to the classical inorganic basic solution, 1 M KOH in ethanol. The hydrolysed fatty acids were derivatized as N(O)-tert.-butyldimethylsilyl (tBDMSi) esters with N-methyl-N-(tert.-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) and compared with the classical derivatives, the methyl esters, made by the BF3-methanol method. Recoveries of fatty acids determined on the standard fatty acids and soybean oil hydrolysed with TMAH were high: about 1.1-2.1- and 2.0-5.4-times, respectively, in all fatty acids compared with the hydrolysis by KOH regardless of derivatization method. The relative standard deviations (RSDs) on the recoveries of standard fatty acids were less than 5% when hydrolysed with TMAH, regardless of derivatives, but when hydrolysed with KOH, RSDs were more than 5% for most fatty acids, especially for long-chain fatty acids. The RSDs on the recoveries of fatty acids on the soybean oil were also very high in the KOH hydrolysis. Fatty acid compositions of soybean oil were similar in the main fatty acids regardless of hydrolysis methods, but showed slightly different values, depending on the methods of derivatization. RSDs were also very high in the KOH hydrolysis. In view of these results, precision of analysis by KOH hydrolysis was very poor, so we could not rely on the data. On the other hand, the reliability of data by TMAH hydrolysis method was very high, so it is a useful new hydrolysis method for extremely small amounts of lipid samples. Both derivatives of 35 standard fatty acids were successfully separated on a HP-1 nonpolar capillary column. tBDMSi derivatives were completely resolved in 70 min by 295 degrees C. In the methyl ester derivatives it took about 80 min to get satisfying resolution, but these derivatives were completely resolved by 250 degrees C. The sensitivity of tBDMSi derivatives was about 1.5-6.3-times higher than that with methyl ester derivatives. The stability of tBDMSi derivatives was constant for about 144 h except arachidic, docosahexanoic, behenic and heneicosanoic acids, which were stable for only 86 h. 相似文献
20.
The mass spectral decomposition modes of a series of 2-imino-4-thiazolidinone derivatives are reported and discussed. The fragmentation patterns and mechanisms postulated have been confirmed by the analysis of the MIKE spectra and using DADI technique and the effects of heteroatoms and substituents on the MIKE spectrum of these compounds are compared with that of 3-substituted hydantoins. 相似文献