INVESTIGATION OF THE SURFACE CHARACTERISTICS AND CATALYTIC ACTIVITY OF Sb_xO_y/SiO_2CATALYSTS FOR VAPOR-PHASE SYNTHESIS OF ISOPRENE FROM ISOBUTYLENE AND FORMALDEHYDE

The surface characteristics and catalytic activity of Sb_xO_Y/ SiO_2 catalysts forvapor-phasc synthesis of isoprene from isobutylene and formaldehyde have been investi-gated by TPR, XRD, XPS, IR and catalytic activity evaluation. The results show that whenthe Sb loadings are less than about 5 wt%,Sb_xO_Y is compIctely dispersed on the surface ofsilica to form a surface compound with Sb(V)=O group and the catalysts have relativelyhigh catalytic activity; when the Sb loadings are more than 5 wt%, in addition to this surfacccompound, the crystalline α-Sb_2O_4 is formed on the support surface and causes rapid de-crease of catalytic activity. It is suggcsted that the catalytic activity of Sb_xO_Y /siO_2 catalystsresults from synetgistic catalysis of the surface compound Sb(V)=O as the basic sites andthe surface silanol Si-OH as the acidie sites. The mechanism of this synergistic catalysis forisoprene production is discussed.     

Systematic variation of the sodium/sulfur promoter content on carbon-supported iron catalysts for the Fischer–Tropsch to olefins reaction

The Fischer–Tropsch to olefins(FTO) process is a method for the direct conversion of synthesis gas to lower C_2–C_4olefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content(1–3 wt%) leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents(1–3 wt% sodium and 0.5–1 wt% sulfur) but a minimum amount of alkali is required to effectively suppress methane and C_2–C_4paraffin formation. A reference catalyst support(carbide-derived carbon aerogel) shows that the optimum promoter level depends on iron particle size and support pore structure.     

Comparison Between Catalytic Activity and Activity Changes During Denaturation by Guanidine Hydrochloride of Enzymes in Crystalline State and in Solution

The catalytic activity and activity changes during denaturation by guanidine hydrochloride of glyceraldehyde-3-phosphate dehydrogenase,lactate dehydrogenase and α-chymotrypsin in crystalline state and in solution have been compared.The catalytic activities are lower in crystalline state than in solution. Enzymes in crystalline state are more stable than in solution during denaturation by guanidine hydrochloride.Ammonium sulfate has different effects on catalytic activities of different enzymes and shows protection on all enzymes studied during denaturation by guanidine hydrochloride.The protection is more obvious at high concentrations of guanidine hydrochloride than at low concentrations.It is suggested that the flexibility or mobility of enzyme is required for the catalytic activity and related to the stability of enzymes. Enzymes with less flexibility or mobility are more stable.     

Effects of Ru nanoparticle sizes confined in cavities of SBA-16 on the catalytic performance of Fischer-Tropsch synthesis reaction

Ru nanoparticles with different sizes confined in the cavities of mesoporous SBA-16 have been successfully synthesized by incipient wetness impregnation method with a Ru loading of 4 wt%. The catalysts were characterized by XRD, N2 adsorption-desorption, H2-TPR, H2-TPD, O2-titration and TEM. The catalytic performance of Fischer-Tropsch synthesis over the catalyst was tested in a fixed-bed reactor. The addition of citric acid in the impregnation procedure shows a significant influence on the size of Ru nanoparticles. The selectivity to C5+ increases, while the selectivities to methane and C2-C4 light hydrocarbons decrease with Ru average particles size from 2.0 nm to 9.3 nm,. The Ru catalyst confined in the SBA-16 with average nanoparticle size of 5.3 nm gives the best activity.     

Effects of CeO_2 preparation methods on the catalytic performance of MoO_3/CeO_2 toward sulfur-resistant methanation

CeO_2 supports were prepared by calcination or precipitation method and 5% MoO_3/CeO_2 catalysts were prepared by incipient-wetness impregnation method. The catalytic performance of the 5% MoO_3/CeO_2 catalysts toward sulfur-resistant methanation was investigated. The results showed that the Mo/Ce-1 catalysts with CeO_2 support prepared by calcination method exhibited the best sulfur-resistant methanation activity and stability with CO conversion as high as 75% while the Mo/Ce-3 catalysts the poorest. The supports and catalysts were characterized by N_2-adsorption–desorption, temperature-programmed reduction(TPR), X-ray diffraction(XRD), Raman spectroscopy(RS) and scanning electron microscope(SEM). The results indicated that the saturated monolayer loading MoO_3 on Ce-3 support was lower than 5% and there were some crystalline MoO_3 particles on the surface of the Mo/Ce-3. The preparation method of CeO_2 had a big influence on the specific surface area, the crystalline of CeO_2, and the catalytic performance of the corresponding Mo-based catalyst for sulfur-resistant methanation.     

Selective hydrogenation of benzene to cyclohexene over Ce-promoted Ru catalysts

Ru-Ce catalysts were prepared by a co-precipitation method.The effects of Ce precursors with different valences and Ce contents on the catalytic performance of Ru-Ce catalysts were investigated in the presence of ZnSO4.The Ce species in the catalysts prepared with different valences of the Ce precursors all exist as CeO2 on the Ru surface.The promoter CeO2alone could not improve the selectivity to cyclohexene of Ru catalysts.However,almost all the CeO2 in the catalysts could react with the reaction modifier ZnSO4 to form(Zn(OH)2)3(ZnSO4)(H2O)3 salt.The amount of the chemisorbed salt increased with the CeO2 loading,resulting in the decrease of the activity and the increase of the selectivity to cyclohexene of Ru catalyst.The Ru-Ce catalyst with the optimum Ce/Ru molar ratio of 0.19 gave a maximum cyclohexene yield of 57.4%.Moreover,this catalyst had good stability and excellent reusability.     

Role of surface defects of carbon nanotubes on catalytic performance of barium promoted ruthenium catalyst for ammonia synthesis

Carbon nanotubes(CNTs) with abundant surface defects are prepared by a liquid oxidation and thermal annealing method. The defective CNTs-D supported Ba–Ru/CNTs-D catalysts exhibit superior catalytic performance in ammonia synthesis with a TOF be increased up to 0.30 s-1, which is 2.5 times of oxidized CNTs-O supported Ba–Ru/CNTs-O catalysts and 5 times of the Ba–Ru/CNTs. The characterizations by CO chemisorption, transmission electron microscope, Raman, and X-ray photoelectron spectroscopy revealed that the uniformly well dispersed Ru NPs can be stabilized on the defective sites of CNTs-D. The great improvement of the catalytic performance and stability of the Ba–Ru/CNTs-D is contributed to the strong interaction between Ru NPs and surface defect of the CNTs.     

STUDY ON POLYMER-Ru-Co BIMETALLIC COMPLEXES CATALYSTS Ⅱ.X-RAY PHOTOELECTRON SPECTROSCOPIC ANALYSIS

Polymer Ru-Co bimetallic complexes have been examined by X-ray photoelectron spectroscopy.The catalyst is highly active only when the mole ratio of Co/Ru is 4: 3. The activity of catalysts does not depend on the total Co/Ru ratio, but on the surface stoichiometry of Co and Ru. When the relative intensities of Co_2_p and Ru_(3d) of XPS peaks are close to each other and both are high,the catalyst exhibits its maximum activity The mechanism ofcatalytic hydroformylation has been discussed.     

Hydrogenolysis of glycerol over HY zeolite supported Ru catalysts

An enhanced active and selective catalyst consisting of ruthenium supported on dealuminated HY zeolite has been prepared by a wet impregnation method. It was found that BET surface area of Ru/HY catalysts significantly increases after HCl treatment. This treatment also increases the concentration of strong acid sites in the catalyst. The hydrogenolysis of glycerol over 5 wt% Ru/HY catalyst was investigated at 190-220 ℃, an initial H2pressure of 3-6 MPa, and in 20 wt% glycerol aqueous solution. The results indicate that HCl treated Ru/HY catalyst shows higher activity compared with the untreated Ru/HY catalyst, and that the glycerol hydrogenolysis efficiency is influenced by the porosity and acidity of the support. A selectivity to 1,2-PDO of 81.3% at a glycerol conversion of 60.1% under 3 MPa H2pressure and 220 ℃ for 10 h was achieved over the modified Ru/HY catalyst with a 1.0 mol/L HCl treatment. It has also been shown that a longer reaction time, a higher temperature and a higher H2pressure have the positive effects on the glycerol hydrogenolysis efficiency of the enhanced Ru/HY.     

SYNTHESIS OF POLYMER-STABILIZED PLATINUM/RUTHENIUM BIMETALLIC COLLOIDS AND THEIR CATALYTIC PROPERTIES FOR SELECTIVE HYDROGENATION OF CROTONALDEHYDE

Polymer-stabilized platinum/ruthenium bimetallic colloids （Pt/Ru） were synthesized by polyol reduction with microwave irradiation and characterized by TEM and XPS. The colloidal nanoparticles have small and narrow size distributions. Catalytic performance of the Pt/Ru colloidal catalysts was investigated on the selective hydrogenation of crontonaldehyde （CRAL）. A suitable amount of the added metal ions and base can improve the selectivity of CRAL to crotylalcohol （CROL） remarkably. The catalytic activity and the selectivity are dependent on the compositions of bimetallic colloids. Thereinto, PVP-stabilized 9Pt/1Ru colloid with a molar ratio of metals Pt：Ru = 9：1 shows the highest catalytic selectivity 77.3% to CROL at 333 K under 4.0 MPa of hydrogen.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.