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《Journal of Industrial and Engineering Chemistry》2014,20(2):379-390
The novel functional composite silica microspheres encapsulated by organophosphonated polystyrene (SGPSNP) has been successfully synthesized. SGPSNP was employed to adsorb Au(III) from simulated wastewater, and it exhibited excellent performance, and the maximum adsorption capacity was 980.39 mg/g at 35 °C. The adsorption process optimization was performed using response surface methodology (RSM), and the analysis of variance (ANOVA) of the quadratic model demonstrated that the model was highly significant. Moreover, the regeneration capacities of SGPSNP were investigated, and it has been found that the adsorption capability remains high after several cycles of adsorption–desorption. 相似文献
3.
《Catalysis Today》2005,99(1-2):43-49
Three single crystalline MoVO based oxides, MoVO, MoVTeO and MoVTeNbO, all of which have the same orthorhombic layer-type structure with the particular arrangement of MO6 (M = Mo, V, Nb) octahedra forming slabs with pentagonal, hexagonal, and heptagonal rings in (1 0 0) plane, were synthesized by hydrothermal method and their catalytic performance in the selective oxidation of propane to acrylic acid were compared in order to elucidate the roles of constituent elements and crystal structure in the course of the propane oxidation. It was observed that the rate of propane oxidation was almost the same over all three catalysts, revealing that Mo and V, which were indispensable elements for the structure formation, were responsible for the catalytic activity for propane oxidation. The Te-containing catalysts showed much higher selectivity to acrylic acid than the MoVO catalyst. Since propene was formed as a main product at low conversion levels over every catalyst, it can be concluded that Te located in the central position of the hexagonal ring promoted the conversion of intermediate propene effectively to acrylic acid. The catalyst with Nb occupying the same structural position of V clearly showed the improved selectively to acrylic acid particularly at high conversion region, because the further oxidation of acrylic acid to COx was greatly suppressed. These conclusions were further supported by the additional studies of the determination of activation energy and catalytic oxidations of intermediate products of the propane oxidation. 相似文献
4.
《Journal of the European Ceramic Society》2005,25(2-3):251-256
Bulk SiBCN ceramics derived from polyborosilazanes of the type [B(C2H4SiRNH)3]n (1a, R = CH3; 2a, R = H; C2H4 = CHCH3, CH2CH2) exhibit an exceptional structural stability at high temperature. Therefore, such quaternary systems are of great scientific and technical interest as fibrous reinforcements intended for high-temperature applications. In this context, the design of novel polyborosilazanes, which display properties tailored for the preparation of SiBCN fibers, is studied. Boron-modified polysilazanes of the type [B(C2H4SiRNCH3)3]n (1b, R = CH3; 2b, R = H) are prepared via aminolysis of the tris(dichlorosilylethyl)boranes B(C2H4SiRCl2)3 (1, R = CH3; 2, R = H). It is shown that the functionalisation of the precursors with NCH3 units improves their processability (i.e. solubility) compared to that of their ammonolysed analogs [B(C2H4SiRNH)3]n (1a, R = CH3; 2a, R = H). In addition to the influence of the NCH3 units, the presence of the SiCH3 functions in such polymers offers the best potential for the preparation of fibers by melt-spinning. As-spun fibers are then converted under controlled atmosphere into high-temperature stable SiBCN fibers according to the polymer-derived ceramic route. 相似文献
5.
《Applied catalysis》1987,29(1):125-140
The Australian brown coal-derived oil mixed with a hydrogenated creosote oil was hydrotreated over NiMo and CoMoγAl2O3 catalysts. The initial catalytic activities varied with the reaction for each catalyst: converting of the hexane-insolubles to the hexane-soluble oils(HDHI) > hydrodesulfurization(HDS) > hydrodenitrogenation(HDN) > hydroconverting of the 623 K+ residues to the 623 K− oils(HDC). A NiMo catalyst showed higher activities than a CoMo catalyst did. The initial catalyst deactivation was significant in the order of HDC > HDN > HDS > HDHI for each catalyst. The degrees of the deactivation were larger for a CoMo catalyst. The analyses of the spent catalysts showed that the pore volumes and the surface areas were decreased markedly by the carbonaceous deposits, in which higher amounts of the N- and O-containing compounds accumulated. The XPS and elemental analyses of the spent catalysts indicated that the decreases in the amounts of sulfur during the course of run were linked with the decreases in the sulfidic states of molybdenum(Mo4+ species) and the promoters. These carbonaceous deposits and the changes in chemical states of the supported metals were interpreted as the main reasons for the initial catalyst deactivation. 相似文献
6.
The effect of scrap automobile catalyst (SAC), a waste material, was investigated as a catalyst for the reduction of nitroarenes to the corresponding amines with sodium borohydride in aqueous ethanol at 5–25 °C. Along with the observed high conversions, the SAC and NaBH4 combination also exhibits a selectively catalyzed reduction in compounds containing other reducible functionalities, such as CN, Br, Cl and I. Recycling automobile wastes into a catalyst for organic reactions will offer both environmental protection and economic advantages. As a result, an effective, easy to use, low-priced and reliable method has been developed. 相似文献
7.
《Applied catalysis》1989,46(2):241-249
The hydrotreatment of some aromatic amines was studied at temperatures ranging from 400 to 450°C and PH2=1 atm under flow conditions. Hydrogenolysis of aromatic amines involves direct cleavage of the C(sp2)N bond without saturation of the aromatic ring. The presence of hydrogen sulphide in the reaction stream has a promotional effect on the hydrogenolysis of C(sp3)N bond and an inhibitive effect on the hydrogenolysis of C(sp2)N bond. The use of a saturated hydrocarbon as diluent facilitates CN bond hydrogenolysis in the presence of hydrogen, irrespective of the carbon being sp2 or sp3 hybridized. 相似文献
8.
Františka Frajkorová Miroslav Hnatko Zoltán Lenčéš Pavol Šajgalík 《Journal of the European Ceramic Society》2012,32(10):2513-2518
The work deals with the preparation of dense SiC based ceramics with high electrical conductivity. SiC samples with different content of conductive TiNbSiCO based phase were hot pressed at 1820 °C for 1 h in Ar atmosphere under mechanical pressure of 30 MPa. The conductive phase is a mixture of 50 wt% TiNbC (molar ratio of Ti/NbC is 1:1.8) and 50 wt% eutectic composition of Y2O3SiO2. Composite with 30% of conductive TiNbSiCO phase showed the highest electrical conductivity 28.4 S mm?1, while the good mechanical properties of SiC matrix were preserved (fracture toughness KIC = 5.4 MPa m1/2 and Vickers hardness 17.8 GPa).The obtained results show that the developed additive system is suitable for the preparation of SiC-based composite with sufficient electrical conductivity for electric discharge machining. 相似文献
9.
《Journal of the European Ceramic Society》2014,34(8):1949-1954
Dense TiC–SiC nanocomposite ceramics were prepared by infiltration of porous TiC scaffolds with a SiOC sol, followed by spark plasma sintering (SPS). The porous nano TiC scaffold was first synthesized by direct carbothermal reduction of a monolithic TiOC precursor obtained from a controlled sol–gel process. The TiC scaffold was infiltrated with a SiOC sol and then the sample was aged in a container for 48 h at 80 °C to convert the sol into gel. After this, the sample was heated at 550 °C to remove the organic components and then 1350 °C to convert the SiOC gel to SiC by carbothermal reduction reaction. The cycle of the infiltration and carbothermal reduction was repeated several times to obtain relatively dense TiC–SiC composite samples. Dense TiC–SiC composite with a uniform nano-sized grain microstructure was obtained by spark plasma sintering at 1800 °C for 5 min under 40 MPa uniaxial pressure. Compared with conventional powder mixing methods, the sol–gel infiltration approach has shown distinct advantages of achieving dense TiC–SiC composites with uniform nano-sized grain structures. 相似文献
10.
In this paper, HgCl2 was loaded by impregnation method to study its property influence and poisoning mechanism on V2O5-WO3/TiO2 SCR-DeNOx catalyst. For HgCl2-containing catalysts, deactivation was observed in simulated gas stream, and its catalytic activity declined with the increase of HgCl2 loadings. Brønsted acid sites (VOH) and VO bond were affected evidently by HgCl2, new NH3 adsorption site ClVOH was generated after HgCl2 addition. Interactions between HgCl2 and V2O5 resulted in the loss of SCR active sites, and –HgCl existed as the stable form on the bridge site. Finally, the probable schematic diagram of HgCl2 poisoning mechanism was also proposed. 相似文献
11.
C2H6 reactions with O2 only form CO2 and H2O on dispersed Pt clusters at 0.2–28 O2/C2H6 reactant ratios and 723–913 K without detectable formation of partial oxidation products. Kinetic and isotopic data, measured under conditions of strict kinetic control, show that CH4 and C2H6 reactions involve similar elementary steps and kinetic regimes. These kinetic regimes exhibit different rate equations, kinetic isotope effects and structure sensitivity, and transitions among regimes are dictated by the prevalent coverages of chemisorbed oxygen (O*). At O2/C2H6 ratios that lead to O*-saturated surfaces, kinetically-relevant CH bond activation steps involve O*O* pairs and transition states with radical-like alkyls. As oxygen vacancies (1) emerge with decreasing O2/alkane ratios, alkyl groups at transition states are effectively stabilized by vacancy sites and CH bond activation occurs preferentially at O** site pairs. Measured kinetic isotope effects and the catalytic consequences of Pt cluster size are consistent with a monotonic transition in the kinetically-relevant step from CH bond activation on O*O* site pairs, to CH bond activation on O** site pairs, to O2 dissociation on ** site pairs as O* coverage decrease for both C2H6 and CH4 reactants. When CH bond activation limits rates, turnover rates increase with increasing Pt cluster size for both alkanes because coordinatively unsaturated corner and edge atoms prevalent in small clusters lead to more strongly-bound and less-reactive O* species and lower densities of vacancy sites at nearly saturated cluster surfaces. In contrast, the highly exothermic and barrierless nature of O2 activation steps on uncovered clusters leads to similar turnover rates on Pt clusters with 1.8–8.5 nm diameter when this step becomes kinetically-relevant at low O2/alkane ratios. Turnover rates and the O2/alkane ratios required for transitions among kinetic regimes differ significantly between CH4 and C2H6 reactants, because of the different CH bond energies, strength of alkylO* interactions, and O2 consumption stoichiometries for these two molecules. Vacancies emerge at higher O2/alkane ratios for C2H6 than for CH4 reactants, because their weaker CH bonds lead to faster scavenging of O* and to lower O* coverages, which are set by the kinetic coupling between CH and OO activation steps. The elementary steps, kinetic regimes, and mechanistic analogies reported here for C2H6 and CH4 reactions with O2 are consistent with all rate and isotopic data, with their differences in CH bond energies and in alkyl binding, and with the catalytic consequences of surface coordination and cluster size. The rigorous mechanistic interpretation of these seemingly complex kinetic data and cluster size effects provides useful kinetic guidance for larger alkanes and other catalytic surfaces based on the thermodynamic properties of these molecules and on the effects of metal identity and surface coordination on oxygen binding and reactivity. 相似文献
12.
A waterborne aliphatic polyurethane-based coating was studied for accelerated ultra-violet (UV), water (WT), and thermal (TH) aging for a period of 1000 h. To monitor the coating durability, samples were tested every 200 h. ATR-FTIR spectroscopy was used to monitor the chemical changes occurring during the aging process. UV–vis with integrating sphere was used to track the change in diffused reflectance, while the optical microscope and the scanning white light interferometry (SWLI) were used for surface characterization. FTIR studies of coatings subjected to UV exposure indicated a decrease in functional groups such as CONH, CH, CO, and COC. The appearance of functional groups such as NH is attributed to chain scission of the polyurethane binder in the coating. Investigation of the degradation mechanism in water and thermal aging showed physical effects through water penetration and the mismatch in the coefficient of thermal expansion as the primary causes of degradation. In all aging scenarios, the reduction of reflectivity was largely due to physical defects caused by the different aging mechanisms. 相似文献
13.
We have developed two efficient thiourea promoted dearomatizing processes involving the cycloadditions of 3-nitroindoles. The C2C3 double bond of the heteroarene can be involved as electron-poor 2π dienophile in [4+2] cycloadditions. While the uncatalyzed process requires harsh conditions, the organocatalyzed reaction takes place at room temperature and atmospheric pressure. The C2C3NO motif of the heteroarene can also react as an electron-poor 4π heterodiene in [4+2] / [3+2] cycloadditions cascades, under high pressure. In contrast to Lewis acid activation, thiourea promotion thus proves efficient even under unconventional activation conditions and in the presence of acid sensitive reactants such as enol ethers. 相似文献
14.
A new series of unsymmetrical cyrhetrenyl and ferrocenyl azines that were monosubstituted [(η5-C5H4)–C(R)N–NCH(5-NO2–2-C4H2O)]M {with MRe(CO)3 and RH (1a) or RMe (1b); MFe(η5-C5H5) and RH (2a) or RMe (2b)} and disubstituted [Fe{(η5-C5H4)–C(Me)N–NCH(5-NO2–2-C4H2O)}2] (3a) were prepared by condensation reactions of the corresponding organometallic hydrazone [(η5-C5H4)–C(R)N–NH2)]M with 5-nitro-2-furaldehyde. The 1H and 13C{1H} NMR spectra indicated that these compounds adopted an (E,E)-configuration about the ˃CN − bond and an s-trans conformation about the N1–N2 bond, and this result was confirmed by X-ray crystallographic analyses of 1a and 2b. The opposite electronic effects of the organometallic fragments correlate with the co-planarity of the [(η5-C5H4)–C(R)N–NCH(5-NO2–2-C4H2O)] system, the reduction potential of the nitro group (E1/2) and the chemical shifts of the iminic carbons. 相似文献
15.
The ligand precursors 2-(R3PN)CH2Py (R = Ph(1a), Cy(2a)) were prepared from reaction of pyridine azide with various phosphine ligands. Reaction of 1a or 2a with RuCl2(CHPh)(Py)2(H2IMes) (Py = pyridine) afforded the ruthenium alkylidene complex RuCl2(CHPh)(PyCH2(NPR3))(H2IMes) (R = Ph(1), Cy(2)). Both catalysts showed good thermal stability and latent behavior toward RCM and ROMP reactions. 相似文献
16.
《Journal of the European Ceramic Society》2017,37(10):3263-3270
A liquid hyperbranched polycarbosilane (LHBPCS) with stoichiometric C/Si ratio but without unsaturated groups was synthesized. Different from traditional thermal crosslinking, ultraviolet (UV) irradiation crosslinking was taken. The molecular weight, the consumption of SiH group and ceramic yield of LHBPCS showed an increase trend with increasing the UV irradiation time. After 30 min of UV irradiation, 71.8 wt% ceramic yield was obtained. In addition, extra divinyldimethylsilane was added into LHBPCS. Under UV irradiation, both the SiH group and vinyl group of divinyldimethylsilane were consumed. But the reaction extend of vinyl group was much faster than that of SiH group. Compared with pure LHBPCS, the mixture of LHBPCS and 5 wt% divinyldimethylsilane gave a higher ceramic yield of 79 wt% after 30 min of UV irradiation. By heating the crosslinked LHBPCS to 1000 °C, a near stoichiometric SiC ceramic was got. It exhibited excellent thermal stability at 1400 °C in air. 相似文献
17.
《Journal of the European Ceramic Society》2005,25(10):1723-1731
This work summarizes the results related to the influence of the starting composition and of microstructure on properties degradation, due to oxidation and corrosion, relatively to the following structural ceramics: Si3N4TiN, Si3N4MoSi2, AlNSiCMoSi2, AlNSiC.The effects of: (i) long-term oxidation in air (100 h), in the temperature range 600–1500 °C and (ii) of long-term corrosion (400 h) in acid or basic aqueous solution at RT, 40 and 70 °C, on the electrical resistivity and mechanical strength of the composites are analysed and compared. The degradation of the properties are related to the characteristics of the surface and sub-surface damage after oxidation and corrosion treatments. 相似文献
18.
《Inorganic chemistry communications》2005,8(7):610-613
Nucleophilic attack of sodium isopropylthiolate on 4,4-dichloro-1,1-diphenyl-2-azabuta-1,3-diene [Cl2CC(H)–NCPh2}] (1) affords the 2-azabutadiene derivative [(i-PrS)2CC(H)–NCPh2] (2). Upon irradiation of Mo(CO)6 in THF in the presence of 2, the chelate complex cis-[(OC)4Mo{(i-PrS)2CC(H)–NCPh2}] (3) is obtained. Coordination on Mo occurs through the imine nitrogen and a thioether group. Polydentate dithioether 2 acts as N,C,S-pincer ligand after orthometallation reaction with Pd(II) or Pt(II). The molecular structures of 2 and (C,N,S)-[(i-PrS)2CC(H)–NC(Ph)C6H4)PtCl] (4b) have been determined by X-ray diffraction studies. 相似文献
19.
Palladium nanoparticles stabilized by PdC(binaphthyl) covalent bonds have been designed and synthesized. This new class of Pd nanoparticles was efficiently used as reusable catalysts for CC bond forming Heck, Suzuki–Miyaura and Sonogashira cross coupling reactions with high turnover. Even after the several catalytic cycles the Pd NPs had the same reactivity and particle size without any apparent agglomerization. 相似文献
20.
《Carbon》2014
Junctions are the key component for 3D CNT-graphene seamless hybrid nanostructures attractive for numerous innovative applications. Growth mechanism of junctions of vertical carbon nanotubes (CNTs) growing from graphene in the presence of iron nanoparticles as catalysts was simulated using quantum mechanical molecular dynamics methods. When nanotube grew on graphene via a “base-growth” mechanism, it was found that the junctions were a mixture of CC and FeC covalent bonds. We further explored the formation mechanisms of pure CC bonded junctions by moving the catalyst during CNT growth or etching and annealing after growth. Our simulations provided possible avenues to produce pure CC bonded junctions that seamlessly connect graphene and nanotubes in the 3D nanostructures. 相似文献