Advances and perspectives in catalytic oxidation of hydrocarbons in liquid phase

This review article summarizes recent advances in catalytic oxidation of hydrocarbons,especially presents two strategies for activation of C-H bonds or molecular oxygen.Based on our own research results,the applications of the two methods in the oxidation of cyclohexane,toluene and ethyl benzene,etc.are introduced,and the perspectives of the two methods are also discussed.     

Influence of interactions between chromium and cerium on catalytic performances of CrO_x–CeO_2/Ti-PILC catalysts for deep oxidation of n-butylamine

A series of CrOx-CeO2/Ti-PILC （PILC is pillared interlayered clay） catalysts for n-butylamine oxidation were prepared using an impregnation method, and the structures, surface acidity distributions, and redox properties of the catalysts were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, H2 temperature-programmed reduction, and NH3 temperature-programmed desorption. The results show that addition of an appropriate amount of CeO2 enhances the interactions between Cr and Ce, and this increases the acid strength and mobility of active oxygen species on the cata- lyst. 8CrCe（6：1）/Ti-PILC（12,20） exhibits the best catalytic performance and control of NOx in n-butylamine oxidation.     

Fabrication of flexible α-MnO_2 nanowire membranes with superior mechanical strength

The Assembly of one-dimensional （1D） nano- structures such as nanowires/nanorods/nanotubes into two- dimensional （2D） macrostructured films is attracting considerable research interest because of their unique properties and wide applications. In this study, flexible membranes were successfully fabricated using α-MnO2 nanowires synthesized through a hydrothermal method. The effects of thickness and post-annealing temperature on the mechanical properties of the membranes were investigated in detail. Nano-indentation measurements showed that the modulus of the as-prepared 11.75 μm-thick membrane reached 5.765 GPa, and the modulus increased with the increasing post-annealing temperature. Thus, the fabricated membranes with superior mechanical strength can have potential applications such as in photocatalysis, filtering, and supporting substrates.     

Enolate chelating N-heterocyclic carbene complexes of Fe(II): Synthesis, structure and their catalytic activity for ring-opening polymerization of ε-caprolactone

The reaction of anhydrous FeBr2 with two equivalents of anionic N-heterocyclic carbene (NaL1 and NaL2), which are generated in situ by the reaction of the corresponding salt [4-R-C6H4COCH2{CH- (NCHCHNiPr)}Br] (R = OCH3, H2L1Br, 1; R = F, H2L2Br, 2) with two equivalents of NaN(SiMe3)2, affords bis-ligand Fe(II) complexes of L12Fe (3) and L22Fe (4) in high yield, respectively. Attempt to synthesize mono-ligand Fe(II) bromide by the 1:1 molar ratio of NaL to FeBr2 is unsuccessful, and the same com- plexes of 3 and 4 were obtained. Both 3 and 4 have been depicted by elemental analysis and X-ray structure determination. Preliminary studies show that both 3 and 4 can be used as single-component catalyst for the ring-opening polymerization of ε-caprolactone, and the catalytic activity of 3 is higher than that of 4.     

Effects of baria on propane oxidation activity of Pd/Al2O3 catalyst: Pd–BaO interactio n and reaction routes

The BaO-modified Pd/Al2O3exhibits much better catalytic activity than Pd/Al2O3for C3H8 oxidation both before and after the hydrothermal aging treatment. Further studies ascribe its good activity to the influence of BaO species on the physicochemical characteristics of the catalyst and the reaction routes. Firstly, the BaO species inhibits the phase transformation of alumina, resulting in higher surface area of the catalysts and hereby a better dispersion of Pd. Secondly, the basic nature and electron-withdrawing effect of barium oxide maintain palladium at high oxidation state, which leads to a higher PdO content on surface of the BaO-modified catalyst. Finally, the formation/decomposition of carbonate/bicarbonate species can be promoted by the addition of BaO, which provide extra reaction routes and are important for the deep oxidation of C3H8.     

Preparation of MCM-41-supported chiral Salen Mn （Ⅲ） catalysts and their catalytic properties in the asymmetric epoxidation of olefins

A secondary amino-modified mesoporous molecular sieve MCM-41 was obtained by reaction of bis(3-(triethoxysilyl)propyl)amine with MCM-41. The chiral Salen-Mn (III) complex was anchored onto the modified MCM-41 by a multi-step grafting method and two heterogenized catalysts with different Mn contents were obtained. The catalysts were characterized by XRD, N2 adsorption, ICP, FT-IR and DR UV-Vis. Their catalysis on asymmetric epoxidation of several olefins was studied with NaClO and m-CPBA as oxidants respectively. It was found that both the activity and enantioselectivity of the cata- lysts decreased after the homogeneous catalyst was heterogenized. The reasons resulting in the de- crease of catalytic performance were discussed.     

Comparative research on the catalytic activities of different molecular sieves for acetalization and ketalization

Molecular sieves with different acidities and pore-sizes have been applied to catalyze the acetalization and ketalization of carbonyl compounds with glycol. A comparative research on the catalytic activities of the catalysts for certain reactions has been carried out to figure out the relationship between the characters of the catalysts and the activities. The results show that the pore-size of the molecular sieves is one of the most important factors that determine the catalytic activity. Appropriate pore-size is needed for the certain reaction.The acidity is another factor that affects the activities. They also have great effects on the recycled activities of the catalysts.     

Preparation and performance of lipophilic α-zirconium phosphate with high thermal stability and its application in thermal-plastic polymers

To prepare lipophilic α-zirconium phosphate with high grafting ratio and thermal stability(OZrP-HT) and explore its potential application in thermal-plastic polymers,a novel method was developed by surface lipophilicity enhancement strategy.The commercial a-zirconium phosphate(a-ZrP) was pre-intercalated by n-propylamine(PA) and grafted by silane coupling agents.Then the pre-intercalated PA was removed by heattreatment,and the obtained OZrP-HT was utilized to fabricate the phosphorous-containing polyester(P-co-PET)/OZrP-HT nanocomposites by melt-blending method.The prepared OZrP-HT and P-co-PET/OZrP-HT nanocomposites were characterized by Wide Angle X-ray Diffraction(WAXD),Fourier Transform Infrared Spectroscopy(FTIR),Thermogravimetric Analysis(TGA),Transmission Electron Microscope(TEM),etc.The results show that OZrP-HT with high grafting ratio(13.78 wt%) and thermal stability(T_(onset)= 368℃) was successfully prepared via this novel method and was uniformly intercalated by P-co-PET molecular chains.OZrP-HT had no significant effect on the fiber processability of P-co-PET polymer,and flame retardant properties of(P-co-PET)/OZrP-HT nanocomposites were improved.This method may be suitable for organic modification of general inorganic layered compounds and could extend the potential applications in thermo-plastic polymers.     

Preparation and oxidation characteristics of ZrC-ZrB2 composite powders with different proportions

ZrC and ZrB2 are both typical ultra-high temperature ceramics,which can be used in the hyperthermal environment.In this study,a method for preparing ultrafine ZrC-ZrB2 composite powder was provided,by using the raw materials of nano ZrO2,carbon black,B4C,and metallic Ca.It is worth pointing out that ZrC-ZrB2 composite powder with any proportion of ZrC to ZrB2 could be synthesized by this method.Firstly,a mixture of ZrC and C was prepared by carbothermal reduction of ZrO2.By adjusting the addition amount of B4C,ZrC was boronized by B4C to generate ZrC-ZrB2 composite powder with different compositions.Using this method,five composite powders with different molar ratios of ZrC and ZrB2(100ZrC,75ZrC-25ZrB2,50ZrC-50ZrB2,25ZrC-75ZrB2,and 100ZrB2)were prepared.When the temperature of boronization and decarburization process was 1473 K,the particle size of product was only tens of nanometres.Finally,the oxidation charac-teristics of different composite powders were investigated through oxidation experiments.The oxidation resistance of ZrC-ZrB2 composite powder continued to increase as the content of ZrB2 increased.     

Microstructure and oxidation resistance of SiC–MoSi2 multi-phase coating for SiC coated C/C composites

In order to improve the anti-oxidation of C/C composites, a SiC–MoSi2multi-phase coating for SiC coated carbon/carbon composites(C/C)was prepared by low pressure chemical vapor deposition(LPCVD) using methyltrichlorosilane(MTS) as precursor, combined with slurry painting from MoSi2 powder. The phase composition and morphology were analyzed by scanning electron microscope(SEM) and X-ray diffraction(XRD) methods, and the deposition mechanism was discussed. The isothermal oxidation and thermal shock resistance were investigated in a furnace containing air environment at 1500 1C. The results show that the as-prepared SiC–MoSi2coating consists of MoSi2 particles as a dispersing phase and CVD–SiC as a continuous phase. The weight loss of the coated samples is 1.51% after oxidation at 1500 1C for 90 h, and 4.79% after 30 thermal cycles between 1500 1C and room temperature. The penetrable cracks and cavities in the coating served as the diffusion channel of oxygen, resulted in the oxidation of C/C composites, and led to the weight loss in oxidation.     

A Cooperative Schema between Web Sever and Search Engine for Improving Freshness of Web Repository

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Electrochemical behavior and corrosion resistance of IrO_2–ZrO_2 binary oxide coatings for promoting oxygen evolution in sulfuric acid solution

In this study, we prepared Ti/IrO_2–ZrO_2 electrodes with different ZrO_2 contents using zirconium-n-butoxide(C_(16)H_(36)O_4Zr) and chloroiridic acid(H_2IrCl_6) via a sol–gel route. To explore the effect of ZrO_2 content on the surface properties and electrochemical behavior of electrodes, we performed physical characterizations and electrochemical measurements. The obtained results revealed that the binary oxide coating was composed of rutile IrO_2, amorphous ZrO2, and an IrO_2–ZrO_2 solid solution. The IrO_2–ZrO_2 binary oxide coatings exhibited cracked structures with flat regions. A slight incorporation of ZrO_2 promoted the crystallization of the active component IrO_2. However, the crystallization of IrO_2 was hindered when the added ZrO_2 content was greater than 30 at%. The appropriate incorporation of ZrO_2 enhanced the electrocatalytic performance of the pure IrO_2 coating. The Ti/70 at%IrO_2–30 at%ZrO_2 electrode, with its large active surface area, improved electrocatalytic activity, long service lifetime, and especially, lower cost, is the most effective for promoting oxygen evolution in sulfuric acid solution.     

Layered Fe(Ⅲ) doped TiO_2 thin-film electrodes for the photoelectrocatalytic oxidation of glucose and potassium hydrogen phthalate

Four types of TiO 2 thin-film electrodes were fabricated from TiO 2 and Fe(III) doped TiO 2 sols using a layer-by-layer dip-coating technique. Electrodes fabricated were TF (pure TiO 2 surface, Fe(III)-TiO 2 bottom layer), FT (Fe(III)-TiO 2 surface, pure TiO 2 bottom layer), TT (both layers pure TiO 2 ) and FF (both layers Fe(III)-TiO 2 ). The photoelectrochemical behavior of these electrodes was characterized using linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and steady-stat...     

Layered Fe（Ⅲ） doped TiO2 thin-film electrodes for the photoelectrocatalytic oxidation of glucose and potassium hydrogen phthalate

Four types of TiO 2 thin-film electrodes were fabricated from TiO 2 and Fe(III) doped TiO 2 sols using a layer-by-layer dip-coating technique. Electrodes fabricated were TF (pure TiO 2 surface, Fe(III)-TiO 2 bottom layer), FT (Fe(III)-TiO 2 surface, pure TiO 2 bottom layer), TT (both layers pure TiO 2 ) and FF (both layers Fe(III)-TiO 2 ). The photoelectrochemical behavior of these electrodes was characterized using linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and steady-state photocurrent measurements in aqueous 0.1 mol L –1 NaNO 3 containing varying concentrations of glucose or potassium hydrogen phthalate (KHP). EIS and LSV results revealed that exciton separation efficiency followed the sequence of TF﹥TT﹥FT > FF. Under a constant potential of +0.3 V, steady-state photocurrent profiles were recorded with varying organic compound concentrations. The TF electrode possessed the greatest photocatalytic capacity for oxidizing glucose and KHP, and possessed a KHP anti-poisoning effect. Enhanced photoelectrochemical performance of the TF electrode was attributed to effective exciton separation because of the layered TF structure.     

Lazy and Partial Assembly with Object Skeletons for Improving the Efficiency of Navigation（extracted）

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Anaerobic oxidation of methane: Geochemical evidence from pore-water in coastal sediments of Qi’ao Island (Pearl River Estuary), southern China

The concentrations of CH4 and SO4^2- in pore-water and the carbon isotope compositions of total dissolved inorganic （TCO2） and OH4 were determined for three coastal sedimentary cores collected from Qi＇ao Island （Pearl River Estuary）, southern China. Results show that methane concentration changes dramatically at the base of the sulfate-reducing zone and sulfate concentration gradients are linear for all stations. In addition, the carbon isotope of methane becomes heavier at the sulfate-methane transition （SMT）, which causes ∑CO2-δ^13C to become the minimum. The geochemical profiles of pore-water render indirect evidence for anaerobic oxidation of methane （AOM）. Based on numerical modeling of AOM and sulfate-reducing rates, the portion of total sulfate reduction occurring via AOM is 9.0%, 84% and 45.5%, respectively, and the percentage of TCO2 added to the pore-water is 4.7%, 72.4% and 29.45% correspondingly for three sites. Furthermore, it is found that the methane concentration, methane diffusive flux and the depth of SMT are controlled by the quantity and quality of sedimentary organic matter incorporated into the sediments. The great amount of organic material is favorable for rapid depletion of sulfate via sedimentary organic matter degradation, and on the other hand, causes the increase of the methane flux in the SMT, which results in a portion of sulfate reduction supported by AOM. Accordingly, the SMT was shifted towards the sediment surface.     

Anaerobic oxidation of methane: Geochemical evidence from pore-water in coastal sediments of Qi’ao Island (Pearl River Estuary), southern China

According to the IPCC report (1992), only 2% of the methane in atmosphere comes from oceans[1]. Never- theless, as we know, the amount of methane produced by marine sediments is far more than this percentage. For example, about 2.9×1011 mol methane was e…     

Synthesis and Application of a Polymeric Crosslinking Agent for Improving Fixation of Vinylsulfone-type Dyes on Cotton by a Pad-drycure Process

A new class of novel polymeric crosslinging agent （NPCA）, which contained silane coupling group and the epoxy groups, was designed and synthesized in our laboratory. NPCA was a non-formaldehyde multifunctional crosslinking polymer. The cotton fabrics dyed with 8.0% （owf） Vinylsulpone-type dyes were treated with 3.0%- 4.0% NPCA, 0.5 mol/L potassium thiocyanate as a catalyst, then padded through two dips and two nips to reach a wet pickup of 80%- 85%, then dried at 80℃ for 2 minutes and cured in oven at 140- 150℃ for 3 minutes. Crocking fastness and fixation （%） were improved with up to 1.0 -1. 5 units, 35%- 50%, respectively. And there was little difference between the color yield of dyed fabrics before and after the treatment at certain conditions. The possible crosslinking mechanism of NPCA was also investigated. It was concluded that NPCA can improve colorfastness of cotton fabric by means of the three-dimensional network, covalent bonding and other molecular forces.     

State space approach for joint estimation of activity and attenuation map from PET emission sinograms

Quantitative estimation of radioactivity map has important clinical implications for better diagnosis and understanding of cancers. Although attenuation map and activity map are usually treated sequentially, they can obviously benefit a great deal when the transmission data is missing. In this paper, we propose a novel scheme of simultaneously solving for attenuation map and activity distribution from emission sinograms. Our strategy combines the measurement model of PET, and the attenuation parameters are treated as random variables with known prior statistics. After the conversion to state space representation, the extended Kalman filtering procedures are adopted to linearize the equations and to provide the joint estimates in an approximate optimal sense. Experiments have been performed on both synthetic data to illustrate its abilities and benefits     

Measurement of Magnetization Curve and Magnetic Relaxation for 2H-NbSe2 Crystals

The characteristics of electronic transport properties: behaviors of magnetization curve and magnetic relaxation of a typical normal superconductor 2H-NbSe2 are investigated. The results show that Tc and △Tc of the samples are 7. 2,0. 18 K, indicating that superconducting energy gap at zero temperature is 1. 1 meV. No fish tail shape is found in the magnetization curves at several temperatures. The relationship between remnant magnetic moment and time reveals that the magnetic flux creep of the sample agrees with the Kim-Anderson thermal activation model with the relaxation rate S=0.000 36 at T=6 K.