Preparation and Characterization of a Perovskite-type Mixed Conducting SrFe0.6Cu0.3Ti0.1O3-δ Membrane for Partial Oxidation of Methane to Syngas

Dense membrane with the composition of SrFe0.6Cu0.3Ti0.1O3-δ （SFCTO） was prepared by solid state reaction method. Oxygen permeation flux through this membrane was investigated at operating temperature ranging from 750℃ to 950℃ and different oxygen partial pressure. XRD measurements indicated that the compound was able to form single-phased perovskite structure in which part of Fe was replaced by Cu and Ti. The oxygen desorption and the reducibility of SFCTO powder were characterized by thermogravimetric analysis and temperature programmed reduction analysis, respectively. It was found that SFCTO had good structure stability under low oxygen pressure at high temperature. The addition of Ti increased the reduction temperature of Cu and Fe. Performance tests showed that the oxygen permeation flux through a 1.5 mm thick SFCTO membrane was 0.35-0.96 ml·min ^-1·cm^-2 under air/helium oxygen partial pressure gradient with activation energy of 53.2 kJ·mol^-1. The methane conversion of 85%, CO selectivity of 90% and comparatively higher oxygen permeation flux of 5 ml·min^-1·cm^- 2 were achieved at 850℃, when a SFCTO membrane reactor loaded with Ni-Ce/Al2O3 catalyst was applied for the partial oxidation of methane to syngas.

Setting and Strength Characteristics of Alkali-activated Carbonatite Cementitious Materials with Ground Slag Replacement

The effect of the ground granulated blast-furnace slag （ GGBFS ） addition, the modulus n （ mole rutio of SiO2 to Na2O ） and the concentrution of sodium silicate solution on the compressive strength of the material, i e alkuli-activated carbonatite cemeutitious material （ AACCM for short ） was investiguted. In addition, it is found that barium chloride has a sutisfiwtory retarding effect on the setting of AACCM in which more than 20% （ by mass ） ground carbonatite was replaced by GGBFS. As a result, a cementitious material, in which ground carbonatite rock served as dominative starting material, with 3-day and 28-day compressive strength greuter them 30 MPa and 60 MPa and with continuous strength gain beyond 90 days was obtained.

Copper-catalyzed asymmetric dearomatizing amination of 2-naphthols:Csp^(2)–N coupling via 1,3-reductive elimination

An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I)complex as a chiral catalyst was presented.A variety of optically activeβ-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions.Mechanistic studies indicated that this Csp^(2)–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-Cu~Ⅲ-amino intermediate in five-membered ring transition states.The origin of enantioselectivity has also been elucidated based on density functional theory calculations.

Urchin-like NiO Superstructures Prepared by Simple Thermal Decomposition Process

Urchin-like Ni O superstructures have been prepared via a thermal decomposition reaction of Ni C_2O_4 at 400 for 1h. The morphology and structure of the synthesized urchin-like superstructures have been characterized by X-ray diffraction, field emission scanning electron microscopy and transmission electron microscopy. The results show that urchin-like Ni O superstructures were a polycrystal with cubic structure and typical diameters of 200 to 500 nm and the self-assembly nanoparticles average diameter is 14 nm. The as-prepared Ni O superstructures have a high Brunauer-Emmett-Teller surface area of about 60.32 m^2/g. The UV-vis spectrum of urchin-like Ni O consists of one peak at 357 nm(3.47 e V).

A New Steady and Water-insoluble Polytungstate： Synthesis, Structure, Characterizations and Photocatalytic Properties

Polyoxometalate （POM）-based materials universally have some inherent flaws, including low recovery, metastability, solubility, etc., which may restrict their practical applications. Modifying the materials with organic-inorganic hybrid complexes is one of the most effective approaches to overcome these deficiencies. Under hydrothermal conditions, a new Wells- Dawson-type polytungstate modified Cd-complex, [Cd（phen）3]3[W18O54（PO4）2]？3H2O （1, phen = 1,10-phenanthroline （C12N2H8））, has been synthesized by selecting Cd2＋ coordinated phen and employing stepwise self-assembly plans. The compound shows good stability and water- insolubility under normal circumstances. Experiments demonstrate that compound 1 has ideal catalytic activity in the degradation reaction of rhodamine B （RhB） under ultraviolet （UV）-light and oxidant H2O2 conditions. Detailed characterizations including X-ray single-crystal diffraction （XRD）, Powder X-ray diffraction （PXRD）, elemental analysis, energy-dispersive X-ray spectroscopy （EDS） analyses, Fourier transform infrared spectroscopy （FT-IR）, UV-Vis-NIR diffuse reflection spectrum （DRS） and XPS spectrum are presented herein. The electrochemical （cyclic voltammetry （CV）） and photocatalytic properties of 1 have also been studied.

Experiment and simulation study on construction of a three-dimensional network model

The construction of a network model is one of the key techniques in organic com-bination of microscopic flow experiment and simulation. The construction method of a three-dimensional network model is presented on the basis of CT scanning images in this paper. A series of CT slice images describing microscopic pore structure and fluid distribution of actual rock is obtained with the help of the in-dustrial microfocus CT system. Based on the extraction of pore space skeleton, pore and throat information, the corresponding network model is established, and the conversion from three-dimensional CT image information to pore-throat size distribution and topological information is also achieved. The feature of this me-thod lies in the fact that complicated pore space of rock may be characterized by pores and throats with a simple shape while keeping the geometry and flow char-acteristics. It is indicated that the calculated results of porosity, permeability, rela-tive permeability curve and microscopic remaining oil distribution match very well the experimental results of water flooding and polymer flooding. This network model may fairly well characterize the rock microscopic pore-throat size and topo-logical characteristics.

Off-on-off luminescent switching of a dye containing imidazo[4,5-f][1,10]phenanthroline

A new acid-base fluorescent switch containing both imidazo[4,5-f][1,10]-phenanthroline and triphenylamine groups has been synthesized.Its fluorescence emissions and absorptions can be reversibiy changed through protonation/deprotonation of imidazole and amine moiety by controlling the intramolecular charge transfer（ICT） process,leading to off-on-off fluorescent molecular switching.

Synthesis and characterization of a new chromophor with acid/base-sensitive fluorescence emission

A new two-photon absorption compound, 2-{4-[（dicyanomethylidene-5,5-dimethylcyclohexl）vinyl]phenyl}imidazo[4,5- f][1,10]phenanthroline （DDVPIP）, was synthesized and characterized. The one-photon excited fluorescence （OPEF） and two- photon excited fluorescence （TPEF） of DDVP1P are sensitive to the acid/base of the solution, which are enhanced in basic solution but weakened in acidic solution. Charge-transfer （CT） states of DDVPIP were calculated through theory methods to explain its acid/ base-sensitive fluorescent properties.

BRANCHING GENERATION DURING THE FREE RADICAL COPOLYMERIZATION OF p-VINYL BENZENE SULFONYL CHLORIDE WITH STYRENE

The branching generation during the free radical copolymerization of chain transfer monomer p-vinyl benzene sulfonyl chloride （VBSC） with styrene was investigated by a simple mathematic model. Chain transfer constant of VBSC was determined to be around 0.3 by fitting the 1H-NMR monitored experimental results with a mathematic model. According to the theoretical analysis, the obtained poIy（VBSC） and its copolymers were substantiated to have a grafting-like main chain with residual pendent sulfonyl chloride groups after consuming most of the vinyl groups. The copolymerization results of VBSC with styrene at varied feed ratios demonstrated that conversion of sulfonyl chloride groups was lower than that of the monomer, which was in agreement with the theoretical results. The glass transition temperature, number average molecular weight and distribution of those obtained polymers were primarily investigated. Comparing with other chain transfer monomers, VBSC has a chain transfer constant much closer to unity therefore a more branched polymer is expected. Additionally, the branched polystyrene with residual sulfonyl chloride groups is hopefully to be further used as ATRP macro- initiators or reactive intermediates to synthesize functional polymers with complex structure.

Theoretical studies of the proton transfer behaviors in molecular complexes analogous to catalytic triad of serine protease:Toward understanding the existence and significance of the low-barrier hydrogen-bond in enzymatic catalysis

A representative acetate-(5-methylimidazole)-methanol system has been employed as a model of catalytic triad in serine protease to validate the formation processes of lowbarrier H-bonds(LBHB) at the B3LYP/6-311++G level of theory,and variable H-bonding characters from conventional ones to LBHBs have been represented along with the proceedings of proton transfer.Solvent effect is an important factor in modulation of the existence of an LBHB,where an LBHB(or a conventional H-bond) in the gas phase can be changed into a non-LBHB(an LBHB) upon solvation.The origin of the additional stabili-zation energy arising from the LBHB may be attributed to the H-bonding energy difference before and after proton transfer because the shared proton can freely move between the proton donor and proton acceptor.Most importantly,the order of magnitude of the stabilization energy depends on the studied systems.Furthermore,the nonexistence of LBHBs in the catalytic triad of serine proteases has been verified in a more sophisticated model treated using the ONIOM method.As a result,only the single proton transfer mechanism in the catalytic triad has been confirmed and the origin of the powerful catalytic efficiency of serine proteases should be attributed to other factors rather than the LBHB.