The Complex of Crosslinked Chitosan with 4＇-formal Benzo-15-crown-5 and Palladium Used as Catalyst for Asymmetrie Hydrogenation of α-phenylethanone

The crosslinked chitosan was grafted by 4＇-formal benzo-15-crown-5 to obtaine crosslinked chitosan with 4＇-formal benzo- 15-crown-5（CCTS-N=CH-B- 15-C-5）. Then it was loaded with palldium chloride to gain the heterogeneous catalyst, which was easily isolated from the reaction system. The influences of the Pd content of the catalyst, solvent, and temperature on asymmetric hydrogenation of a-phenylethanone have been studied. The catalyst has been found to catalyze the hydrogenation ofa-phenylethanone into the chiral alcohol, α-phenyl ethanol under the mild condition. The optical yield of （R）- 1-phenylethanol could be obtained as 97.1% under the following conditions： temperature, 30℃; solvent, ethanol; Pd content, 1.43 mmol/g; substrate concentration, 0.02 g/mL due to the cooperative effect of crown ether and chitosan polymer. The stability of this catalyst was also studied at the same time. This chiral natural crosslinked chitosan-palladium complex catalyst could be reused without appreciable change in optical catalytic activity, which will be useful for designing crosslinked-chitosan-based adsorption for metal ions for asymmetric hydrogenation.     

MoO3/SO4^2- —TiO2 catalyst for transesterification of dimethyl cabonate with phenol

A new MoO3/SO4^2- -TiO2 catalyst was prepared by a conventional impregnation of SO42-/TiO2 as carrier with an aqueous solution of ammonium molybdate and used for the synthesis of transesterification of dimethyl carbonate （DMC） with phenol.A series of MoO3/SO42--TiO2 catalysts with different MoO3 loadings were investigated and characterized using X-ray diffraction （XRD）,Fourier transform infrared spectrometer （FTIR）,NH3-temperature programmed desorption （NH3-TPD） and X-ray photoelectron spectroscopy （XPS）.The results show that MoO3 loading is related to the activity of transesterification reaction.With the increase of MoO3 loading,the activity of transesterification reaction increases.The sulfur species in the catalyst have an influence on the molybdenum species,and lead to an increase in the electropositive of molybdenum,which promotes the catalytic activity of MoO3/SO42--TiO2.Among the series of catalysts prepared,MoO3/SO42--TiO2 with 10% MoO3 and 823 K calcinated is found to be the most active catalyst for transesterification reaction.Under the reaction conditions of 453 K and 12 h,the conversion of DMC is 30.5 %,and the yields of MPC and DPC reach 21.2 % and 8.7 %,respectively.     

The Complex of Crosslinked Chitosan with 4′-formal Benzo-15-crown-5 and Palladium Used as Catalyst for Asymmetric Hydrogenation of α-phenylethanone

The crosslinked chitosan was grafted by 4′-formal benzo-15-crown-5 to obtaine crosslinked chitosan with 4′-formal benzo-15-crown-5(CCTS-N=CH-B-15-C-5). Then it was loaded with palldium chloride to gain the heterogeneous catalyst, which was easily isolated from the reaction system. The influences of the Pd content of the catalyst, solvent, and temperature on asymmetric hydrogenation of α-phenylethanone have been studied. The catalyst has been found to catalyze the hydrogenation of α-phenylethanone into the chiral alcohol, α-phenyl ethanol under the mild condition. The optical yield of (R)-1-phenylethanol could be obtained as 97.1% under the following conditions: temperature, 30 ℃; solvent, ethanol; Pd content, 1.43 mmol/g; substrate concentration, 0.02 g /mL due to the cooperative effect of crown ether and chitosan polymer. The stability of this catalyst was also studied at the same time. This chiral natural crosslinked chitosan-palladium complex catalyst could be reused without appreciable change in optical catalytic activity, which will be useful for designing crosslinked-chitosan-based adsorption for metal ions for asymmetric hydrogenation.     

Catalysis of Active Carbon Supporting Transition Metal Oxides for Pyrotechnical Reagent with Potassium Perchlorate

In order to improve the pyrotechnical reagent with potassium perchlorate,composite catalyst of active carbon supporting transition metal oxides (TMO),Fe2O3 and CuO,were prepared and added into pyrotechnical reagent with potassium perchlorate.Accelerating rate calorimeter (ARC) was used to study the catalysis of pyrotechnical reagent which is consisted of potassium perchlorate and composite catalyst.Composite catalyst of both Fe2O3 and CuO supported by active carbon can catalyze pyrotechnical reagent with potassium perchlorate.Furthermore,it can lower the apparent activation energy and accelerate the reaction with a smaller quantity than that with Fe2O3 and CuO.The maximal reaction rate of pyrotechnical reagent with potassium perchlorate mixed with Fe2O3/active carbon and CuO/active carbon is 8.31 min-1 and 9.13 min-1,which is 1.74 times and 1.91 times of pyrotechnical reagent mixed with no catalyst;time to maximal rate was 18.99 min and 1.96 min respectively,which is lower than pyrotechnical reagent mixed with no catalyst by 86.46% and 98.67% ;the apparent activation energy is 368.10 kJ·mol-1 and 325.29 kJ·mol-1,which is lower than pyrotechnical reagent mixed with no catalyst by 31.89% and 39.81% respectively.     

Facile Synthesis of 2PbCO3·Pb(OH)2 Microcrystals and Its Catalytic Behavior for Transesterification of Dimethyl Carbonate with Phenol

Polyhedron lead hydroxide carbonate （2PbCO3·Pb（OH）2 ） microcrystals have been prepared in solution phase via a facile method in the presence of surfactant cetyltrimethylammonium bromide （CTAB）. All the samples were characterized by powder X-ray diffraction ,pattern （XRD）, field-emission scanning electron mi- croscopy （FE-SEM）, high-resolution transmission electron microscopy （HRTEM）, and selected area electron diffraction （SAED）. The possible growth mechanism was discussed. 2PbCO3·Pb（OH）2 microcrystals were found to be a novel and efficient catalyst for the synthesis of diphenyl carbonate （DPC） by transesterification of dimethyl carbonate （DMC） with phenol. Compared with some other catalysts, such as AlCl3, ZnCl2, and Mg5（CO3）4（OH）2, 2PbCO3·Pb（OH）2 microcrystals are stable and show relatively high activity at low catalyst amount. When the reaction was carried out at 180 12, with a molar ratio of phenol to DMC of 2：1, a reaction time 14 h, and a catalyst amount 0.2% （molar ratio to phenol）, the selectivity of DPC and methyl phenyl carbonate （MPC） was 14.7% and 78.8%, respectively.     

Degradation of residual formaldehyde in fabric by photo-catalysis

The residual formaldehyde （HCHO） in fabric was degraded using photo-catalysis assisted by the compound catalyst of nano-TiO2 and nano-ZnO. The effects of several factors on the degradation, such as the composing of catalyst, irradiation time, pH value and the H2CHO concentration of the immersed solution were investigated. Results showed that H2CHO of the immersed solution had degraded 93% after 5 h irradiation, and the degradation ratio of formaldehyde could be improved and the aging of the fabric can be avoided with the addition of ZnO nanoparticles and pH value of the immersed-fibric solution. The fabric with residual formaldehyde about 1 800 μg/g can be efficiently treated to satisfy the China National Standard （GB/2912.1-1998） with the photo-catalytic degradation.     

In Situ Growth of Vanadium Oxide on Reduced Graphene Oxide for the Low-Temperature NO-SCR by NH_3

The vanadium oxide/reduced graphene oxide(V_2 O_5/rGO) composite catalyst which determined the selective catalytic reduction activity(SCR) of NO with NH_3 was prepared by a simple solvothermal method. The physicochemical properties of the catalysts were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), Raman, X-ray energy spectrometer(XPS) and N_2 sorption isotherm measurement(BET). Results of NH_3-SCR showed that the NO conversion of V_2 O_5/rGO catalyst could reach 54.3% at 100 ℃. And the removal of NO increased to 74.6% when the temperature was up to 220 ℃. By characterizing the microstructure and morphology of the V_2 O_5/rGO catalysts prepared by in-situ growth and mechanical mixing methods, it was further shown that V_2 O_5 nanoparticles were highly dispersed and in situ growth on the rGO surface. Based on X-ray energy spectrometer, V_2 O_5/r GO catalyst had good low temperature denitrification performance due to the chemical adsorption oxygen and low-valent vanadium oxide contained in V_2 O_5/rGO catalyst, which was beneficial to the redox reaction between V_2 O_5 and graphene.     

On the ｛P2,P3｝-Factor of Cubic Graphs

Ler G = （ V, E） be a finite simple graph and Pn denote the path of order n. A spanning subgraph F is called a { P2, P3 }-factor of G if each component of F is isomorphic to P2 or P3. With the path-covering method, it is proved that any connected cubic graph with at least 5 vertices has a { P2, P3 }-factor F such that｜P3（F）｜P2（F）｜, where P2（F） and P3（F） denote the set of components of P2 and P3 in F, respectively.     

Pretreatment of copper-bearing refractory gold ores by bio-heap leaching

The refractory gold ores associated with rich copper and trapped in pyrite and quartz were studied. With conventional technique （all-sliming cyanidation）, the gold recovery rate is only 51.78%. To eliminate the negative effects of copper and pyrite on cyanidation and increase the gold recovery rate, the investigation on bio-heap leaching pretreatment was made, by which Cu would be dissolved and gold would be liberated from pyrite. The experiment adopted mixed bacteria, mainly ThiobaciUus ferrooxidan （named T.fl ）, as the bacterial catalyst for bio-preconditioning and was carried out in a PVC column with a diameter of 20 cm and a height of 1.3 m loaded with gold ores. The temperature was controlled between 28 and 30℃, the pH value was kept between 2.0-2.5, and the flux of sprinkling bacterial liquid was maintained 0.80 L/h. After 45-day＇s bio-oxidization, among the samples sizing from 0 to 5 mm, the oxidation rates of Cu, Fe and S were respectively 44.62%, 28.16% and 25.46%, and the gold recovery rate by cyaniding increased to 80.35%. The bio-heap leaching pretreatment can therefore effectively dissolve Cu and liberate gold from pyrite and lead to the increase of gold extraction.     

Decoioration and mineralization of yeast wastewater by using Ce-Fe/Al2O3 as heterogeneous photo-Fenton catalyst

Decoloration and mineralization of yeast wastewater were investigated by using Ce-Fe/Al2O3 as a heterogeneous photo-Fenton catalyst in fluidized bed reactor in order to solve the problem of yeast wastewater discharge. The experimental results were assessed in terms of total organic carbon（TOC） reduction. The operational and reaction conditions affecting the efficiencies of TOC removal such as initial pH value, H2O2 concentration, catalyst loading and UV power were studied. The results show that TOC is reduced from 347.6 mg/L to 10.8 mg/L, color is changed from 500 units to 0 under the conditions as follows： initial pH value 6. 0, H2O2 concentration of 1. 000 g/L, catalyst loading of 5 g/L, reaction duration of 120 rain and reaction temperature of 30 ℃. The irradiated Ce-Fe/Al2O3 catalyst was complexed with 1,10-phenanthroline and then it was subjected to Fourier transform infrared spectroscopy and diffuse reflectance spectroscopy to confirm the formation of Fe（Ⅱ） in the solid state. Heterogeneous photo-Fenton reaction proves to be effective for the treatment of yeast wastewater.     

Investigation of nanocrystalline structure in selected carbonaceous materials

The structural parameters of nine Indian coals were determined by X-ray diffraction （XRD） and Kaman spectroscopy. The study revealed that the coals contain crystalline carbon of turbostratic structure with amorphous carbon. The stacking height （Lc） and interlayer spacing （rico2） of the crystallite structure of the coals ranged from 1.986 to 2.373 nm and from 0.334 to 0.340 nm, respectively. The degree of graphitization was calculated to range from 42% to 99%, thereby confirming the ordering of the carbon layers with the increase in coal rank. An exponential correlation was observed among the aromaticity （fa）, the lateral size （La）, and the rank （I20/I26）, suggesting that the coal crystallites are nanocrystalline in nature. A very strong correlation was observed between the structural parameters （fa, d002, Lc, the H/C ratio, and I20/I26）, the volatile matter content, and the elemental carbon content, indicating the structures of coals are controlled by the degree of contact metamorphism. The Raman spectra exhibited two prominent bands： the graphitic band （G） and the fn＇st-order characteristic defect band （D）. The deconvolufion resulted in five peaks： G, D1, D2, D3, and D4. The intense D1 band, which appeared at -1350 cm^-1, corresponds to a lattice vibration mode with Alg symmetry. The D2 mode, which appeared at -1610 cm^-1, arises from the structural disorder as a shoulder on the G band.     

Influences of synthesis methods and modifier addition on the properties of Ni-based catalysts supported on reticulated ceramic foams

A method of synthesizing Ni-based catalysts supported on α-Al2O3-based foams was developed. The foams were impregnated with aqueous solutions of metal chlorides under an air atmosphere using an aerosol route. Separate procedures involved calcination to form oxides and drying to obtain chlorides on the foam surface. The synthesized samples were subsequently reduced with hydrogen. With respect to the Ni/Al2O3 catalysts, the chloride reduction route enabled the formation ofa Ni coating without agglomerates or cracks. Further research included catalyst modification by the addition of Pd, Cu, and Fe. The influences of the additives on the degree of reduction and on the low-temperature reduction effectiveness （533 and 633 K） were examined and compared for the catalysts obtained from oxides and chlorides. Greater degrees of reduction were achieved with chlorides, whereas Pd was the most effective modifier among those investigated. The reduction process was nearly complete at 533 K in the sample that contained 0.1wt% Pd. A lower reduction temperature was utilized, and the calcination step was avoided, which may enhance the economical and technological aspects of the developed catalyst production method.     

Desulfurization ability of refining slag with medium basicity

The desulfurization ability of refining slag with relative lower basicity （B） and Al2O3 content （B = 3.5-5.0; 20wt%-25wt% Al2O3） was studied. Firstly, the component activities and sulfide capacity （Cs） of the slag were calculated. Then slag-metal equilibrium experiments were carried out to measure the equilibrium sulfur distribution （Ls）. Based on the laboratorial experiments, slag composition was optimized for a better desulfurization ability, which was verified by industrial trials in a steel plant. The obtained results indicated that an MgO-saturated CaO-Al2O3-SiO2-MgO system with the basicity of about 3.5-5.0 and the Al2O3 content in the range of 20wt%-25wt% has high activity of CaO （αCaO）, with no deterioration of Cs compared with conventional desulfurization slag. The measured Ls between high-strength low-alloyed （HSLA） steel and slag with a basicity of about 3.5 and an Al2O3 content of about 20wt% and between HSLA steel and slag with a basicity of about 5.0 and an Al2O3 content of about 25wt% is 350 and 275, respectively. The new slag with a basicity of about 3.5-5.0 and an Al2O3 content of about 20wt% has strong desulfurization ability. In particular, the key for high-efficiency desulfurization is to keep oxygen potential in the reaction system as low as possible, which was also verified by industrial trials.     

Properties of a new dental photocurable resin based on the expanding monomer and three-component photoinitiator system

The purpose of this study was to use. a three-component photoinitiation system comprising 1wt% CQ （camphorquinone）, 2wt% DMAEMA （2-（dimethylamino） ethyl meth acrylate） and 2wt% ph^2I^＋PF6^- （diphenyliodonium hexafluorophosphate） to initiate the copolymerization of the matrix resins which combine bisphenol-S-bis （3-methacrylate-2-hydroxy propyl） ether （BisS-GMA） with the expanding monomer unsaturated spiro orthoesters 2-methylene-l,4,6-tdspiro[4,4] nonane （MTOSN）, for minimizing the volumetric shrinkage that generally occurs during polymerization. It was hypothesized that MTOSN would expand volumetrically during polymerization under the three-component photoinitiator system and further reductions in volumetric shrinkage would be obtained. The performance study which consists of degree of conversion and condition of the ring-opening reactions of MTOSN, volumetric shrinkage and mechanical properties including tensile bond strength, compressive strength and Vicker＇s hardness were carried out respectively by Fourier transfer infrared, the dilatometer and the universal testing machine. The results supported that the dental composites based on the expanding monomer and three-component photoinitiator system engendered a greater decrease of volumetric shrinkage and better mechanieal properties.     

Use of lime mud from paper mill as a heterogeneous catalyst for transesterification

Lime mud(LM),a solid waste from the paper mill,is used as an economic and environmental friendly heterogeneous basic catalyst for transesterification,which is accompanied by characterization of X-ray fluorescence,thermogravimetric-differential thermal analysis,X-ray diffraction,N2adsorption,and Hammett indicator method.To investigate the performance of the achieved catalyst,which is activated through calcination,the aspects of calcination temperature,reaction time,mole ratio of methanol to oil,catalyst addition percentage,and reaction temperature are concerned.Characterization of catalyst reveals that LM could be activated through calcination to transform the carbonate and hydrate of calcium into the oxide forms and higher calcination temperature could lead to stronger basic strength.However,N2adsorption results indicate that higher temperature causes the sintering of the catalyst and shrinkage of the catalyst grains.When LM is activated at 800°C(LM-800)and the reaction is carried out at 64°C with a methanol to oil mole ratio of 15:1,catalyst addition percentage of 6%,and reaction time of 2h,the maximum transesterification conversion of 94.35%could be achieved.Reusability of LM-800 is also investigated compared with laboratory grade CaO in five reaction cycles and the results indicate that the catalysts derived from LM can be used as an economic and efficient catalyst for biodiesel production.     

A Method for Calculating Fractal Dimension of Amicrons and Fractal Simulation of Boundary Micro-Topography

A simple and practical method to calculate the fractal dimension （FD） of amicron＇s projective surface profile based on fractal theory is proposed. Taking AI（OH）3 material particles as an example, the scanning electron microscope （SEM） photos of particles were processed using an image.processing software （IPS） Photoshop. Taking the pixel as a fixed yardstick with the enlargement of the size of the particle image, the box-dimension and circumference-area （C-S） methods were used to calculate the FD of the surface profile of the particle. The FD of 1.2623 of the classic Koch curve is obtained, which approximates the true value of 1.2628. The complexities of the object＇s boundary and surface micro-topography are simulated successfully by a generator method.     

Synthesis,characterization and electrochemical recognition of metal ions of three new ferrocenyl derivatives containing pyridyl moiety

Three new ferrocene （Fc） based receptors with pyridyl moiety, named methyl-6- ferrocenoylacetyl-2-pyridine carboxylate （FcLl）, 1,1＇-（2,6-bispyridyl）bis-3-ferrocenyl-l,3-propanedione （FcL2）, ferrocenecarboxaldehyde-2,6-dipicolinoyhydrazone （FcL3） were synthesized, and further characterized by elemental analysis, IR spectra, UV-Vis spectra, 1H and 13C NMR. The electrochemical properties and ion sensing properties of FcL1, FcL2 and FcL3 were also investigated by means of cyclic voltammetry in ethanol solution with 0.1 mol/L LiC104 as the supporting electrolyte. The E~ values of the receptors increase with the scanning rate increasing at high scanning rate, and Ipa/Ipo approaches unity, indicating that the redox reaction is basically reversible. Their recognition performances to different metal cations such as Cd（II）, Co（II）, Cu（II）, Hg（II）, Mn（II）, Ni（II）, Zn（II） show that the FcL1 is responsive to Cu（II） with the maximum electrochemical shift of the FcL1 for Cu（II）of about 72.0 mV, whereas the FcL2 is responsive to Cu（II） and Mn（II） with shift of 102 mV and 109 mV, respectively, and the FcL3 is responsive to Hg（II） and Mn（II） with the shift of 53.0 mV and 54.0 mV, respectively. All the results show that these receptors may have potential applications in electrochemical sensor technology, material science, and molecular devices.     

Structure and dielectric properties of ZnO and Nb<Subscript>2</Subscript>O<Subscript>5</Subscript> doped BaO-TiO<Subscript>2</Subscript> system microwave ceramics

The microwave dielectric properties and microstructure of BaTi4.3ZnyO9.6＋y ＋0.02 mol% SnO2＋0.01 mol% MnCO3＋x mol% Nb2O5（x=0-0.05, y=0-0.08） system ceramics were studied as a function of the amount of ZnO and Nb2O5 doped. Addition of （y=0-0.05） ZnO and （x=0-0.025） Nb2O5 enhanced the reactivity and decreased the sintering temperature effectively. It also increased the dielectric constant ε r and quality factor Q（=1/tan 8） of the system due to the substitution of Ti^4＋ ions with incorporating Zn^2＋and Nb^5＋ ions, which was analyzed by the reaction ZnO＋Nb2O5＋ 3 TiTxTi →ZnTi＋ 2NbTi＋3TiO2. When the system doped with （y=0.05） ZnO and （x=0.025） Nb205 were sintered at 1 160 ℃ for 6 h, the εr. Qf0 value and rfwere 36.5, 42 000 GHz, and＋1.8 ppm/℃, respectively, at 5 GHz.     

Design and analysis of two-layer anonymous communication system

A new architecture for scalable anonymous communication system（SACS） was proposed. The users were divided into several subgroups managed by different sub-blenders, and all sub-blenders were managed by the main-blender using two layers management scheme. The identity information of members are distributed on different sub-blenders, which makes each member keep much less information and network overload greatly reduce. The anonymity and the overhead of the new scheme were analyzed and compared with that of Crowds, which shows the cost of storage and network overhead for the new scheme largely decreases while the anonymity is little degraded. The experiment results also show that the new system architecture is well scalable. The ratio of management cost of SACS to that of Crowds is about 1：25 while the value of P（1｜H1＋） only increases by 0.001-0.020, which shows that SACS keeps almost the same anonymity with Crowds.     

Photocatalytic oxidation of Rhodamine B in a three-phase internal circulating fluidized bed with TiO2/SiO2 as photocatalyst

A novel photoreactor of three-phase internal circulating fluidized bed was applied to the degradation of Rhodamine B with TiO2/SiO2 catalyst and TiO2 powder,respectively.The experimental results showed that the photocatalytic activity of TiO2/SiO2 catalyst was much higher than that of TiO2 powder under the same condition,and the half life of Rhodamine B using TiO2/SiO2 was 9.5 min,much lower than 63 min when using TiO2 powder.Moreover,TiO2/SiO2 had a good adsorption capacity of Rhodamine B,which played an important role on degradation.In addition,it was found that the degradation kinetics of Rodamine B with TiO2/SiO2 catalyst did not follow the first order reaction.The degradation kinetics model in terms of the adsorption process of catalyst and the analytic solution of reactant degradation rate in liquid phase could be deduced,which consisted of two parts.The first part was due to the adsorption,while the second part was due to the photocatalysis.In the beginning of the reaction,the adsorption process was dominant.However,when the adsorption achieved a balance,the degradation of Rhodamine B in liquid phase and solid phase was mainly caused by photocatalysis and the degradation kinetics model conformed to the first order reaction.