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.     

Polyoxometalates Pillared Hydrotalcite： Synthesis and Catalysis in Transesterification of Dimethyl Carbonate and Phenol

The salts of para-tungstic and para-molybdic were heterogenized for their effective use as solid catalysts in the transesterification reaction of dimethyl carbonate and phenol by inserting them between the layers of Mg₂Al-hydrotalcite. These catalysts were characterized by FT-IR spectra and X-ray powder diffraction. Polyoxometalates (POMs) clusters were intercalated into the interlayer of layered double hydroxide (LDH) via anion exchange with organic acid precursor in Mg₂Al-LDH, and the integrity of the clusters ^6- and ^6- was maintained. The intercalated para-molybdic cluster showed high catalytic activity and reusability in the transesterification under mild reaction conditions. When the reaction was carried out at 180?℃, with a molar ratio of phenol to DMC of 1∶1, a reaction time 10?h, and a catalyst amount 1%(wt), the conversion of phenol was 10.0%, the selectivities of diphenyl carbonate and methyl phenyl carbonate were 10.7% and 86.1%, respectively.     

Microwave-assisted hydroxylation of benzene to phenol with H_2O_2 over FeSO_4/SiO_2

Hydroxyl radicals HO are generated under Fenton-like (Fe2++H2O2→HO?+OH?+Fe3+) catalytic conditions upon microwave irradiation. Liquid-phase direct catalytic oxidation of benzene to phenol was obtained using FeSO4 supported on silica gel as a solid catalyst and hydrogen peroxide as the oxidant. The effects of various parameters, such as the different solvents, the amount of solvent used, the amount of catalyst used, the reaction time, the reaction temperature and the amount of hydrogen peroxide used on the yield of phenol were studied to identify optimum reaction conditions. Conventionally heated reaction gives a phenol yield of 0.6%. A higher phenol yield of 13.9% with a selectivity of 100% is obtained when the reaction mixture was irradiated with micro-wave energy. It is concluded that microwave irradiation offers more effective control of energy input for hydroxyl radical generation that is appropriate for various synthetic reactions.     

Preparation,characterization of superacid SO4 2−/ZrO2-SiO2 and its activity on catalytic synthesis of methyl p-nitrobenzoate

Solid superacid SO42-/Zr O2-SiO2 was prepared by dip-impregnation method, and its catalytic activity was tested with esterification of p-nitrobenzoic acid and methanol. The optimum conditions were also found, that is, the molar ratio between silica and zirconia was 10:1, the calcination temperature was 550 ℃ and the soaked consistency of H2SO4 was 1.0 mol?L-1. Under the conditions that the ratio of methanol to acid(m L/g) was 12:1, the amount of catalyst was 0.5 g, the reaction time was 5 h and the stirring speed was 800 r?min-1, the yield of methyl p-nitrobenzoate could reach up to 90.5%. Then the characterizations of cataslyst, including the acidity and types of acidic centers, specific surface area and surface structure was respectively examined by Hammett indicator, in-situ pyridine IR, BET method, FT-IR(KBr), transmission electron microscope(TEM), and X-ray diffraction(XRD). The results showed that the catalyst SO42-/Zr O2-SiO2 was superacid with high specific surface area due to Ho-12.70. It contained acidic sites of Lewis and BrΦnsted, and its surface structure changed after esterification. The zirconia crystal was mainly tetragonal and silica crystal was not found.     

Synthesis of a macromer, MPEGAA, used to prepare an AMPS-modified polyacrylic acid superplasticizer

A macromer, methoxypolyethylene glycol acrylate （MPEGAA）, was synthesized by direct esterification using methoxypolyethylene glycol （MPEG-1200） and acrylic acid （AA） as the main materials. MPEGAA was then used to prepare a polyacrylic acid superplasticizer modified with 2-acrylamido-2- methylpropane sulfonic acid （AMPS）. A single-factor test was performed to investigate the effects of the molar ratio of acid to alcohol （n（AA）/n（MPEG））, inhibitor amount, catalyst amount, temperature, and time of esterification on the synthesis of MPEGAA. The experimental results showed that the optimal esterification conditions were as follows： n（AA）/n（MPEG）, 3.5：1; amount of hydroquinone （as an inhibitor）, 1.2%; amount of para-toluenesulfonic acid （as a catalyst）, 5.5%; reaction temperature, 95 ~C; and reaction time, 6 h. The AMPS- modified polyacrylic acid superplasticizer prepared under the optimal esterification conditions enabled the achievement and maintenance of high cement dispersibility. At an admixture amount of 0.15%, the cement paste fluidity was initially as high as 300 mm, and then decreased to 315 mm after 1 h and to 290 mm after 2 h.     

A Comparative Study on the Pozzolanic Activity between Nano-SiO2 and Silica Fume

The pozzolanic activity of nano-SiO2 and silica fume was comparatirely stndied by X-ray diffraction （ XRD ） , differential scanning calorimetry （DSC）, scanning electron micrascopy （SEM） and the compressive , bond and bending streugths of hardened paste and concrete were also measured. Results indicate that the compressive strength development of the paste made from Ca（OH）2 and nano-SiO2, the reaction rate of Ca（ OH）2 with nano- SiO2 and the velocity of C-S-H gel formation from Ca （ OH）2 with nano-SiO2 showed marked increases over those of Ca（ OH）2 with silica fume. Furthermore, the bond strength at the interface between aggregate and hardened cement paste, and the bending strength of concrete incorporated with 3% .NS increased more than those with SF, especially at early ages. To sum up, the pozzolanic activity of nano-SiO2 was much greater than that of silica fume. The results suggest that with a small amount of nano-SiO2, the Ca（ OH）2 crystal at the interface between hardened cement paste and aggregate at early ages may be effectively absorbed in high performance concrete.     

Influence of Aluminum Ions Implantation on Corrosion Behavior of Zircaloy-2 Alloy in 1M H2SO4

The specimens were implanted with aluminum ions with fluence ranging from 1× 10^16 to 1× 10^17 ions/cm^2 to study the effect of aluminum ion implantation on the aqueous corrosion behavior of zircaloy-2 by metal vapor vacuum arc source （MEVVA） at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy （XPS） and Auger electron spectroscopy （AES）, respectively. Transmission electron microscopy （TEM） was used to examine the microstructure of the aluminum-implanted samples. Glancing angle X-ray diffraction （GAXRD） was employed to examine the phase transformation due to the aluminum ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-2 in a 1 M H2SO4 solution. It is found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-2 implanted with aluminum ions. Finally, the mechanism of the corrosion behavior of aluminum- implanted zircaloy-2 was discussed.     

Preparation and characterization of three-dimensional chrysanthemun flower-like calcium carbonate

Calcium carbonate with three-dimensional chrysanthemun flower-like structure was successfully prepared from calcium chloride and sodium carbonate ethanol/water mixed solution by a simple precipitation method,using trisodium citrate as crystal modifier.The experimental results show that the three-dimensional structure of chrysanthemun flower-like calcium carbonate is built up with several symmetrical micrometer multi-layer petals arranged around the multi-layer pancake-liked center,and the micrometer center and petals are assemblied by a large number of nanometer spherical particles with size 10-20 nm.It is found that the amount of trisodium citrate,the ethanol volume content has an important influence on the formation of this morphology.A possible mechanism is proposed to explain the formation of three-dimensional chrysanthemun flower-like calcium carbonate according the results.Scanning electron microscopy(SEM),X-ray powder diffraction(XRD),flourier transform infrared spectroscopy(FT-IR),thermogravimety analysis(TG),transmission electron microscopy(TEM) equipped with energy-dispersive X-ray(EDX),and selected area electron diffraction(SAED) were used to characterize the crystals.     

Influence of Sodium Carbonate Amount on Crystalline Phase and Structure Stability for Doping Nickel Hydroxide

Alpha nickel hydroxide has better performances than commercial beta nickel hydroxide. However, the main defect is that α-phase is difficult to synthesize and easily transformed to β-phase Ni(OH)_2 upon aging in a strong alkaline solution. In this study, the Al-Co, Al-Yb, Yb-Co and Al-Yb-Co multiple doping was used respectively. By controlling the amount of sodium carbonate, the α-Ni(OH)_2 was prepared by ultrasonic-assisted precipitation. And the influence of sodium carbonate on the crystalline phase and structure stability for alpha nickel hydroxide was studied. The results demonstrate that, with increasing amount, the biphase nickel hydroxide transforms to pure alpha nickel hydroxide gradually, and the structure stability is also improved. When the amount of sodium carbonate is 2 g, the sample still keeps α-Ni(OH)_2 after being aged for 30 days, for Al-Yb-Co-Ni(OH)_2. And when the amount is less than 2 g, the phase transformations exist in the samples with different extents. These results demonstrated that the amount of sodium carbonate is a critical factor to maintain the structural stability of α-Ni(OH)_2.     

Influences of Carboxyl Methyl Cellulose on Performances of Mortar

Carboxyl methyl cellulose （CMC） was mixed into mortar to improve the waterretention performance of mortar, the quality of floated coat of aerated concrete became better. The consistency and compression strength of mortar with CMC were studied. The water absorption was studied with the method of filter paper. The micro mechanism was researched with X-ray diffraction and scanning electron microscopy（SEM）. The experimental results show the water-holding performance of mortar with CMC is largely improved and it is better when the mixed amount is about 1.5%; the compression strength had a descending trend with the increase of CMC; CMC reacted with calcium hydroxide（CH） into the deposition of calcium carboxyl methyl cellulose.     

Preparation of Ni/PZT core-shell nanoparticles and their electromagnetic properties

The Ni nanoparticles coated with Pb(Zr,Ti)O_3(PZT) were synthesized by a sol-gel method and in situ reaction. And their structure, oxidation resistance, and electromagnetic properties were investigated. The X-ray diffraction patterns(XRD) exhibited that a small amount of impure phase characterized to Ni(OH)_2 was detected from the ammonia-treated Ni nanoparticles and the ammonia-treated Ni nanoparticles coated with PZT. After being pre-treated with aqueous ammonia, the PZT coating layer was more uniform and about 10 nm in thickness. The oxidation resistance of the ammonia-treated Ni nanoparticles coated with PZT, compared with that of the non-treated ones, was improved by about 66 ℃. The PZT shell layer prepared by in-situ reaction can greatly reduce the dielectric constant and improve the natural resonance loss at high frequency, so as to obtain the optimal impedance matching performance of the electromagnetic wave transmission.     

Preparation and characterization of high photoactive TiO2 catalyst using the UV irradiation-induced sol-gel method

High photoactive TiO2 catalyst was prepared using the sol-gel method through UV irradiation during the formation stage of nuclei. The surface morphology and microstructure of the prepared catalyst were characterized using scanning electron microscopy （SEM）, X-ray diffraction patterns （XRD）, and Fourier transform infrared spectroscopy （FF-IR）. The photoactivity was evaluated by the degradation of methylene blue. The results show that the photocatalysis of the prepared catalyst is higher than that of conventional heat-treated particles. The higher photoactivity is a combined result of favorable microstructure, appropriate hydroxyl groups, and active sites of Ti^3＋ ions on the surface of TiO2. It is concluded that the ultraviolet irradiation-induced sol-gel method is an effective method to enhance the photocatalysis of TiO2.     

Preparation and photocatalytic activity of Gd-doped TiO2 nanofibre

In order to realize the photocatalysis of TiO2 in the sunlight and directly apply it to waste water treatment, the Gd-doped TiO2 nanofibre was synthesized using two-step synthesis method as follows： Firstly, potassium carbonate, titanium dioxide and proper gadolinium oxide （dopant） were calcined in the muffle at high temperature and the doped gadolinium K2Ti4O9 fibres were obtained; secondly, the fibre was heated using glycerol as solvent until Gd-doped TiO2 nanofibres were obtained. The synthesized samples were characterized using scanning electron microscopy, transmission electron microscopy and X-ray diffraction. The results show that Gd-doped TiO2 nanofibre heat-treated by glycerol solvent can inhibit the agglomeration, so the grain diameter of the fibre is smaller than that without heat-treated with glycerol. Meanwhile, the diameter of the fibre decreases with the increase of the heating temperature and time. 97%- 98% of Gd-doped TiO2 nanofibre is anatase. The photocatalysis results showed that the photocatalysis activity of Gd-doped TiO2 nanofibre is just a little lower than that of TiO2 powder.     

New technique of comprehensive utilization of spent Al2O3 -based catalyst

A new technology was developed to recover multiple valuable elements from the spent Al2O3-based catalyst by X-ray phase analysis and exploratory experiments. The experimental results show that in the condition of roasting temperature of 750 ℃ and roasting time of 30 min, molar ratio of Na2O to Al2O3 of 1.2, the leaching rates of alumina, vanadium and molybdenum in the spent catalyst are 97.2%, 95.8% and 98.9%, respectively. Vanadium and molybdenum in sodium aluminate solution can be recovered by precipitators A and B, and the precipitation rates of vanadium and molybdenum are 94. 8% and 92. 6%. Al（OH）3 was prepared from sodium aluminate solution in the carbonation decomposition process, and the purity of Al2O3 is 99. 9% after calcination, the recovery of alumina reaches 90. 6% in the whole process; the Ni-Co concentrate was leached by sulfuric acid, a nickel recovery of 98. 2% and cobalt recovery over 98.5% can be obtained under the experimental condition of 30% H2SO4, 80 ℃, reaction time 4 h, mass ratio of liquid to solid 8, stirring rate 800 r/min.     

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.     

Microstructure Study of Ti-24Al-14Nb-3V Alloy

The microstructure of Ti-24Al-14NB-3V intermetallic alloy with solution treated was investigated by trans mission electron microscopy (TEM) and selected area electron diffraction (SAD) in conjunction with X-ray energydispersive spectroscopy (EDS) techniques. It shown that =50% ductile βo-phase and small amount of O phase,and α2 with the number of dislocations having c-component resulted in increasing slip system of the material, havecontributed to a good combination of strength and ductility at room temperature. Owing to some reciprocal planes ofsimilarity between α2 and O Phases, to distinguish both of two phases, a series of diffraction patterns obtained bytilting around one reciprocal direction of the phase are needed based on the systematic extinction and reciprocalplanes sequences occurred in the diffraction patterns, if those patterns are not containing one of three reciprocal unitvectors, a*, b*, c* in terms of the crystal unit cell, a, b, c.     

Synthesis and coloring properties of Cd（S1-xSex） pigments by precipitate-hydrothermal method

Cd（S1-xSex） pigments （red to yellow） were synthesized by precipitate-hydrothermal method. The structure, morphology and hue of the powder were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, energy dispersive X-ray spectroscopy （EDAX） and CIE chromaticity. The optimum synthesis conditions were obtained and reaction mechanism was further analyzed as well. The results show that molar ratio of S to Se, pH value and hydrothermal reaction conditions have great effects on the hues of the pigments. Pigments with vivid hues are obtained under the conditions that pH value is about 13.0, hydrothermal reaction condition is at 140 ℃ for 4 h or at 160 ℃ for 6 h. The reaction mechanism is that Se^2- of Cd（S1-xSex） substitutes S^2- of CdS and then forms a continuous solid solution.     

One-pot synthesis of cyclic aldol tetramer and ?, β-unsaturated aldol from linear aldehydes using quaternary ammonium combined with sodium hydroxide as catalysts

One-pot synthesis of cyclic aldol tetramer and α, β-unsaturated aldol from C3-C8 linear aldehydes using phase-transfer catalyst(PTC), quaternary ammonium, combined with sodium hydroxide as catalysts was investigated. Butanal was subjected for detail investigations to study the effect of parameters. It was found that the selectivity of cyclic aldol tetramer depends greatly on the operating conditions of the reaction, especially the PTC/butanal molar ratio. The average selectivity of 2-hydroxy-6-propyl-l, 3, 5-triethyl-3-cyclohexene-1-carboxaldehyde(HPTECHCA) was 54.41% using tetrabutylammonium chloride combined with 14%(mass fraction) Na OH as catalysts at 60 °C for 2 h with a PTC-to-butanal molar ratio of 0.09:1. Pentanal was more likely to generate cyclic aldol tetramer compared with other aldehydes under the optimum experimental conditions. Recovery of the PTC through water washing followed by adding enough sodium hydroxide from the washings was also demonstrated.     

Microstructural evolution during self-propagating high-temperature synthesis of Ti-Al system

In order to investigate the microstructural evolution during self-propagating high-temperature synthesis （SHS） of Ti-Al powder mixture with an atomic ratio of Ti： Al=1：1, a combustion front quenching method （CFQM） was used for extinguishing the propagating combustion wave, and the microstructures on the quenched sample were observed with scanning electron microscope （SEM） and analyzed with energy dispersive spectrometry （EDS）. In addition, the combustion temperature of the reaction was measured, and the phase constituent of the synthesized product was inspected by X-ray diffraction （XRD）. The results showed that the combustion reaction started from melting of the Al particles, and the melting resulted in dissolving of the Ti particles and forming of Al3Ti grains. As the Al liquid was depleted, the combustion reaction proceeded through solid-state diffusion between the solid Al3Ti and the solid Ti. This led to the forming of TiAl and Ti3Al diffusing layers. In addition, the combustion reaction is incomplete besides TiAl, there are a large amount of Ti3Al and TiAl3 and a small amount of Ti in the final product. This incompleteness chiefly results from the using of coarser Ti powder.     

Preparation and Optical Properties of V2O5 Nanotube Arrays

V2 O5 nanotube arrays in porous atomic alumina （ PAA ） template were obtained from V2O5 sols prepared by melt quenching method. X-ray powder diffraction and selected area electron diffraction investigations demonstrate that V2O5 nanotubes are orthorhombic. Results by scanning electron mieroscopy and transmission electron microscopy results shove that V2O5 nanotubes with a uniform diameter form highly ordered arrays. The diameter and length of the nanotubes depend on the pore diameter and the thickness of the PAA template used. It is proved that the sol-gel template process is a cost-saving , simple and readily-controlled method to prepare metal oxides nanomaterials .Owing to the quantum size effect. the optical absorption edge of V2O5 nanotubes in PAA ehibits a significant blue shift with respect to that of bulk V2O5.