Synthesis of Ti-Ce-Si Binary and Ternary Nanocomposite Photocatalyst by Supercritical Fluid Drying Technology

Ti-Ce, Ti-Si binary and Ti-Ce-Si ternary novel nanocomposite oxide photocatalysts were prepared with cheap inorganic salts TiCI4, Na2SiO3·9H2O and Ce（NO3）3·6H2O as precursors by supercritical fluid drying （SCFD） technology. The catalysts were characterized by means of XRD and TEM. The particle size of nanocomposite oxide photocatalysts synthesized by SCFD method is about 6 - 11 nm, which is smaller than those obtained by common drying method （CD）. The phase transformation from anatase to rutile was inhibited by SCFD technology. The peaks of SiO2 and CeO2 in XRD patterns indicate that a SiO2 amorphorous phase exists in all the samples and CeO2 is well dispersed on the surface of TiO2. The orthogonal test was designed to optimize the preparing conditions. It is found that ceria dop;.ng enhances the photocatalyric activity markedly, and the optimum doping of CeO2 is 0.1%. The thermal stability of photocatalyst can be improved ; the growth of particle-size and the decrease of surface area can be prohibited by doping of SlOe. Heat-treatment is a necessary factor to induce chemistry change of Ti-Si surface. The optimum heat-treating temperature is 600℃. A novel and efficient Ti-Ce-Si ternary nanocomposite was prepared by SCFI） method with strong thermal stability and high photoactivity in the photodegratation of phenol.

Synthesis and Characterization of TiO_2-CeO_2 Nanocomposite by Supercritical Fluid Drying

TiO_2-CeO_2 nanocomposite particles were prepared with Ce(NO_3)_3·6H_2O and TiCl_4 as precursors by the codeposition method and supercritical fluid drying (SCFD) technology. The particles prepared were characterized by means of XRD, TEM and FTIR. The results show that SCFD can give rise to the direct synthesis of the anatase TiO_2-CeO_2,and the particle size is 6～11 nm under 500 ℃ thermal-treated,smaller than that by common drying (CD). The phase transformation from anatase to rutile is inhibited by supercritical fluid drying technology. The peak of CeO_2 is not observed in XRD patterns,Ce-O band vibration was present in FTIR spectrum,which indicates that CeO_2 is well dispersed on the surface of TiO_2.

Effect of Drying Methods on the Structure and Combustion Activity of Mn-Substituted Hexaaluminate Catalysts

Conventional oven drying (COD) and supercritical drying (SCD) methods wereapplied to the preparation of Mn-substituted hexaaluminate (BaMnAl_(11)O_(19-α)) catalysts. Theeffect of drying methods on phase composition, specific surface area, pore structure, reductionbehavior of Mn^(3+) ions, and combustion activity of the samples was investigated. The homogenousmixing of the components in the sol-gel process could be maintained by SCD, and the hexaaluminatephase was almost the only phase of the resulting materials after calcination. H_2-TPR revealed thatthe Mn^(3+) ions in the sample obtained by SCD were easier to be reduced than that by COD. Moreover,the samples obtained by SCD have higher surface area, narrower pore size distribution, and highercombustion activity than those obtained by COD.

Preparation of TiO_2-MoO_3 nano-composite photo-catalyst by supercritical fluid dry method

A series of TiO 2-MoO 3 nano-composite photocatalysts were prepared by supercritical fluid dry method(SCFD) and an impregnation technique with TiCl 4 and (NH 4) 6Mo 7O 24 ·4H 2O as the starting materials. The catalysts were characterized by the means of XRD, TEM and UV-Vis. Methyl orange was used as model compound for the evaluation of their catalytic activities. The results indicated that the photo-catalyst prepared by SCFD had the advantages of small size(12.84 nm), narrow distribution and good dispersivity. The presence of small amount of Mo in composite catalyst gives rise to the red shift of its absorbance wavelength, decrease of its energy gap and increase of the utility of visible light. Furthermore, higher surface acidity of the photo-catalyst was obtained as the result of the addition of MoO 3. Compared with pure TiO 2, the catalytic activity of the TiO 2-MoO 3 nano-composite photo-catalyst was improved significantly. As the doping concentration of the composite catalysts was controlled at 0.6%(molar percentage), 100% degradation of methyl orange was achieved with in 1.2 h irradiation time.

Preparation of (Ti, Sn)O_2 Nano-Composite Photocatalyst by Supercritical Fluid Dry Combination Technology

A series of TiO2-SnO2 nano-sized composite photo-catalysts containing Sn (9.3%-30.1%) were prepared from TiCI4 and SnCl4·5H2O by using sol-gel, supercritical fluid dry and solid-phase reaction (SCFD) combination technology. Characterizations with X-ray diffraction (XRD), transmission electron microscopy (TEM) and Fourier Transform Infrared Spectroscopy (FTIR) showed that, in addition to anatase type TiO2, a new active phase (Ti, Sn)O2 (with particle size of 2.0-4.3 nm) formed, and there were no SnO2 crystals observed in the range of the doping concentration studied. Photo-catalytic reaction of phenol was used as a model reaction to evaluate the catalytic activities of the obtained catalysts. Compared with pure TiO2 or Ti-Sn catalyst prepared with general sol-gel method, Ti-Sn nano-composite photo-catalyst thus obtained showed significant improvement in catalytic activity. The photo-catalytic degradation rate of phenol could reach as high as 93.5% after 7 h. The preparation conditions of the new phase (Ti, Sn)O2 were investigated and its catalytic mechanism was proposed. The photo-catalytic particles prepared using SCFD combination technology exhibited small particle size, large surface area and high activity.

Preparation of Different Metal Substituted Hexaaluminate and Its Catalytic Performance of Methane Combustion

Different metal substituted hexaaluminate catalysts （Ba0.8 La0.2 MAl11 O19-α） were the M = Mn, Fe, Co, Cu were prepared using alumina sol as the （NH4）2CO3 coprecipitation precursor and supercritical drying （SCD） method. Meanwhile the catalysts were characterized using BET, XRD, TEM, UV-Vis-DR and O2-TPD techniques. The rod-like hexaaluminate nanoparticles with high surface area ranging from 42 to 73 m^2·g^-1 were obtained after calcinations at 1200℃. The XRD results reveal that the main crystal phase of the catalyst is hexaaluminate and small amount of α-Al2O3 existed except for Ba0.8La0.2MnAl11O19-α catalyst. Moreover, the UV-Vis-DR results verify that Fe^3＋ , Mn^3＋ occupy the Oh sites in the hexaaluminate structure while Co^3＋ , Cu^2＋ locate at the Oh and Td sites.

THE FABRICATION OF CARBON AEROGELS BY GELATION IN ISOPROPANOL WITH BASIC CATALYST

A new method for the fabrication of carbon aerogels is reported in this paper. Resorcinol and furfural were gelated in isopropanol with basic catalysts and then dried directly under isopropanol supercritical condition, followed by carbonization under nitrogen atmosphere. The bulk densities of carbon aerogels obtained are in the range of 0.21g/cm3~0.27g/cm3 and the sizes of the interconnected carbon nano-particles are in the range of 20nm^30nm. All of the aerogel samples exhibit high BET surface areas in the range of 730m2/g^900m2/g. The bulk density, micro-pore volume, meso-pore volume and meso-pore diameter can be controlled by gelation conditions such as R/I ratio and R/C ratio.

Study on Properties of Composite Oxides TiO_2/SiO_2

The nanometer particles of TiO_2 and TiO_2/SiO_2 oxides wereprepared by sol-gel supercritical fluid drying method. The propertiesof TiO_2 and TiO_2/SiO_2 were characterized by means of BET(Brunner-Emmett- Teller method), TEM (transmission electronmicroscopy), SEM (scanning electron microscopy), XRD (X-ray diffrac-tion) and FTIR (Fourier transform-infrared) techniques. The effectsof different preparation route, prehydrolysis and non-prehydrolysis,on the properties of TiO_2/SiO_2 oxide were also examined.

Synthesis and Photocatalytic Property of the ZrO_2/TiO_2 Pillared Laponite

The ZrO2/TiO2 pillared laponite （Ti-Zr-lap） photocatalysts were prepared with intercalation reaction by supercritical fluid drying （SCFD）,and characterized by XRD,TEM,SEM and BET surface area analysis,and the photocatalytic properties of Ti-Zr-lap were investigated by degradation of azo dye acid red B （ARB）.The results showed that the ZrO2/TiO2 pillared structures in laponite could be formed,with the mass fraction of （Zr4＋＋Ti4＋）/laponite （Xm） increasing,the basal spacing and the BET surface area of Ti-Zr-lap significantly increased.The Ti-Zr-lap used as photocatalyst had the advantages of stable and porous layered structure,large surface area with the anatase type TiO2.Compared with the Ti-Zr-lap dried by air drying,the Ti-Zr-lap dried by SCFD showed better photocatalytic property which was very close to that of P25 TiO2.Using the Ti-Zr-lap as photocatalyst with the optimum Xm of 0.16 and the calcination temperature of 500 ℃,under the conditions of the initial concentration of ARB 20 mg/L,photocatalyst concentration of 1.5 g/L and irradiation time 60 min,the decoloring rate of ARB could achieve 98.3%,indicating that the Ti-Zr-lap had excellent photocatalytic property.

Synthesis and Characterization of Nanoscale Mullite Powder

Nanoscale mullite powder were synthesized via Sol-gel-SCFD and middle temperature treatment by using AIP( aluminum-isopropoxde) and TEOS ( tetraethyl orthosili-cate) as starting materials. Both of the binary aerogel of alumina-silica and calcined nanoscale materials were investigated by using TG-DSC ( thermogravimetry-differentialscanning calorimeter) , TEM( transmission electron microscope) , XRD(X-Ray diffractometer ) and specific surfacearea and porosimetry. TG-DSC indicated the removal of most of the volatiles, i.e. 15.98% up to about 700℃ ,and in the DSC curve , existence of two exothermic peak atabout 445℃ and 1015℃ may be due to the crystallizationof Si-O-Al-O in diphasic gels and mullitization and a small endothermic peak at about 805℃ indicated the decomposition of structural water molecules . On the colligation of the results of TG-DSC, XRD and TEM, the beginning temperature of mullitization in Al2O3-SiO2 aerogel system can be confirmed at about 1015℃. XRD results also showed the formation of mullite at the range 1100-1200℃. TEM and surface area and porosimetry results showed that the nanosized mullite were calcinated at 1100and 1200℃ exhibited size 30 nm and 50 nm, specific surface area 138.91 m2/g and 95.81 m2/g.

Mesoporous poly(ionic liquid)s with dual active sites for highly efficient CO_(2)conversion

Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.

Processing and Sintering of Agglomerate-free CaO-ZrO2 Powder

Coprecipitation supercritical fluid drying technology has been employed to synthesize calcia-stabilized zirconia ultrafine powder with low-cost inorganic salts as the starting materials. The sintering behaviors of these powders were also investigated. The results showed that supercritical fluid drying could effectively alleviate the hard agglomeration of grains during the gel drying process, and the morphology of the powder retained the network texture of the original gel. The resulting particles were characterized by small particle size (5-20 nm), better monodispersity and high surface area, which gave rise to high activity and sinterability. Consequently, these powders could readily be compacted into the desired shape and their densification could be carried out in shorter time and at lower temperatures. For instance, nanometer-sized powder calcined at 600癈 for 2 h could be cold-pressed into a green body and sintered at 1100?for 0.5 h to attain a dense body with bulk density of 5.9718 g/cm3 and specific pore volume of 0.0008 cm3/g.

Atmospheric Drying UHMWPE Membranes via Multiple Stage Extractant Exchange Drying Technique

Ultra-high molecular weight polyethylene(UHMWPE)membranes were prepared by 5 wt%UHMWPE/parafn oil gels via thermally induced phase separation method and dried in air without signifcant collapse.The UHMWPE membranes were annealed at 110℃ for increasing the pores size in order to decrease the capillary forces.Furthermore,a new multiple stage extractant exchange drying(MSEED)technique was adopted to decrease the shrinkage of the UHMWPE membranes.Specifcally,the parafn oil was extracted by dichloromethane,then dichloromethane was replaced by ethanol,next ethanol could be exchanged to other liquid which is non-afnity with UHMWPE,for example water.UHMWPE membranes(annealing for 25 min)dried by dichloromethane-ethanol-water-air process have the lowest volume shrinkage of 16.5%and the porosity is as high as 88.29%.Moreover,compared with supercritical CO_(2)(SC-CO_(2))drying,atmospheric drying UHMWPE membranes have a lower pure water permeance,but a higher carbon particles rejection.

Effects of preparation methods of support on the properties of nickel catalyst for hydrogenation of m-dinitrobenzene

Using tetraethyl orthosilicate(TEOS)as the pre-cursor of silica,the silica aerogel and xerogel,which were used as supports of nickel-based catalysts for liquid hydroge-nation of m-dinitrobenzene to m-phenylenediamine,were prepared by the sol-gel method combined with supercritical drying(SCD)and conventional drying,respectively.Then,a series of nickel-based catalyst samples supported on these supports were prepared by the incipient wetness impregna-tion method with an aqueous solution of nickel nitrate as well as lanthanum nitrate as impregnation liquids.Based on the characterization results of nitrogen adsorption-desorption(BET),X-ray diffraction(XRD),temperature programmed reduction(TPR),temperature-programmed desorption of hydrogen(H2-TPD),and catalytic activity evaluation,the physico-chemical properties and catalytic performances of the catalysts were investigated.The results show that the nickel crystallites on the binary nickel catalyst using silica aerogel as support are of smaller particle size.However,com-pared with the sample supported on silica xerogel,the nickel catalyst supported on the silica aerogel exhibits lower activity and selectivity for the hydrogenation of m-dinitrobenzene because it has a lesser amount of active sites and weaker absorption ability to reactants caused by sintering of the nickel crystallites.The addition of promoter La2O3 could increase the activity and selectivity of the catalysts.Among all the nickel-based catalyst samples prepared,the La2O3 promoted ternary nickel-based catalyst supported on silica xerogel exhibits the highest activity and selectivity for the hydrogenation of m-dinitrobenzene to m-phenylenediamine,which could be attributed to its highest active surface area and appropriate absorption strength to reactants.Over this prom-ising catalyst,the conversion of m-dinitrobenzene and the yield of m-phenylenediamine could reach 97.0%and 93.1%,respectively,under proper reaction conditions of hydrogen pressure 2.6 MPa,temperature 373 K,and reaction time 1 h.