Novel promoting effects of cerium on the activities of NO_x reduction by NH_3 over TiO_2-SiO_2-WO_3 monolith catalysts

A series of catalysts were prepared by doping different loadings of CeO2 over TiO2-SiO2-WO3 and used for the selective catalytic reduction of NOx by NH3. The experimental results showed that the selective catalytic reduction（SCR） performance and SO2-resistant ability of TiO2-SiO2-WO3 were greatly enhanced by the introduction of cerium. The catalyst containing 10% CeO2 showed the highest NO conversion in a wide temperature range and good N2 selectivity with broad operation temperature window at the gas hourly space velocity（GHSV） of 30000 h–1, which was a very promising catalyst for NOx abatement from diesel engine exhaust. The catalysts were characterized by X-ray diffraction（XRD）, scanning electron microscopy with energy dispersive X-ray spectroscopy（SEM-EDS）, N2 adsorption-desorption（BET） and X-ray photoelectron spectroscopy（XPS）. The characterization results showed that the bigger pore radius, higher surface atomic concentration and dispersion of Ce and the abundant adsorbed oxygen on the surface of catalyst contributed to the best NH3-SCR performance of CeO2/TiO2-SiO2-WO3 catalyst containing 10% CeO2.     

Activity improvement of Pt/C catalysts by adding CeO2 nanoparticles

Carbon-supported platinum catalysts were prepared by NaBH4 reduction of metal precursors and the CeO2 nanoparticles were pre-pared by citric acid sol-gel method.The structure and morphology of two kinds of nanoparticles were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM),respectively.The Pt particles were uniformly dispersed on the carbon surface and showed the rod-like morphology.The CeO2 was spherical in shape.The appropriate amount of CeO2 nanoparticles was added into Pt/C sys-tems to improve activity of the catalysts.Several electrochemical techniques such as cyclic voltammogram (CV),chronoamperometry (I-t) and electrochemical impedance spectroscopy (EIS) were used to investigate the properties of CeO2-Pt/C catalysts for methanol electrooxidation in 1 mol/L CH3OH+0.5H2SO4 aqueous solutions.The results revealed that compared with Pt/C catalysts CeO2-Pt/C exhibited a higher activity and stability for methanol electro-oxidation.Moreover,the effect of CeO2 content on the activity of Pt/C catalysts was discussed in detail.     

Phase control of magnetron sputtering deposited Gd2O3 thin films as high-κ gate dielectrics

Gd2O3 thin films as high-κ gate dielectrics were deposited directly on Si（001） substrates by magnetron sputtering at a pressure of 1.3 Pa and different temperatures. X-ray diffraction results revealed that all the films grown from 450 to 570 ℃ were crystalline, and the Gd2O3 thin films consisted of a mixture of cubic and monoclinic phases. The growth temperature was a critical parameter for the phase constituents and their relative amount. Low temperature was favorable for the formation of cubic phase while higher temperature gave rise to more monoclinic phase. All the Gd2O3 thin films grown from different temperatures exhibited acceptable electrical properties, such as low leakage current density （JL） of 10-5 A/cm^2 at zero bias with capacitance equivalent SiO2 thickness in the range of 6-13 nm. Through the comparison between films grown at 450 and 570 ℃, the existence of monoclinic phase caused an increase in JL by nearly one order of magnitude and a reduction of effective dielectric constant from 17 to 9.     

Characteristic of macroporous CeO2-ZrO2 oxygen carrier for chemical-looping steam methane reforming

Chemical-looping steam methane reforming （CL-SMR） is a novel process towards the production of pure hydrogen and syngas, consisting ofa syngas production reaction and a hydrogen production reaction. Macroporous CeQ-ZrO2 oxygen carders with different pore sizes prepared by colloidal crystal templating method and characterized by techniques of scalming electron microscopy （SEM）, transmission electron microscopy （TEM）, Brunauer-Emmett-Teller （BET）, X-ray diffraction （XRD） and temperature pro- grammed reduction （H2-TPR） were tested in CL-SMR process. For comparison, nonporous CeO2-ZrO2 oxygen carrier prepared by precipitation method was also investigated. It was found that macroporous CeO2-ZrO2 oxygen carriers owned higher reducibility and reactivity in CL-SMR process than nonporous samples. For the macroporous CeO2-ZrO2 sample, the decline of pore size could im- prove the reducibility and reactivity. The macroporous sample with a pore size of 100 nm （labeled as Ce-Zr-100） showed the highest performance for the co-production of syngas and hydrogen during the successive CL-SMR redox cycles. After 10 redox cycles, it still retained good porous structure and reducibility. It was found that the porous structure could accelerate the oxygen release from bulk to surface, leading to a good mobility of oxygen and higher reducibility. In addition, it was also favorable for diffusion and penetration of methane and water steam into the sample particles to accelerate the reaction rate.     

Direct fabrication of cerium oxide hollow nanofibers by electrospinning

Electrospinning technique was used to fabricate PVP/Ce(NO3)3 composite mierofibers. Different morphological CeO2 nanofibers were obtained by calcination of the PVP/Ce(NO3)3 composite microfibers and were characterized by scanning electron microscopy (SEM),Transmission electron microscopy (TEM), X-ray diffraction (XRD), thermal gravimetric and differential thermal analysis (TG-DTA), and (FHR). SEM micrographs indicated that the surface of the composite fibers was smooth and became coarse with the increase of calcination temperatures. The diameters of CeO2 hollow nanofibers (300 nm at 600 ℃ and 600 nm at 800 ℃) were smaller than those of PVP/Ce(NO3)3 composite fibers (1-2 μm). CeO2 hollow nanofibers were obtained at 600 ℃ and CeO2 hollow and porous nanofibers formed by nanoparti-ties were obtained at 800 ℃. The length of the CeO2 hollow nanofibers was greater than 50 μm. XRD analysis revealed that the composite microfibers were amorphous in structure and CeO2 nanofibers were cubic in structure with space groupO5H-FM3m when calcination tem-peratures were 600-800 ℃. TG-DTA and FTIR revealed that the formation of CeO2 nanofibers was largely influenced by the calcination temperatures. Possible formation mechanism of CeO2 hollow nanofibers was proposed.     

Preparation and Characterization of Sol-Gel Derived Au Nanoparticle Dispersed Y2O3：Eu Films

Gold nanoparticles dispersed Y2O3 films were prepared through a sol-gel method by using yttrium acetate and Au nanoparticles colloid as precursors. The films were characterized by X-ray diffraction （XRD）, transmission electron microscopy （TEM） and UV-VIS absorption spectra. XRD patterns and TEM images of Y2O3 ＋ Au films give the same resuits on structure and particle size as that of pure Y2O3 films. The surface plasma resonance （SPR） of Au nanoparticles in Y2O3 ＋ Au film was observed around 550 nm in the absorption spectrum and its position shifts to red with increasing annealing temperature is caused by the increase of dielectric constant of Y2O3 matrix and the size of Au nanoparticles. The second and third order nonlinear optical effects of Y2O3 ＋ Au films were also observed. The photoluminescent properties of Y2O3 ： Eu ＋ Au films were investigated and results indicate that there exist an energy transfer from Eu^3 ＋ to Au nanoparticles and this energy transfer decreases the emission of Eu^3 ＋ in Y2O3 ： Eu ＋ Au film.     

Hydrogen production by steam reforming of ethanol over copper doped Ni/CeO2 catalysts

High surface area CeO2 was prepared by the surfactant-assisted route and was employed as catalyst support. The 0-3 at.% Cu doped Cu-Ni/CeO2 catalysts with 10 wt.% and 15 wt.% of total metal loading were prepared by an impregnation-coprecipitation method. The influence of Cu atomic content on the catalytic performance was investigated on the steam reforming of ethanol (SRE) for H2 production and the catalysts were characterized by N2 adsorption, inductively coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM), temperature-programmed rerduction (TPR) and H2-pulse chemisorption techniques. The activity and products distribution behaviors of the catalysts were significantly affected by the doped Cu molar content based on the promotion effect on the dispersion of NiO particles and the interactions between Cu-Ni metal and CeO2 support. Significant increase in the ethanol conversion and hydrogen selectivity were obtained when moderate Cu metal was doped into the Ni/CeO2 catalyst. Over both of the 10Ni98.5Cu1.5/CeO2 and 15Ni98.5Cu1.5/CeO2 catalysts, more than 80% of ethanol conversion and 60% of H2 selectivity were obtained in the ethanol steam-reforming when the reaction temperature was above 450 ℃.     

Fabrication of copper-ceria hybrid composite electrode for electrocatalytic oxidation of methanol

Copper-ceria hybrid composite electrode prepared by electrochemical co-deposition was examined for their redox process and electrocatalytic activities towards the oxidation of methanol.The structure and morphology of electrodes were characterized by X-ray diffraction(XRD)and scanning electron microscopy(SEM),respectively.XRD pattern of the copper-ceria hybrid composite electrode exhibited some diffraction peaks of CeO2 and SEM micrograph showed that it was composed of grains and flakes.The energy dispersive spectroscopy(EDS)spectrum of this area also showed the presence of cerium.Cyclic voltammetry,CO stripping and chronoamperometry were performed to characterize electrocatalytic property of the prepared samples.In cyclic voltammetry studies and chronoamperometry,copper-ceria hybrid composite electrode towards oxidation of methanol showed a significantly higher response and long term stability.CO stripping results indicated the facile removal of intermediate poisoning species CO in the presence of CeO2,which was helpful for CO and methanol electro-oxidation.     

Synthesis of CeO_2/fly ash cenospheres composites as novel photocatalysts by modified pyrolysis process

A novel fly ash cenospheres(FACs)-supported CeO2 composite(CeO2/FACs) was successfully synthesized by the modified pyrolysis process.The prepared composites were characterized by X-ray diffraction(XRD), scanning electron microscopy(SEM), X-ray photoelectron spectroscopy(XPS), and diffuse reflection spectra(DRS) techniques.XRD results indicated that the CeO2 film coated on cenospheres was a face-centered cubic structure.SEM images confirmed that the CeO2 film was relatively compact.XPS results showed that Ce was present as both Ce4+ and Ce3+ oxidation states in CeO2 film coated on FACs substrate.The bandgap of the composite was narrower compared with the pure CeO2.The as-prepared material exhibited good photocatalytic activity for the decolorization of methylene blue(MB) under visible light irradiation, and the first-order reaction rate constant(k) of 0.0028 min–1 for CeO2/FACs composite was higher than 0.0015 min–1 of pure CeO2.The fact that they floated on water meant that CeO2/FACs composites were easily recovered from water by filtration after the reaction.The recycling test revealed that the composites were quite stable during the MB photocatalytic decolorization.The CeO2/ FACs catalyst was therefore promising for practical use in the degradation of pollutants or water cleanup.     

Synthesis and characterization of Sb-doped SnO2-（CeO2-TiO2） composite thin films deposited on glass substrates for antistatic electricity and UV-shielding

Sb-doped SnO2(ATO)-(CeO2-TiO2) thin Films were deposited on glass substrates using the mixed solution including CeO2-TiO2 precursor and ATO particles by sol-gel dip coating process.ATO particles were prepared using low-temperature hydrothermal process.The mixed molar ratio of ATO to(CeO2-TiO2) vs the properties of CeO2-TiO2 thin film was investigated.The optical properties of the films were characterized by UV-visible transmission and infrared reflection spectra,the sheet resistance of ATO particles and films were measured by rubber sheeter(MYI-50) and four-point probe(HisuperGroup Inc,SDY-5),the surface morphology and structure of the films were analyzed using 3D Digitale Mikroskop and X-ray diffraction(XRD),respectively.The results showed that the ATO precursor solution lost weight completely at about 500 oC,and the ATO particles was obtained,which indicated the same rutile lattice structure as SnO2.The glass substrates coated with ATO-(CeO2-TiO2) thin films showed better properties in antistatic electricity(104-106 Ω/),shielding UV(almost 100%),visible light transmission(70%) and infrared reflection(>30%).     

Electrocatalytic enhancement of methanol oxidation by adding CeO2 nanoparticle on porous electrode

The polyaniline/polysulfone(PAN/PSF) composite films were prepared by electropolymerization,and then CeO2-Pt particles were codeposited into this composite film to obtain the CeO2-Pt-modified polyaniline/polysulfone(CeO2-Pt/PAN/PSF) electrodes.Their morphol-ogy and chemical component were characterized by field emission scanning electron microscopy(FESEM) and energy dispersive X-ray spectroscopy(EDS),respectively.The results showed that the composite film had bi-layer structure with asymmetrical pores,and platinum and cerium oxide particles were homogeneously dispersed in the modified film electrodes.The cyclic voltammetry(CV) and electrochemical impedance spectroscopy(EIS) techniques were applied to investigate the electrocatalytic activity of the Pt-CeO2/PAN/PSF electrodes.It was indicated that appropriate amount of CeO2 could enhance the catalytic activity of Pt for methanol electro-oxidation.Chronoamperometry(i-t) measurements revealed that the Pt-CeO2/PAN/PSF electrode was relatively endurable for intermediate production.In addition,different mix-ing amounts of Pt and CeO2 nanoparticles were also investigated in detail.     

Epitaxial growth and characterization of Gd2O3-doped HfO2 film on Ge （001） substrates with zero interface layer

The GHO （Gd2O3-doped HfO2） films were epitaxially grown on Ge （001） substrates adopting cube-on-cube mode with zero interface layer using pulsed laser deposition （PLD）. Reflection high-energy electron diffraction （RHEED） and high-resolution transmission electron microscopy （HRTEM） observation revealed a sharp interface of GHO/Ge and orientation relationship corre-sponding to （001）GHO//（001）Ge and [011] GHO//[011]Ge. The band offset for GHO/Ge stack was evaluated to be 3.92 eV for va-lence band and 1.38 eV for conduction band by X-ray photoelectron spectrum. Small equivalent oxide thickness （0.49 nm） and inter-face state density （7×1011 cm-2） were achieved from Au/Ti/GHO/Ge/Al capacitors.     

Structure and Waveguide Properties of Sol-Gel Derived Gd2O3 Films

Pure and rare earth doped gadolinium oxide (Gd2O3) waveguide films were prepared by a simple sol-gel process and dip-coating method. Structure of Gd2O3 films annealed at different temperature was investigated by X-ray diffraction and transmission electron microscopy. Oriented growth of (400) face of Gd2O3 has been observed when the films were deposited on amorphous substrate. The refractive index and thickness of films were determined by m-lines spectroscopy. The laser beam (λ= 632.8 nm) was coupled into the film by a prism coupler and the propagation length is about 3.5 cm. Luminescence properties of europium ions doped films were measured by waveguide fluorescence spectroscopy, which shows disordered environment for Eu^3 at 400℃.     

Controllable preparation of CeO2 nanostructure materials and their catalytic activity

Well-crystalline CeO2 nanostructures with the morphology of nanorods and nanocubes were synthesized by a template-free hydro-thermal method. X-ray diffraction (XRD), transmission electron microscopy (TEM), Brunauer-Emmett-Teller (BET) nitrogen adsorp-tion-desorption measurements were employed to characterize the synthesized materials. The reducibility and catalytic activity of nanostruc-tured CeO2 were examined by hydrogen temperature-programmed reduction (H2-TPR) and CO oxidation. The results showed that CeO2 nanorods could be converted into CeO2 nanocubes with the increasing of the reaction time and the hydrothermal temperature, CeO2 nanorods became longer gradually with the increasing of the concentrations of NaOH. H2-TPR characterization demonstrated that the intense low-temperature reduction peak in the CeO2 nanorods indicated the amount of hydrogen consumed is larger than CeO2 nanocubes. Meantime the CeO2 nanorods enhanced catalytic activity for CO oxidation, the total conversion temperature was 340 oC. The reasons were that CeO2 nanorods have much smaller crystalline sizes and higher surface areas than CeO2 nanocubes.     

Synthesis of mesoporous CeO2-MnOx binary oxides and their catalytic performances for CO oxidation

Mesoporous CeO2-MnOx binary oxides with different Mn/Ce molar ratios were prepared by hydrothermal synthesis and characterized by scanning electron microscopy （SEM）, N2 sorption, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and H2 temperature-programmed reduction （H2-TPR）. The characterization results indicated that the CeO2-MnOx catalysts exhibited flower-like microspheres with high specific surface areas, and partial Mn cations could be incorporated into CeO2 lattice to form solid solution. The CeO2-MnOx catalysts showed better catalytic activity for CO oxidation than that prepared by the coprecipitation method. Furthermore, the CeO2-MnOx catalyst with Mn/Ce molar ratio of 1 in the synthesis gel （Ce-Mn-1） exhibited the best catalytic activity, over which the conversion of CO could achieve 90% at 135 ℃. This was ascribed to presence of more Mn species with higher oxida- tion state on the surface and the better reducibility over the Ce-Mn-I catalyst than other CeO2-MnOx catalysts.     

Effect of Zn Doping on Transport Properties of La2/3 Sr1/3 Mn1 - x Znx O3 Films

La2/3 Sr1/3 Mn1-x ZnxO3films （x =0.05, 0.1,0.3, and 0.5） were prepared using magnetron sputtering method, and the effect of Zn doping on transport properties of the films was studied. An analysis of X-ray diffraction showed that the main phase of the bulk target was orthorhombic and the films had better epitaxial character. It was found that the films with x =0.05 and x =0.1 exhibited typical insulator-metal transition. No transition of the films with x≥0.3 was observed and the dominant transport was variable-range hopping due to observable secondary phase ZnO. These could be attributed to the Zn doping effect on manganites.     

Preparation of La MnO_3/graphene thin films and their photocatalytic activity

A novel photocatalyst of La MnO3/graphene thin films with the perovskite-type was synthesized by sol-gel process assisted with spin-coating methods on glass substrates.The prepared samples were characterized by scanning electron microscopy(SEM), transmission electron microscopy(TEM), X-ray diffraction(XRD), Brumauer-Emmett-Teller(BET) surface area analyzer, X-ray photoelectron spectroscopy(XPS) and UV-vis diffuse reflectance spectroscopy.Results showed that after the introduction of graphene, the perovskite structure was unchanged and the size of La MnO3 particles was about 22 nm, which uniformed growth in graphene sheet.Determination of contact angle indicated that the contact angle of glass substrate decreased and the hydrophilicity improved after treating with H2SO4 and APTES.The UV-Vis photocatalytic activity of the photocatalysts was evaluated by the degradation of diamine green B.La MnO3/graphene thin films had better photocatalytic ability than La MnO3 and Ti O2 films.The obtained k was 0.5627 and 0.3441 h–1 corresponding to La MnO3/graphene films and Ti O2 films, respectively.     

Synergetic catalysis of ceria and titania for selective reduction of NO

The promotional effect of the interaction between titania and ceria on the catalytic performance for selective reduction of NO was studied.The catalysts,CeO 2,TiO 2,CeO 2 /TiO 2 and Ti x Ce 1-x O 2,were synthesized and tested in NH 3-Selective catalytic reduction(SCR) of NO,and the samples were characterized by the Brunaller,Emmett and Teller(BET absorbed gas N 2),X-ray diffraction(XRD),high resolution transmission electron microscopy(HR-TEM),and temperature programmed desorption(TPD NH 3) techniques.The improvement mechanism of the interaction between the titania and ceria had been explored and discussed from two aspects of micro-structure and surface acidity.The interaction between the titania and ceria greatly improved the catalytic activity but had little effect on the active temperature.It was first reported that the acid amount determined the catalytic activity and the acid strength determined the active temperature for NH 3-SCR of NO.     

Synthesis of cerium-doped MCM-48 molecular sieves and its catalytic performance for selective oxidation of cyclohexane

Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high （0.04 or 0.059）, there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.     

Ultrasonic synthesis, characterization and formation mechanism of aggregated nanorings of EuF3

The aggregated nanorings of EuF3 were synthesized via ultrasonic irritation in aqueous solution. The products were characterized by X-ray powder diffraction （XRD）, scanning electron microscopy （SEM）, and transmission electron microscopy （TEM）. XRD pattern proved that the crystalline phase of the EuF3 rings was hexagonal. The SEM and TEM images indicated that the as-prepared EuF3 nanocrystals had ring-like morphology and were aggregated by numerous small crystallites （about 10-15 nm in diameter）; the outer diameter of the rings was in the range of 200--300 nm, while the inner diameter was in the range of 50-80 nm with a thickness of 30-40 nm. Moreover, the time-depend experiments were carried out to disclose the formation mechanism of the as-prepared ring-like nanostructures.