Influence of morphology on basicity of CeO_2 and its use in 2-chloroethyl ethyl sulfide degradation

Three CeO_2 samples with different morphologies, i.e., cubes, rods, and spindles, were synthesized and investigated for 2-chloroethyl ethyl sulfide(2-CEES) degradation. The samples were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, the Brunauer-Emmett-Teller method, and temperature-programmed CO_2 desorption. It was found that morphologies of CeO_2 could strongly affect the surface properties and the 2-CEES degradation activities. The surface basicity and the continuous 2-CEES degradation activity of spindle-like CeO_2 were much better than those of the other CeO_2 samples, although all the samples had identical chemical compositions. That was benefited by the largest surface area, abundant microcracks, and surface oxygen vacancies of the spindle-like CeO_2.     

Cerium,manganese and cerium/manganese ceramic monolithic catalysts.Study of VOCs and PM removal

Ceramic supported cerium, manganese and cerium-manganese catalysts were prepared by direct impregnation of aqueous precursor, and characterized by scanning electron microscopy(SEM), X-ray diffraction(XRD), Brunauer-Emmett-Teller method(BET), temperature programmed reduction(H_2-TPR), X-ray photoelectron spectroscopy(XPS) acidity measurements and electrical conductivity. The catalytic activity was evaluated for volatile organic compounds(VOC)(ethanol, methyl ethyl ketone and toluene) oxidation. Additionally, catalysts were tested in particulate matter(PM) combustion. The characterization results indicated that Ce was in the form of Ce~(4+) and Ce~(3+), and Mn existed in the form of Mn~(4+) and Mn~(3+) on the surface of the Mn/AC sample and in the form of Mn~(4+) in the Ce/Mn/AC monolith. VOC oxidation results revealed that the Ce/Mn/AC sample showed an excellent performance compared with ceramic supported CeO_2(Ce/AC) and MnO_x(Mn/AC) samples. The PM combustion was also higher on Ce/Mn/AC monoliths. The enhanced catalytic activity was mainly attributed to the Ce and Mn interaction which enhanced the acidity, conductivity and the reducibility of the oxides.     

Effect of praseodymium additive on CeO_2(ZrO_2)/TiO_2 for selective catalytic reduction of NO by NH_3

A series of praseodymium added CeO_2(ZrO_2)/TiO_2 catalysts separately prepared by methods of sol-gel and impregnation were tested for selective catalytic reduction of NO, and characterized by X-ray diffraction(XRD), N_2-brumauer-emmett-teller(N_2-BET), NH_3-temperature programmed desorption(NH_3-TPD), H_2-temperature programmed reduction(H_2-TPR), PL spectra, Raman spectra, electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS), respectively. Influence of preparation method on catalytic performance was studied. Results showed that the influence of Pr addition on catalytic performance of the CeO_2(ZrO_2)/TiO_2 catalysts was different between the sol-gel method and the impregnation method. The Pr addition tended to interact with TiO_2 and formed the structure of Ti-O-Pr in the sol-gel method while it was more likely to interact with CeO_2 forming the structure of Ce-O-Pr in the impregnation method. The total acid amount and redox properties of the catalysts prepared by sol-gel method decreased with the addition of Pr element, which resulted in decrease of catalytic activity. In contrast, the Pr-added catalyst prepared by impregnation method was found to possess easier reducibility, more total acid amount and higher proportion of Ce~(3+) species, which was favourable for higher catalytic activity.     

Effect of cerium oxide prepared under different hydrothermal time on electrocatalytic performance of Pt-based anode catalysts

In this paper,CeO_2 with a pore size of 2-4 nm was synthesized by hydrothermal method.The CeO_2 modified graphene-supported Pt catalyst was prepared by the microwave-assisted ethylene glycol reduction chloroplatinic acid method,and the effect of the addition of CeO_2 prepared by different hydrothermal reaction time on the catalytic performance of Pt-based catalysts was investigated.The microstructures of CeO_2 and catalysts were characterized by X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),specific surface area and pore size analyzer(BET),scanning electron microscopy(SEM) and electron spectroscopy(EDAX),transmission electron microscopy(TEM),and the catalysts electrochemical performance was tested by electrochemical workstation.The results show that the catalytic performance of the four catalysts with CeO_2 is better than that of the catalyst without CeO_2.Adding CeO_2 with a specific surface area of 120.15 m~2/g prepared by hydrothermal reaction time of 39 h to Pt/C synthesis catalyst,its electrocatalytic performance,stability and resistance to poisoning are the best.The electrochemical active surface area is 102.83 m~2/g,the peak current density of ethanol oxidation is 757.17 A/g and steady-state current density of 1100 s is 108.17 A/g which shows the lowest activation energy for ethanol oxidation reaction.When the cyclic voltammogram is scanned for 500 cycles,the oxidation peak current density retention rate is 87.74%.     

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℃.     

ScF_3的水热法制备及掺Ce~(3+)光谱性质研究

首次用低温水热法制备了ScF_3晶体及其掺杂Ce~(3+)的粉体.通过X射线粉末衍射(XRD),扫描电镜(SEM),荧光光谱(FS)对样品进行了表征.结果表明,所用氟化物的种类和反应温度对ScF_3的制备至关重要.以NaF作为原料更容易得到纯的ScF_3.当水热温度为120℃时,产物为ScF_3晶体,而温度升高至180℃时则为NaScF4复合氟化物.所制备的ScF_3呈针尖棒状放射形.考察了ScF_3:Ce~(3+)粉体荧光光谱性质,讨论了其与同类型的稀土氟化物的荧光光谱的比较.     

Catalytic oxidation of formaldehyde over CeO_2-Co_3O_4 catalysts

A series of CeO_2-Co_3O_4 mixed oxide catalysts with different Co/(Co+Ce) atomic ratios were synthesized by citric acid sol-gel method and used for catalytic oxidation of formaldehyde(HCHO). Many techniques such as Brumauer-Emmett-Teller(BET), X-ray diffraction(XRD), scanning electron microscopy(FE-SEM), temperature programmed reduction(H_2-TPR), temperature-programmed desorption(O_2-TPD) and X-ray photoelectron spectroscopy(XPS) were used to characterize catalysts. The results of catalytic performance tests showed that the catalyst CeO_2-Co_3O_4 with Co/(Co+Ce) ratio of 0.95 exhibited the best performance, and the temperature of complete oxidation of HCHO was 80 oC. The analytical results indicated that the addition of CeO_2 enhanced the specific surface area of Co_3O_4 and the fine dispersion of both of them. Moreover, the strong interaction between CeO_2 and Co_3O_4 resulted in the unique redox properties, which enhanced the available surface active oxygen and led to high valence state of cobalt oxide species. All those effects played crucial roles in the excellent performance of CeO_2-Co_3O_4 for the HCHO oxidation.     

Systematic study of Ce3+ on the structural and magnetic properties of Cu nanosized ferrites for potential applications

Ce~(3+) substituted Cu-spinel nanoferrites CuCe_xFe_(2-x)O_4(x=0.00, 0.02, 0.04, 0.06, 0.08 and 0.10) were synthesized via sol-gel self-combustion hybrid route. Single phase spinel ferrite of Cu nanoferrites were examined using X-ray diffraction(XRD) analysis whereas the multiphase structure was observed as Ce contents increased from x=0.06. Field emission scanning electron microscopy(FESEM), Thermogravimetric and differential thermal analysis(TGA and DTA) and Fourier transform infrared spectroscopy(FTIR) were used to find out the morphology phase and metal stretching vibrations of Ce~(3+) substituted nanocrystalline ferrites. The crystallite size was increased and found in the range of 25-91 nm. The agglomerations in Cu ferrite samples increase as the Ce~(3+) concentration increases. The magnetic properties such as remanence, saturation magnetization, coercivity, Bohr magneton and magnetocrystalline anisotropy constant(K) were determined using M-H loops recorded from a vibrating sample magnetometer(VSM). Saturation magnetization, remanence and coercivity are increased as the Ce~(3+)contents increase in Cu nanocrystalline samples. Moreover, law of approach to saturation(LoA) was used to calculate the maximum value of saturation for Ce-doped Cu nanoferrites. The soft magnetic behaviour of the Cu nanoferrite is observed as compared to the samples substituted with the increased Ce contents in Cu nanocrystalline ferrite. Bohr magneton and magnetocrystalline anisotropy are found to increase with the substitution of rare earth Ce~(3+) contents in Cu spinel nanocrystalline ferrite. Cedoped Cu nanocrystalline ferrites with excellent properties may be suitable for potential applications in sensing, security, switching, core, multilayer chip inductor, biomedical and microwave absorption applications.     

Preparation and performance of CeO_2 hollow spheres and nanoparticles

CeO_2 hollow spheres were synthesized by polystryrene sphere(PS) templates and CeO_2 nanoparticles were prepared by a facile method. The as-obtained products were characterized by scanning electron microscopy(SEM), N_2 adsorption-desorption, X-ray diffraction(XRD), Fourier transform infrared spectroscopy(FTIR) and UV-vis diffuse reflectance spectra. The results showed that the structure of the obtained CeO_2 hollow spheres was hollow microsphere with a diameter of 380 nm and the average particle size of CeO_2 nanoparticles was about 1700 nm. The two samples' Brunauer-Emmett-Teller(BET) surface area was 67.1 and 37.2 m~2/g. The CeO_2 hollow spheres had a better performance than nanoparticles at UV-shielding because of higher surface area and the structure of hollow sphere.     

A novel n-CeO_2/n-CdO heterojunction nanocomposite for enhanced photodegradation of organic pollutants under visible light irradiation

In this study,a series of novel visible light driven n-CeO_2/n-CdO heterojunction(CeO_2/CdO)nanoco mposites we re successfully fabricated by simple ultrasonication method.Several characte rization tools including X-ray diffraction(XRD),scanning electro n microscopy(SEM),transmission electron microscopy(TEM)and UV-vis diffuse reflectance spectroscopy(UV-DRS),etc.,were utilized to investigate the physicochemical properties of the catalyst and confirm the formation of heterojunction.Under visible light irradiations,the photocatalytic activities of the as-prepared CeO_2/CdO nanocomposites were evaluated by degrading of Congo red(CR)and Rhodamine B(RhB)solutions.As a result,the CeO_2/CdO(mass percentage ratio 1:3)nanocomposite displays remarkable performance for CR and RhB degradation.The enhancement in the photocatalytic performance of CeO_2/CdO(1:3)nanocomposite can be attributed not only to the strong visible-light absorption region,separating the photogenerated electronhole pairs but also to the formation of n-n type heterojunction.The results also indicate that the CeO_2/CdO(1:3)nanocomposite has good stabilization and high reusability.In addition,the mechanism is proposed for the coupled semiconductors and possible reasons for the enhancement of visible-light photocatalytic efficiency are also discussed.This work can provide a new gateway to fabricate visible photocatalysts and promising candidate catalysts for poisonous wastewater treatment in the near future.     

Luminescent properties of Ba3Gd（BO3）3：Eu^3＋ phosphor for white LED applications

Luminescent material Ba3Gd(BO3)3 doped with Eu3+ ion was prepared by high temperature solid-state method. The preparing conditions, luminescent properties, and particle morphology of Ba3Gd(BO3)3:Eu3 + phosphor were studied with X-ray diffraction (XRD), fluorescence spectroscopy, and scanning electron microscopy (SEM). The results obtained by XRD showed that pure phase of Ba3Gd(BO3)3 was obtained at 1000℃. Images from SEM displayed that the particles of Ba3Gd(BO3)3:Eu3+ phosphor had a spherical shape with an average diameter of about 200-400 nm. The luminescence spectra showed that Ba3Gd(BO3)3:Eu3+ phosphor was effectively excited by the near ultraviolet (UV) light (396 nm) and blue light (466 nm). The main emission peaks of Ba3Gd(BO3)3:Eu3+ phosphor were assigned to the supersensitive transition 5D0-7F2 (611 and 616 nm) of Eu3+ ion when samples were excited at 255 and 396 nm, respectively, and the luminescent intensity of Ba3Gd(BO3)3:Eu3+ at 611 and 616 nm reached to the maximum when the doped content of Eu3+ ion was 10mol.%. Therefore, this phosphor could be a promising red component for possible applications in the field of white LED.     

Structure Property and Visible Upconversion of Er^3＋ Doped Gd2O3 Nanocrystals

Gd2O3:Er nanoparticles were prepared by a simple sol-gel method, The structure properties ot Gd2O3:Er were studied by X-ray diffraction, transmission electron microscopy, Raman spectroscopy and Fourier transform infrared spectroscopy. The visible up-converted luminescence spectra of Er^3 were investigated under excitation to ^4I9/2 level by 785nm laser. Laser power, Er^3 ion concentration and temperature dependences of the upconverted emissions were investigated to understand the upconversion mechanisms. Excited state absorption and energy transfer process are discussed as the possible mechanisms for the upconversion.     

Polyhemoglobin-superoxide dismutase-catalase as a blood substitute with antioxidant properties

Polyhemoglobin-superoxide dismutase-catalase is designed to function as an oxygen carrier with antioxidant properties. This is based on cross-linking hemoglobin with superoxide dismutase and catalase (PolyHb-SOD-CAT). This study describes the structural and antioxidant properties of this solution. Our studies show that superoxide dismutase and catalase retain their enzymatic activity following glutaraldehyde polymerization with 8:1 and 16:1 glutaraldehyde:hemoglobin ratio. We have analyzed the optimal SOD/CAT ratios to prevent oxidation of hemoglobin in the presence of oxygen free radicals. The circulation half-life of crosslinked hemoglobin, SOD, and catalase in Sprague-Dawley rats correlates with the degree of polymerization as determined by high-performance molecular weight gel filtration. PolyHb-SOD-CAT decreases the formation of oxygen radicals compared with PolyHb in a rat intestinal ischemia-reperfusion model.     

Preparation and characterization of Ce_(1-x)Pr_xO_2 supports and their catalytic activities

In this work, the addition of praseodymium(Pr) into ceria as a mixed oxide support in a form of Ce_(1-x)Pr_xO_2(x = 0.01,0.025, 0.050, 0.075 and 0.10) was prepared using a co-precipitation method. The structural and textural properties of the synthesized supports were characterized by X-ray diffraction(XRD), N_2 adsorption-desorption, Raman spectroscopy, H_2-temperature programmed reduction(H_2-TPR) and H_2-chemisorption. Upon addition of Pr, XRD patterns and Raman spectra indicated an enlargement of ceria unit cell and the characteristics Raman broad peak at 570 cm~(-1) which was attributed to the existence of oxygen vacancies in the ceria lattice. This indicated that some Ce~(4+) ions in ceria were replaced by larger Pr~(3+) cations. To evidence the incorporation of Pr~(3+) cations into ceria lattice,X-ray absorption near edge structure(XANES) was employed. The results showed that the oxidation states of Ce in mixed oxide supports were slightly lower than 4+ while those of Pr were still the same as a precursor salt. Therefore, the incorporation of Pr~(3+) into ceria lattice would lead to strain and unbalanced charge and result in oxygen vacancies. The reducibility of Ce_(1-x)Pr_xO_2 mixed oxide supports was investigated by H_2-TPR and temperature-resolved X-ray absorption spectroscopy experiment under reduction conditions. XANES spectra of Ce L_3 edges showed a lower surface reduction temperature(Ce~(4+)to Ce~(3+)) of Ce_(0.925)Pr_(0.075)O_2 than that of CeO_2 which agreed with H_2-TPR results. H_2-chemisorption indicated that Pr promoted the dispersion of the metal catalyst on the mixed oxide support and increased the adsorption site for CO. For WGS reaction, 1% Pd/mixed oxide support had higher WGS activity than 1%Pd/ceria. The increase of WGS activity was due to the increase of Pd dispersion on the support and the existence of oxygen vacancies produced from incorporation of Pr into the ceria lattice.     

Catalytic performance of a Pt-Rh/CeO_2-ZrO_2-La_2O_3-Nd_2O_3 three-way compress nature gas catalyst prepared by a modified double-solvent method

A Pt-Rh three-way catalyst(M-DS) supported on CeO_2-ZrO_2-La_2O_3-Nd_2O_3 and its analogous supported catalyst(DS) were developed via a modified double-solvent method and conventional double-solvent method, respectively. The as-prepared catalysts were characterized by N_2 adsorption-desorption, X-ray diffraction(XRD), CO-chemisorption, X-ray photoelectron spectroscopy(XPS) and hydrogen temperature-programmed reduction(H_2-TPR). The preformed Pt nanoparticles generated using ethanol as a reducing agent on M-DS presented enhanced Pt dispersion regardless of aging treatment as confirmed by XRD and CO-chemisorption measurements. The textural properties and reduction ability of M-DS were maintained to a large extent after aging treatment. This result was consistent with those of the N_2 adsorption-desorption and H_2-TPR, respectively. Meanwhile, the XPS analysis demonstrated that higher Pt~0 species and larger Ce~(3+) concentration could be obtained for M-DS. In the conversion of a simulated compressed natural gas(CNG) vehicle exhaust, both fresh and aged M-DS showed a significant enhancement in the activity and N_2-selectivity. Particularly, the complete conversion temperature(T_(90)) of CH_4 over the aged M-DS catalyst was 65 oC lower than that over the aged catalyst by conventional double-solvent method.     

Autoxidation of ubiquinol-6 is independent of superoxide dismutase

Ubiquinone (Q) is an essential, lipid soluble, redox component of the mitochondrial respiratory chain. Much evidence suggests that ubiquinol (QH2) functions as an effective antioxidant in a number of membrane and biological systems by preventing peroxidative damage to lipids. It has been proposed that superoxide dismutase (SOD) may protect QH2 form autoxidation by acting either directly as a superoxide-semiquinone oxidoreductase or indirectly by scavenging superoxide. In this study, such an interaction between QH2 and SOD was tested by monitoring the fluorescence of cis-parinaric acid (cPN) incorporated phosphatidylcholine (PC) liposomes. Q6H2 was found to prevent both fluorescence decay and generation of lipid peroxides (LOOH) when peroxidation was initiated by the lipid-soluble azo initiator DAMP, dimethyl 2,2'-azobis (2-methylpropionate), while Q6 or SOD alone had no inhibitory effect. Addition of either SOD or catalase to Q6H2-containing liposomes had little effect on the rate of peroxidation even when incubated in 100% O2. Hence, the autoxidation of QH2 is a competing reaction that reduces the effectiveness of QH2 as an antioxidant and was not slowed by either SOD or catalase. The in vivo interaction of SOD and QH2 was also tested by employing yeast mutant strains harboring deletions in either CuZnSOD and/or MnSOD. The sod mutant yeast strains contained the same percent Q6H2 per cell as wild-type cells. These results indicate that the autoxidation of QH2 is independent of SOD.     

Foliar application of rare earth elements on soybean(Glycine max(L)):Effects on biometrics and characterization of phytotoxicity

This study aims at investigating the effects of foliar application of aqueous solutions of La~(3+)and Ce~(3+)nitrates on soybean plants(Glycine max).First,we observe that Triton HW 1000 surfactant at 0.01 vol%reduces droplets contact angle and increases their drying time.Under greenhouse conditions,the foliar treatments do not affect chlorophyll content,plant height,number of leaves,number of pods,number of seeds per pod,and average seed weight.However,the treatments induce phytotoxicity since foliar injuries appear after the spraying.Microprobe X-ray fluorescence spectroscopy combined to scanning electron microscopy shows that the leaf lesions are positively correlated to accumulation of Ce and La on the leaf surface and also promote structural alteration to the epidermal cells.X-ray absorption near edge structure shows that the La and Ce nitrates are partially bio transformed into oxides by the leaves which might explain the harmful effects.     

Preparation of γ-Gd2S3 via thermolysis of Gd[S2CN（C4Hs）]a-phen coordination

Pure γ-Gd 2 S 3 was synthesized by the thermolysis of a single Gd[S 2 CN(C 4 H 8 )] 3 ·phen complex precursor in a flow of argon carrier gas containing sulfur vapor. The complex precursor was decomposed into amorphous Gd 2 S 3 and carbon at about 350 °C. Crystalline γ-Gd 2 S 3 could be achieved at temperature exceeding 600 °C, and the obtained γ-Gd 2 S 3 presented a very high degree of crystallinity at 800 °C. Carbon prevented the formation of Gd 2 O 2 S impurity in the preparation of γ-Gd 2 S 3 . However, the carbon blackened the product. At temperature ≥1000 °C, the residual carbon impurity could be efficiently removed by introducing sulfur into the system for the volatile CS 2 could be formed in situ via the reaction of sulfur with the deposited carbon. In the meantime, S also promoted the crystallization of γ-Gd 2 S 3 remarkablely.     

Manganese dipyridoxyl diphosphate: MRI contrast agent with antioxidative and cardioprotective properties?

Manganese dipyridoxyl diphosphate (MnDPDP) is a contrast agent for magnetic resonance imaging (MRI) of the liver. Aims of the study were to examine if MnDPDP possesses superoxide dismutase (SOD) mimetic activity in vitro, and if antioxidant protection can be demonstrated in an ex vivo rat heart model. Superoxide (*O-2) and hydroxyl radicals (*OH-) were generated in xanthine oxidase and Fenton reactions. Spin adducts with 5,5-dimethyl-1-pyrroline-N-oxide were detected by electron spin resonance spectroscopy. Contractile function and enzyme release were monitored in rat hearts during hypoxia-reoxygenation. Low microM concentrations of MnDPDP and its metabolite Mn dipyridoxyl ethylene-diamine (MnPLED) dismutated *O-2, but showed no activity in Fenton or catalase reactions. MnDPDP 30 microM improved contractile function and reduced enzyme release in rat hearts during reoxygenation. It is concluded that MnDPDP and MnPLED possess SOD mimetic activities and may thereby protect the heart in oxidative stress.