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1.
林晓敏  李莉萍  苏文辉 《化学学报》2007,65(10):989-993
利用溶胶-凝胶方法在800 ℃焙烧10 h后, 合成了固溶体Ce1-xNdxO2-δ (x=0.05~0.55), X射线衍射(XRD)测试表明固溶体已经形成立方萤石结构; 电子顺磁共振谱(EPR)研究表明在固溶体Ce1-xNdxO2-δ中随着掺杂量x的增大, Ce3+离子含量减少, 说明掺杂Nd3+离子可以抑制Ce4+的还原; 交流阻抗谱的测量表明固溶体Ce0.9Nd0.1O2-d 具有离子导电特性, 600和700 ℃时的电导率分别为4.25×10-3和1.12×10-2 S•cm-1, 活化能为0.68 eV.  相似文献   

2.
The large‐scale industrial production of acetic acid (HAc) from carbonylation of methanol has enabled intense research interest from direct hydrogenation of HAc to acetaldehyde (AA). Herein, a series of cerium‐iron oxide solid solution supported metallic cobalt catalysts were prepared by modified sol‐gel method and were applied in gas‐phase hydrogenation of HAc to AA. A synergistic effect between the hydrogenation metal cobalt and Ce‐Fe oxide solid solution is revealed. Specifically, oxygen vacancies provide the active sites for adsorption of HAc, while highly uniformly dispersed metallic Co adsorbs H2 and activates the reduction of HAc into AA. Moreover, the metallic Co can also assist the cyclical conversion between Fe3+/Fe2+ and Ce3+/Ce4+ on the surface of Ce1‐xFexO2‐δ supports. The unique effect substantially enhances the ability of the support material to rapidly capture oxygen atoms from HAc. It is found that the catalyst of 5% Co/Ce0.8Fe0.2O2‐δ with the highest concentration of oxygen vacancy presents the best catalytic performance (i.e. acetaldehyde yield reaches 49.9%) under the optimal reaction conditions (i.e. 623 K and H2 flow rate = 10 mL/min). This work indicates that the Co/Ce‐Fe oxide solid solution catalyst can be potentially used for the selective hydrogenation from HAc to AA. The synergy between the metallic Co and Ce1‐xFexO2‐δ revealed can be extended to the design of other composite catalysts.  相似文献   

3.
The spinel Li‐Mn‐O‐F compound cathode materials were synthesized by solid‐state reaction from calculated amounts LiOH‐H2O, MnO2(EMD) and LiF. The results of the electrochemical test demonstrated that these materials exhibited excellent electrochemical properties. It's initial capacity is ‐ 115 mAh.g1 and reversible efficiency is about 100%. After 60 cycles, its capacity is still around 110 mAh.g1 with nearly 100% reversible efficiency. The spinel Li‐Mn‐O‐F compound possibly has two structure models: interstitial model [Li]‐[Mn3+xMn4+2‐x]O4Fδ, in which the fluorine is located on the interstice of crystal lattice, and substituted model [Li]‐[Mn3+xMn4+2‐x]O4‐δFδ, which the fluorine atom substituted the oxygen atom. The electrochemical result supports the interstitial model [Li][Mn3+xMn4+2‐x]O4Fδ.  相似文献   

4.
CeO2-based solid solutions with a fluorite structure are promising materials as electrolytes of medium-temperature electrochemical devices: electrolytic cells, oxygen sensors, and solid oxide fuel cells. In this work, studies are presented of the effect of the dopant cation radius and its concentration on the physico-chemical properties of the Ce1 − x Ln x O2 − δ solid solutions (x = 0–0.20; Ln = La, Nd, Sm, Eu, Gd, Dy, Ho, Er, Yb) and also of multicomponent solid solutions of Ce1 − x Ln x/2Ln′ x/2O2 − δ (x = 0–0.20; Ln = Sm, La, Gd and Ln′ = Dy, Nd, Y) and Ce1 − xy Sm x M y O2 − δ (M = Ca, Sr, Ba) obtained using the solid-phase synthesis technique. Electric properties of the samples were studied in the temperature range of 623–1173 K and in the oxygen partial pressure range of 0.01–10−22 MPa. The values of oxygen critical pressure ( pO2 * )\left( {p_{O_2 }^* } \right) are presented, at which the ionic and electron conductivity values are equal. The values were calculated on the basis of experimental dependences at 1023 K at the assumption that the ionic conductivity value is determined only by the dopant concentration and its effective ionic radius and is independent of the oxygen partial pressure.  相似文献   

5.
Composition‐tailored Mn1?xRuxO2 2 D nanosheets and their reassembled nanocomposites with mesoporous stacking structure are synthesized by a soft‐chemical exfoliation reaction and the subsequent reassembling of the exfoliated nanosheets with Li+ cations, respectively. The tailoring of the chemical compositions of the exfoliated Mn1?xRuxO2 2 D nanosheets and their lithiated nanocomposites can be achieved by adopting the Ru‐substituted layered manganese oxides as host materials for exfoliation reaction. Upon the exfoliation–reassembling process, the substituted ruthenium ions remain stabilized in the layered Mn1?xRuxO2 lattice with mixed Ru3+/Ru4+ oxidation state. The reassembled Li–Mn1?xRuxO2 nanocomposites show promising pseudocapacitance performance with large specific capacitances of approximately 330 F g?1 for the second cycle and approximately 360 F g?1 for the 500th cycle and excellent cyclability, which are superior to those of the unsubstituted Li–MnO2 homologue and many other MnO2‐based materials. Electrochemical impedance spectroscopy analysis provides strong evidence for the enhancement of the electrical conductivity of 2 D nanostructured manganese oxide upon Ru substitution, which is mainly responsible for the excellent electrode performance of Li–Mn1?xRuxO2 nanocomposites. The results underscore the powerful role of the composition‐controllable metal oxide 2 D nanosheets as building blocks for exploring efficient electrode materials.  相似文献   

6.
以超高比表面炭材料为模板,硝酸盐为氧化物前体,通过改进的模板路线制备了具有较高比表面积的纳米CexFe1-xO2固溶体.采用X射线衍射、拉曼光谱、物理吸附和透射电镜对制备的样品进行了表征.结果表明,α-Fe2O3,CexFe1-xO2固溶体和CeO2的粒子尺寸为5~15nm,CeO2中部分Ce4 离子被Fe3 离子取代,从而形成了CexFe1-xO2固溶体.乙醇水蒸气重整反应结果显示,CexFe1-xO2固溶体比相应的α-Fe2O3和CeO2具有更高的催化活性和对氢气的选择性.  相似文献   

7.
A series of the solid‐solution phosphors Lu3?x?yMnxAl5?xSixO12:yCe3+ is synthesized by solid‐state reaction. The obtained phosphors possess the garnet structure and exhibit similar excitation properties as the phosphor Lu3Al5O12:Ce3+, but with an effectively improved red component in the emission spectrum. This can be attributed to the energy transfer from Ce3+ to Mn2+. Our investigation reveals that electric dipole–quadrupole interactions dominate the energy‐transfer mechanism and that the critical distance determined by the spectral overlap method is about 9.21 Å. The color‐tunable emissions of the Lu3?x?yMnxAl5?xSixO12:yCe3+ phosphor as a function of Mn3Al2Si3O12 content are realized by continuously shifting the chromaticity coordinates from (0.354, 0.570) to (0.462, 0.494). They indicate that the obtained material may have potential application as a blue radiation‐converting phosphor for white LEDs with high‐quality white light.  相似文献   

8.
The NdIII coordination compounds [Nd(4‐pytza)3(H2O)2] · 2H2O ( 1 ) and [Nd(4‐pytza)2(H2O)4]Cl · 2H2O ( 2 ) [H4‐pytza = 5‐(4‐pyridyl)tetrazole‐2‐acetic acid] were synthesized by reactions of K4‐pytza and NdCl3 · 6H2O at different pH values. Single crystal X‐ray diffraction analysis reveals that 4‐pytza ligands in 1 in a μ1,3‐COO synsyn or μ1,1,3‐COO bridging mode coordinate to two central NdIII atoms to display a dinuclear unit, which is connected by one of these 4‐pytza ligands acting in end‐to‐end bridging mode to form a 1D ladder‐like chain. Different from 1 , each 4‐pytza in 2 with a μ1,3‐COO synanti bridging mode coordinates to two NdIII atoms to display a 1D zigzag chain. Furthermore, the luminescence properties of 1 and 2 were investigated at room temperature in the solid state.  相似文献   

9.
采用高温固相反应法制备了非化学计量组成的Ba1.03Ce0.8 Ho0.2O3-α 固体电解质,用XRD和SEM对其相组成和表面及断面形貌进行了表征。用气体浓差电池方法测定了材料在600~1000 ℃温度范围内,干燥空气、湿润空气和湿润氢气气氛中的离子迁移数;用交流阻抗谱技术测定了它们在各实验气氛中的电导率。研究了材料的离子导电特性,并与BaCe0.8Ho0.2O3-α 和Ba0.97Ce0.8Ho0.2O3-α 的性能进行了比较。结果表明:该材料为单相钙钛矿型斜方晶结构。在600~1000 ℃温度范围内、干燥空气中,是氧离子与电子空穴的混合导体,氧离子迁移数为0.10~0.36;在湿润空气中,是质子、氧离子与电子空穴的混合导体,质子迁移数为0.11~0.01,氧离子迁移数为0.34~0.30;在湿润氢气气氛中,是纯质子导体,质子迁移数为1。在600~1000 ℃温度范围内,干燥空气、湿润空气和湿润氢气气氛中,非化学计量组成材料(x = 1.03,0.97)的电导率高于化学计量组成材料(x = 1)的电导率,其中,Ba1.03Ce0.8 Ho0.2O3-α的电导率最高 (1000 ℃时、在干燥空气气氛中:3.92×10-2 S·cm-1;在湿润空气气氛中:3.46×10-2 S·cm-1;在湿润氢气气氛中:2.10×10-2 S·cm-1)。Ba1.03Ce0.8 Ho0.2O3-α材料的离子导电性优于BaCe0.8Ho0.2O3-α 和Ba0.97Ce0.8Ho0.2O3-α。  相似文献   

10.
While the gold(I)‐catalyzed glycosylation reaction with 4,6‐O‐benzylidene tethered mannosyl ortho‐alkynylbenzoates as donors falls squarely into the category of the Crich‐type β‐selective mannosylation when Ph3PAuOTf is used as the catalyst, in that the mannosyl α‐triflates are invoked, replacement of the ?OTf in the gold(I) complex with less nucleophilic counter anions (i.e., ?NTf2, ?SbF6, ?BF4, and ?BAr4F) leads to complete loss of β‐selectivity with the mannosyl ortho‐alkynylbenzoate β‐donors. Nevertheless, with the α‐donors, the mannosylation reactions under the catalysis of Ph3PAuBAr4F (BAr4F=tetrakis[3,5‐bis(trifluoromethyl)phenyl]borate) are especially highly β‐selective and accommodate a broad scope of substrates; these include glycosylation with mannosyl donors installed with a bulky TBS group at O3, donors bearing 4,6‐di‐O‐benzoyl groups, and acceptors known as sterically unmatched or hindered. For the ortho‐alkynylbenzoate β‐donors, an anomerization and glycosylation sequence can also ensure the highly β‐selective mannosylation. The 1‐α‐mannosyloxy‐isochromenylium‐4‐gold(I) complex ( Cα ), readily generated upon activation of the α‐mannosyl ortho‐alkynylbenzoate ( 1 α ) with Ph3PAuBAr4F at ?35 °C, was well characterized by NMR spectroscopy; the occurrence of this species accounts for the high β‐selectivity in the present mannosylation.  相似文献   

11.
Nanoscale iron‐doped zirconia solid‐solution aerogels are prepared via a simple ethanol thermal route using zirconyl nitrate and iron nitrate as starting materials, followed by a supercritical fluid drying process. Structural characteristics are investigated by means of powder X‐ray diffraction (XRD), thermal analyses (TG/DTA), N2 adsorption measurements and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The results show that the resulting iron‐doped solid solutions are metastable tetragonal zirconia which exhibit excellent dispersibility and high solubility of iron oxide. Further, when the Fe:(Fe+Zr) ratio x is lower than 0.10, all of the Fe3+ ions can be incorporated into ZrO2 by substituting Zr4+ to form Zr1?xFexOy solid solutions. Moreover, for the first time, an additional hydroxyl group band that is not present in pure ZrO2 is observed by DRIFTS for the Zr(Fe)O2 solid solution. This is direct evidence of Fe3+ ions incorporated into ZrO2. These Zr1?xFexOy solid solutions are excellent catalysts for the solvent‐free aerobic oxidation of n‐hexadecane using air as the oxidant under ambient conditions. The Zr0.8Fe0.2Oy solid‐solution catalyst demonstrates the best catalytic properties, with the conversion of n‐hexadecane reaching 36.2 % with 48 % selectivity for ketones and 24 % selectivity for alcohols and it can be recycled five times without significant loss of activity.  相似文献   

12.
The ion conductors Li4+xAlxSi1‐xO4‐yLi3PO4 (x = 0 to 0.5, y = 0 to 0.6) were prepared by the Sol‐Gel method. The powder and sintered samples were characterized by DTA‐TG, XRD, SEM, and AC impedance techniques. The conductivity and sinterability increased when y increased from 0 to 0.4 in the Li4+xAlxSi1‐xO4‐yLi3PO4. The particle size of the powder samples is about 0.13 μm. The maximum conductivity at 20 °C is 3.128 × 10?5s cm?1 for Li4.4Al0.4Si0.6O4‐0.4 Li3PO4.  相似文献   

13.
Poly(vinyl alcohol)‐graft‐poly(1,4‐dioxan‐2‐one) (PVA‐g‐PPDO) with designed molecular structure was synthesized by a solid‐state polymerization. The solid‐state copolymerization was preceded by a graft copolymerization of PDO initiated with PVA as a multifunctional initiator, and Sn (Oct)2 as a coininitiator/catalyst in a homogeneous molten state. The polymerization temperature was then decreased and the copolymerization was carried out in a solid state. The products prepared by solid‐state polymerization were characterized by 1H NMR and DSC, and were compared with those synthesized in the homogeneous molten state. The degree of polymerization (Dp), degree of substitution (Ds), yield and the average molecular weight of the graft copolymer with different molecular structure were calculated from the 1H NMR spectra. The results show that the crystallization process during the solid‐state polymerization may suppress the undesirable inter‐ or intramolecular side reactions, then resulting in a controlled molecular structure of PVA‐g‐PPDO. The results of DSC measurement show that the molecular structures determine the thermal behavior of the PVA‐g‐PPDO. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3083–3091, 2006  相似文献   

14.
Mn4+‐doped fluoride phosphors have been widely used in wide‐gamut backlighting devices because of their extremely narrow emission band. Solid solutions of Na2(SixGe1?x)F6:Mn4+ and Na2(GeyTi1?y)F6:Mn4+ were successfully synthesized to elucidate the behavior of the zero‐phonon line (ZPL) in different structures. The ratio between ZPL and the highest emission intensity υ6 phonon sideband exhibits a strong relationship with luminescent decay rate. First‐principles calculations are conducted to model the variation in the structural and electronic properties of the prepared solid solutions as a function of the composition. To compensate for the limitations of the Rietveld refinement, electron paramagnetic resonance and high‐resolution steady‐state emission spectra are used to confirm the diverse local environment for Mn4+ in the structure. Finally, the spectral luminous efficacy of radiation (LER) is used to reveal the important role of ZPL in practical applications.  相似文献   

15.
Earlier studies have shown a strong correlation between the enthalpy of formation, ΔHf,ox, and the ionic conductivity, σi, near room temperature in doped ceria systems, which are promising solid electrolytes for intermediate‐temperature solid oxide fuel cells (IT‐SOFCs). The present work demonstrates that this correlation holds at the operating temperature of IT‐SOFCs, 600–700 °C. Solid solutions of Ce1?xNdxO2?0.5x, Ce1?xSmxO2?0.5x, and Ce1?xSm0.5xNd0.5xO2?0.5x are studied. The ΔHf,ox at 702 °C is determined by considering the excess heat content between 25 and 702 °C combined with the value of ΔHf,ox at 25 °C. Both σi and ΔHf,ox show maxima at x=0.15 and 0.20 for the singly and doubly doped ceria, respectively, suggesting that the number of mobile oxygen vacancies in these solid solutions reaches a maximum near those compositions. An increase in temperature results in a shift of the maximum in both ΔHf,ox and σi towards higher concentrations. This shift results from a gradual increase in dissociation of the defect associates.  相似文献   

16.
Oxidative dehydrogenation of ethane (ODE) is limited by the facile deep oxidation and potential safety hazards. Now, electrochemical ODE reaction is incorporated into the anode of a solid oxide electrolysis cell, utilizing the oxygen species generated at anode to catalytically convert ethane. By infiltrating γ‐Al2O3 onto the surface of La0.6Sr0.4Co0.2Fe0.8O3‐δ‐Sm0.2Ce0.8O2‐δ (LSCF‐SDC) anode, the ethylene selectivity reaches as high as 92.5 %, while the highest ethane conversion is up to 29.1 % at 600 °C with optimized current and ethane flow rate. Density functional theory calculations and in situ X‐ray photoelectron spectroscopy characterizations reveal that the Al2O3/LSCF interfaces effectively reduce the amount of adsorbed oxygen species, leading to improved ethylene selectivity and stability, and that the formation of Al‐O‐Fe alters the electronic structure of interfacial Fe center with increased density of state around Fermi level and downshift of the empty band, which enhances ethane adsorption and conversion.  相似文献   

17.
The cerium oxidation states in single catalyst particles of Pt/Ce2Zr2Ox (x=7 to 8) were investigated by spatially resolved nano X‐ray absorption fine structure (nano‐XAFS) using an X‐ray nanobeam. Differences in the distribution of the Ce oxidation states between Pt/Ce2Zr2Ox single particles of different oxygen compositions x were visualized in the obtained two‐dimensional X‐ray fluorescent (XRF) mapping images and the Ce LIII‐edge nano X‐ray absorption near‐edge structure (nano‐XANES) spectra.  相似文献   

18.
High‐temperature flame spray pyrolysis is employed for finding highly efficient nanomaterials for use in lithium‐ion batteries. CoOx‐FeOx nanopowders with various compositions are prepared by one‐pot high‐temperature flame spray pyrolysis. The Co and Fe components are uniformly distributed over the CoOx‐FeOx composite powders, irrespective of the Co/Fe mole ratio. The Co‐rich CoOx‐FeOx composite powders with Co/Fe mole ratios of 3:1 and 2:1 have mixed crystal structures with CoFe2O4 and Co3O4 phases. However, Co‐substituted magnetite composite powders prepared from spray solutions with Co and Fe components in mole ratios of 1:3, 1:2, and 1:1 have a single phase. Multicomponent CoOx‐FeOx powders with a Co/Fe mole ratio of 2:1 and a mixed crystal structure with Co3O4 and CoFe2O4 phases show high initial capacities and good cycling performance. The stable reversible discharge capacities of the composite powders with a Co/Fe mole ratio of 2:1 decrease from 1165 to 820 mA h g?1 as the current density is increased from 500 to 5000 mA g?1; however, the discharge capacity again increases to 1310 mA h g?1 as the current density is restored to 500 mA g?1.  相似文献   

19.
By precipitation with ammonia of ethanolic solutions containing the appropriate proportions of gallium and aluminium nitrate, following by calcination of the resulting gels at 773 K, mixed Ga2O3/Al2O3 oxides having Ga:Al ratios of 9:1, 4:1, 1:1, 1:4 and 1:9 were obtained. Powder X‐ray diffraction showed that these mixed metal oxides form a series of solid solutions having the spinel‐type structure; also shown by γ‐Al2O3 and γ‐Ga2O3. The specific surface area (determined by nitrogen adsorption at 77 K) was found to range from 160 m2 g?1 for the mixed oxide having Ga:Al = 9:1 up to 370 m2 g?1 for that having Ga:Al = 1:9. High resolution MAS NMR showed that Ga3+ and Al3+ ions occur at both tetrahedral and octahedral sites in the spinel‐type structure of the mixed metal oxides, although there is a preferential occupation of tetrahedral sites by Ga3+ ions. A proportion of penta‐coordinated Al3+ ions was also found. IR spectra of carbon monoxide adsorbed at 77 K showed that the mixed metal oxides have a considerable Lewis acidity, related mainly to tetrahedrally coordinated metal ions exposed at crystal surfaces. The characteristic infrared absorption band of coordinated (adsorbed) CO appears in the range 2205–2190 cm?1, and its peak wavenumber is nearly independent of Ga:Al ratio in the mixed gallia‐alumina oxides.  相似文献   

20.
The oxonitridoaluminosilicate chloride Pr10[Si10?xAlxO9+xN17?x]Cl was obtained by the reaction of praseodymium metal, the respective chloride, AlN and Al(OH)3 with “Si(NH)2” in a radiofrequency furnace at temperatures around 1900 °C. The crystal structure was determined by single‐crystal X‐ray diffraction (Pbam, no. 55, Z = 2,a = 10.5973(8) Å, b = 11.1687(6) Å, c = 11.6179(7) Å, R1 = 0.0337). The sialon crystallizes isotypically to the oxonitridosilicate halides Ce10[Si10O9N17]Br, Nd10[Si10O9N17]Br and Nd10[Si10O9N17]Cl, which represent a new layered structure type. The structure refinement was performed utilizing an O/N‐distribution model according to Paulings rules, i.e. nitrogen was positioned on all bridging sites and mixed O/Noccupation was assumed on the terminal sites resulting in charge neutrality of the compounds. The Si and Al atoms were refined equally distributed on their three crystallographic sites, due to their poor distinguishability by X‐ray analysis. The tetrahedra layers of the structure consist of condensed [(Si,Al)N2(O,N)2] and [(Si,Al)N3(O,N)] tetrahedra of Q2 and Q3 type. The chemical composition of the compound was derived from electron probe micro analyses (EPMA).  相似文献   

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