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1.
A series of palladium-substituted La2CuO4, corresponding to the formula La2Cu1 −xPdxO4 (x = 0−0.2) were prepared by metal nitrate decomposition in a polyacrylamide gel. This method allows an easy incorporation of palladium in the mixed-oxides, which are formed at moderate temperature with rather high specific areas (13–17 m2/g). The partial substitution of copper for palladium allows a strong improvement of the three-way catalytic activity, in particular for NO reduction. The light-off temperatures for the conversions of CO, NO and C3H6 decreased markedly when increasing the palladium content, the activity of catalysts La2Cu0.9Pd0.1O4 and La2Cu0.8Pd0.2O4 being comparable to that of a Pt-Rh/CeO2–Al2O3 catalyst for NO reduction, and higher for CO and C3H6 oxidation.

All the La2Cu1 − x PdxO4 catalysts are activated under reacting conditions. This activation corresponds to the destruction of the mixed-oxide structure, with formation of reduced Pd0 ions atomically dispersed, surrounded by Cu+ and Cu2+ species on a lanthanum oxycarbonate matrix. This high dispersion state of the two transition metals in various oxidation states is supposed to originate from the initial La2Cu1 −xPdxO4 structure.  相似文献   


2.
Proton conducting solid oxide fuel cell (H-SOFC) is an emerging energy conversion device, with lower activation energy and higher energy utilization efficiency. However, the deficiency of highly active cathode materials still remains a major challenge for the development of H-SOFC. Therefore, in this work, K2NiF4-type cathode materials Pr2-xBaNi0.6Cu0.4O4+δ (x=0, 0.1, 0.2, 0.3), single-phase triple-conducting (e-/O2-/H+) oxides, are prepared for intermediate temperature H-SOFCs and exhibit good oxygen reduction reaction activity. The investigation demonstrates that doping Ba into Pr2-xBaNi0.6Cu0.4O4+δ can increase its electrochemical performance through enhancing electrical conductivity, oxygen vacancy concentration and proton conductivity. EIS tests are carried at 750℃ and the minimum polarization impedances are obtained when x=0.2, which are 0.068 Ω·cm2 in air and 1.336 Ω·cm2 in wet argon, respectively. The peak power density of the cell with Pr1.8Ba0.2Ni0.6Cu0.4O4+δ cathode is 298 mW·cm-2 at 750℃ in air with humidified hydrogen as fuel. Based on the above results, Ba-doped Pr2-xBaNi0.6Cu0.4O4+δ can be a good candidate material for SOFC cathode applications.  相似文献   

3.
The structural and electronic properties of selected compositions of SnxTi1−xO2 solid solutions (x=0, 1/24, 1/16, 1/12, 1/8, 1/6, 1/4, 1/2, 3/4, 5/6, 7/8, 11/12, 15/16, 23/24 and 1) were investigated by means of periodic density functional theory (DFT) calculations at B3LYP level. The calculations show that the corresponding lattice parameters vary non-linearly with composition, supporting positive deviations from Vegard’s law in the SnxTi1−xO2 system. Our results also account for the fact that chemical decomposition in SnxTi1−xO2 system is dominated by composition fluctuations along [0 0 1] direction. A nearly continuous evolution of the direct band gap and the Fermi level with the growing value of x is predicted. Ti 3d states dominate the lower portion of the conduction band of SnxTi1−xO2 solid solutions. Sn substitution for Ti in TiO2 increases the oxidation–reduction potential of the oxide as well as it renders the lowest energy transition to be indirect. These two effects can be the key factors controlling the rate for the photogenerated electron–hole recombination. These theoretical results are capable to explain the enhancement of photoactivity in SnxTi1−xO2 solid solutions.  相似文献   

4.
Layered Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Crx]O2 materials with x = 0, 0.01, 0.02, 0.03, 0.05 are prepared by a solid-state pyrolysis method. The oxide compounds were calcined with various Cr-doped contents, which result in greater difference in morphological (shape, particle size and specific surface area) and the electrochemical (first charge profile, reversible capacity and rate capability) differences. The Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Crx]O2 powders were characterized by means of X-ray diffraction (XRD), charge/discharge cycling, cyclic voltammetry, and SEM. XRD experiment revealed that the Li[Ni(1−x)/3Mn(1−x)/3Co(1−x)/3Crx]O2 (x = 0, 0.01, 0.02, 0.03, 0.05) were crystallized to well layered -NaFeO2 structure. The first specific discharge capacity and coulombic efficiency of the electrode of Cr-doped materials were higher than that of pristine material. When x = 0.02, the sample showed the highest first discharge capacity of 241.9 mAh g−1 at a current density of 30 mA g−1 in the voltage range 2.3–4.6 V, and the Cr-doped samples exhibited higher discharge capacity and better cycleability under medium and high current densities at room temperature.  相似文献   

5.
Novel Ir-substituted hexaaluminate catalysts were developed for the first time and used for catalytic decomposition of high concentration of N2O. The catalysts were prepared by one-pot precipitation and characterized by X-ray diffraction (XRD), N2-adsorption, scanning electronic microscopy (SEM) and temperature-programmed reduction (H2-TPR). The XRD results showed that only a limited amount of iridium was incorporated into the hexaaluminate lattice by substituting Al3+ to form BaIrxFe1−xAl11O19 after being calcined at 1200 °C, while the other part of iridium existed as IrO2 phase. The activity tests for high concentration (30%, v/v) of N2O decomposition demonstrated that the BaIrxFe1−xAl11O19 hexaaluminates exhibited much higher activities and stabilities than the Ir/Al2O3-1200, and the pre-reduction with H2 was essential for activating the catalysts. By comparing BaIrxFe1−xAl11O19 with BaIrxAl12−xO19 (x = 0–0.8), it was found that iridium was the active component in the N2O decomposition and the framework iridium was more active than the large IrO2 particles. On the other hand, Fe facilitated the formation of hexaaluminate as well as the incorporation of iridium into the framework.  相似文献   

6.
This paper describes the study of a pink ceramic pigment based on the optical properties of Cr-doped structures, having into account environmental considerations. The research is focused on the optimisation of the synthesis parameters in order to minimise the amount of pollutant Cr(VI) in the washing liquids and enhance chromatic coordinates. In a first stage, the Al2−xCrxO3 solid solution was studied. Nevertheless, the observation that ZnO was required in the frit to stabilise the pink colour after glazing made us to conduct the research towards the optimisation of the ZnAl2−xCrxO4 system. X-ray diffraction (XRD) indicates a solid solution formation based on the gahnite structure; moreover, no Cr(VI) and B contents were found in the analysis of the washing liquids. Thus, this research enabled us to produce a pink pigment with low environmental impact and good chromatic coordinates. Further study of the pigment applied in a glaze showed evidence of the importance of the glaze composition for the colour development and stability of the ceramic pigments.  相似文献   

7.
The aim of the present work is to obtain ceramic materials with a hexagonal structure and high density, hardness and mechanical strength at lower synthesis temperature. Ceramic samples with nominal composition La1−xCaxAl11−yzMgyTizO18 (x=0–1; y=0–3; z=0–3,5) are prepared. The samples are sintered at temperature 1500 °C by one-stage and two-stage ceramic technology. By X-ray diffraction and scanning electron microscopy, predominant phase LaAl11O18 and second phases LaAlO3 and -Al2O3 are identified. Ceramic materials are characterized with high physico-mechanical properties and may be find application for production of mill bodies and materials for immobilization of nuclear waste.  相似文献   

8.
为了制备低成本、高色度的钴蓝颜料,本文以高岭土为载体,以Al2O3和Co3O4为主要原料,通过引入ZnO、CaO及MgO不同金属氧化物,采用固相法制备了高色度(CoxM1-xAl2O4)/高岭土复合颜料(M为Ca2+、Mg2+或Zn2+)。系统考察了研磨时间、煅烧温度、煅烧时间和不同金属氧化物掺量对复合颜料呈色性能的影响规律。研究表明,在煅烧温度1 200 ℃、研磨时间12 h和n(Co2+)/n(M2+)为3:2时,制得的复合颜料具有最好的呈色性能(L*=53.68,a*=7.58,b*=-62.89)。同时,引入不同的金属元素,可实现对复合颜料颜色的调控,引入Ca2+后,所制备的CoxCa1-xAl2O4复合颜料偏红相,而引入Zn2+后,所制备的CoxZn1-xAl2O4复合颜料偏绿相。通过相关表征,提出了复合颜料的呈色机理,在颜料制备过程中,引入与Co2+离子半径接近的Mg2+或Zn2+,Mg2+或Zn2+可进入CoAl2O4的四面体配位中,部分替代Co2+,形成MgAl2O4-CoAl2O4或ZnAl2O4-CoAl2O4的固溶体,而引入离子半径较大的Ca2+,形成CaAl2O4和CoAl2O4的均相混合物。最后,将制得复合颜料应用到有机硅耐热涂料中,可以明显提高有机硅涂料的热稳定性。  相似文献   

9.
Catalytic methane combustion and CO oxidation were investigated over AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 (x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe4+ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m2 g−1 range. XRD analysis showed that LaFeO3, NdFeO3, SmFeO3 and LaFe1−xMgxO3 (x·0.3) are single phase perovskite-type oxides. Traces of La2O3, in addition to the perovskite phase, were detected in the LaFe1−xMgxO3 catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO3 of a very small fraction of Fe4+ which reduces to Fe3+. The fraction of Fe4+ in the LaFe1−xMgxO3 samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO2 below 973 and 773 K, respectively. For the AFeO3 materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe1−xMgxO3 catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase (x=0.3). Concerning the CO oxidation, the order of activity for the AFeO3 materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe1−xMgxO3 catalysts decreases at high magnesium content.  相似文献   

10.
Perovskites of different La1−xSrxAl1−yyFeyMgyO3−δ compositions (x=0, 0.1, 0.15, 0.2 and y=0.1, 0.3, 0.5, 0.8) were prepared from a reactive precursor slurry of hydrated oxides. Each sample was aged between 16 and 26 h up to 1473 K. Activity in methane combustion (1%/air) was determined in a plug-flow reactor, with 1 g catalyst and 24 l/h flowrate. Gradual decrease in activity due to thermal aging was observed, the degree of activity loss being composition dependent. Nevertheless, activity of samples aged at 1370 K was nearly independent of composition. The best thermal stability showed LaAl0.65Fe0.15Mg0.2O3 perovskite. None of the magnesium substituted perovskites performed better than a La0.85Sr0.15Al0.87Fe0.13O3 reference sample.  相似文献   

11.
Ceramics with a composition close to BaZn2Ti4O11 were synthesized according to various substitutional mechanisms in order to verify an existence of a homogeneity range in the vicinity of this composition. Structural and microstructural investigations showed that the crystal structure of BaZn2Ti4O11 was formed in the homogeneity range corresponding to the formula BaZn2 − xTi4O11 − x (0 < x < 0.1). Densely sintered BaZn2 − xTi4O11 − x (0 < x < 0.1) ceramics exhibited a dielectric constant around 30, τf = −30 ppm/K and high Q × f values, which increased from 68,000 GHz at x = 0 to 83,000 GHz at x = 0.05. Structurally, the deficiency of Zn in BaZn2 − xTi4O11 − x (0 < x < 0.1) resulted in a slight decrease in the unit-cell volume. The influence of secondary phases in the BaZn2Ti4O11-based materials on the microwave dielectric properties was also investigated. A presence of small amounts of ZnO, BaTiO3, hollandite-type solid solutions (BaxZnxTi8 − xO16) and BaTi4O9 caused a decrease in Q × f values.  相似文献   

12.
The evolution of the cathode material of Li/V2O5 cells upon lithium intercalation is studied by Electron Paramagnetic Resonance (EPR) spectroscopy. Below one lithium per V2O5(x < 1), where the electrochemical process is completely reversible, VIV ions of the - and δ-Lix V2O5 phases are detected by EPR. Within this intercalation range, the shape of the EPR signal is dominated by the strong exchange interactions between magnetically concentrated VIV ions of the Lix V2O5 phases. The intercalation range x > 1 is characterized by a new EPR signal attributed to magnetically diluted vanadyl ions VO2+. It is shown that these species do not belong to the Lix V2O5 matrix, but most probably originate from the liberation of surface vanadyl ions during the irreversible transformation of δ-Lix V2O5 into γ-Lix V2O5. On the basis of these results, a mechanism to explain the partial irreversibility of the electrochemical processes is proposed. A third EPR signal is also observed for x 1. This signal is attributed to an electron-hole defect in Lix V2O5, originating from a local charge compensation of the vanadyl vacancies.  相似文献   

13.
Ten weight percent BBZS (Bi2O3, B2O3, ZnO and SiO2) glass was added to x(Ba4Nd9.333Ti18O54) − (1 − x)(BaLa4Ti4O15) (BNLT, 0 ≤ x ≤ 1) composite dielectric ceramics to lower their sintering temperature whilst retaining microwave properties useful for low temperature co-fired ceramic and antenna core technology. With the addition of 10 wt% BBZS glass, dense BNLT composite ceramics were produced at temperatures between 950 and 1140 °C, depending on composition (x), an average reduction of sintering temperature by 350 °C. X-ray diffraction, scanning and transmission electron microscopy and Raman spectroscopy studies revealed that there was limited inter-reaction between BLT/BNT and the BBZS glass. Microwave property measurement showed that the addition of BBZS glass to BNLT ceramics had a negligible effect on r and τf, although deterioration in the measured quality factor (Qf) was observed. The optimised composition (xBNT − (1 − x)BLT)/0.1BBZS (x = 0.75) had r  61, τf  38 ppm/°C and Qf  2305 GHz.  相似文献   

14.
LaxSr2−xMnO4 (0 ≤ x ≤ 0.8) oxides were synthesized and single-phase K2NiF4-type oxides were obtained in the range of 0.1 ≤ x < 0.5. The catalytic activity of LaxSr2−xMnO4 for NO–CO reaction increased with increasing x in the range of solubility limit of La. La0.5Sr1.5MnO4 showed the highest activity among LaxSr2−xMnO4 prepared in this study, but its activity was inferior to perovskite-type La0.5Sr0.5MnO3. Among the Pd-loaded catalysts, however, Pd/La0.8Sr1.2MnO4 showed the higher activity and the selectivity to N2 than Pd/La0.5Sr0.5MnO3 and Pd/γ-Al2O3. The excellent catalytic performance of Pd/La0.2Sr1.2MnO4 could be ascribable to the formation of SrPd3O4 which was detected by XRD in the catalyst but not in the other two catalysts.  相似文献   

15.
The construction of efficient photocatalysts has received much attention in wastewater treatment. In this study, Nb-doped NaTaO3 was prepared with different doping ratio by a facile hydrothermal method. The prepared catalysts were analyzed by X-ray diffraction, scanning electron microscopy, Brunauer-Emmett-Teller (BET) theory, ultraviolet–visible diffuse reflectance spectroscopy. Then the synthesized catalysts were employed to degrade a model pollutant, methylene blue (MB), under a 250 W mercury lamp. The characterization tests confirm that Nb was successfully doped into the crystal structure of NaTaO3 and the modified NaNbxTa1-xO3 (x is the doping ratio; x = 0.25, 0.5, 0.75) samples were formed, which were in regular cubic shapes just like pure NaTaO3. The synthesized NaNbxTa1-xO3 (x = 0.25, 0.5, 0.75) had improved specific surface area and narrowed band gaps compared with pure NaTaO3. In photocatalytic degradation experiments, NaNb0.75Ta0.25O3 presented the best photocatalytic activity ascribed to the narrow band gap and the high surface area, degradating 95.7% of MB after 180 min of reaction, which was even twice the ability of pure NaTaO3. Besides, the effects of possible inorganic anions and cations in wastewater on photocatalytic degradation were investigated. Electron spin resonance (ESR) tests and capture experiments were also conducted and a possible photocatalytic mechanism was proposed. This work provides a direction for constructing superior NaTaO3-based photocatalysts to be widely utilized in environmental protection.  相似文献   

16.
高折射率和非线性光学玻璃可以用于高速光开关、光学存储器、新型光纤和光学运算元件等,其研究受到各国科技工作者的高度重视,本文采用熔融淬冷法制备了组成为(85-x)B2O3-15K2O-xSb2O3(x=70, 75, 80, 85)的4组玻璃,测试了玻璃样品的密度、折射率、热学性能、拉曼光谱和吸收光谱,利用玻璃样品的吸收光谱计算了其直接允许光学带隙、间接允许光学带隙及Urbach能量。结果表明:随着Sb2O3含量的增加,玻璃样品的密度从4.445g/cm3逐渐增加到4.767g/cm3,折射率从1.9438增加到2.0058,玻璃转变温度从291℃降低到260℃,玻璃析晶温度从463℃降低到370℃,直接光学带隙从3.2775eV降低到3.1379eV,间接光学带隙从3.1444eV降低到3.0256eV,Urbach能量从0.137eV逐渐减小到0.107eV。说明Sb2O3-K2O-B2O3系统玻璃可以作为新型的非线性光学玻璃候选材料之一。  相似文献   

17.
In this work, the detailed oxygen reduction reaction (ORR) catalytic performance of M-N4xOx (M= Fe, Co, and Ni; x = 1–4) has been explored via the detailed density functional theory method. The results suggest that the formation energy of M-N4xOx shows a good linear relationship with the number of doped O atoms. The adsorption manner of O2 on M-N4xOx changed from end-on (x = 1 and 2) to side-on (x = 3 and 4), and the adsorption strength gradually increased. Based on the results for binding strength of ORR intermediates and the Gibbs free energy of ORR steps on the studied catalysts, we screened out two highly active ORR catalysts, namely Co-N3O1 and Ni-N2O2, which possess very small overpotentials of 0.27 and 0.32 V, respectively. Such activities are higher than the precious Pt catalyst. Electronic structure analysis reveals one of the reasons for the higher activity of Co-N3O1 and Ni-N2O2 is that they have small energy gaps and moderate highest occupied molecular orbital energy levels. Furthermore, the results of the density of states reveal that the O doping can improve the electronic structure of the original catalyst to tune the adsorption of the ORR intermediates.  相似文献   

18.
To clarify the effect of substitutional electron doping on the thermoelectric figure of merit (ZT = S2σTκ−1) of Ruddlesden–Popper phase SrO(SrTiO3)n (or Srn+1TinO3n+1), measurements were conducted for several thermoelectric parameters, e.g. electrical conductivity (σ), Seebeck coefficient (S) and thermal conductivity (κ), of (Sr1−xREx)n+1TinO3n+1 (n = 1 or 2, RE (rare earth): La or Nd, x = 0.05 and 0.1) dense ceramics prepared by a conventional solid-state reaction and hot-pressing technique. Crystal structures of the resultant ceramics were represented as (Sr1−xREx)n+1 TinO3n+1 evaluated by powder X-ray diffraction followed by the Rietveld analysis. All the ceramics exhibited electrical conductivity and the σ values simply depended on the dopant concentration, indicating that both La3+ and Nd3+ ions act as electron donors. The |S| values increased with temperature due to decrease in the chemical potential. Significant reduction of the κ values was observed as compared to cubic-perovskite SrTiO3. The ZT value increased with temperature and reached 0.15 at 1000 K for (Sr0.95La0.05)3Ti2O7.  相似文献   

19.
Rutile-type Cr/V/Sb mixed oxides, catalysts for the ammoxidation of propane to acrylonitrile, were prepared and characterized. For atomic ratios between components equal to Cr/V/Sb 1/x/1 and 1/x/2 the systems were monophasic, but different types of compounds formed depending on the ratio between the three metals. The compositional parameter which most affected the nature of the compound formed was the (Cr+V)/Sb atomic ratio. When this ratio was between 2 and ≈1, a rutile Cr3+/V4+/Sb5+ mixed oxide of composition Cr1VxSb1O4+2x developed (0<x<1), which in practice corresponds to a solid solution between 1 CrSbO4 and x VO2. When the (Cr+V)/Sb ratio was between 0.5 and ≈1, a rutile Cr3+/V3+/Sb3+/Sb5+ mixed oxide of composition CrVxSb1+x+2zO4+4x+4z developed (0<x<1), which corresponds to a solid solution between 1 Cr3+Sbz3+Sb1+z5+O4+4z and x VSbO4. The distinction between the two classes of compounds was not clear-cut, and when the (Cr+V)/Sb atomic ratio was around 1, mixed oxides containing both V3+ and V4+ formed. Values of the (Cr+V)/Sb atomic ratio lower than ≈0.5 led to the additional formation of antimony oxide.  相似文献   

20.
A series of the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H2-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts the surface phase structure were the Ce1−xCuxO2−x solid solution, -Al2O3 and γ-Al2O3. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce1−xCuxO2−x solid solution. The Cu component of the Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce1−xCuxO2−x solid solution and the Al2O3 washcoats and the FeCrAl support.  相似文献   

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