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1.
La1-xSrxFeO3-δ系钙钛矿材料的表征和性能   总被引:5,自引:0,他引:5       下载免费PDF全文
采用甘氨酸-硝酸盐(GNP)法合成了中温固体氧化物燃料电池阴极材料La1-xSrxFeO3-δ(x=0.0~0.6)系列粉体。用FTIR、TG-DTA、XRD等对产物形成过程及结晶学特征进行了研究,考察了合成样品与Sm0.2Ce0.8O1.9(SDC)的化学相容性;利用碘滴定法测定了该系列产物中Fe元素的平均表观化合价和氧的非化学计量值。结果表明,所合成的系列样品均形成具有ABO3型结构的钙钛矿固溶体。随A位取代Sr含量的增加,IR谱图上560 cm-1附近B-O键伸缩振动的红外吸收峰蓝移,意味着钙钛矿产物中Fe-O键的共价性成分增强。实验还发现,Fe元素的平均化合价先随样品中Sr含量的增加而升高,并以La0.6Sr0.4FeO3-δ样品达最高,而后降低;样品中氧的非化学计量值则随掺Sr量的增加单调增大。四探针法电导测量结果表明,在x≤0.4时,La1-xSrxFeO3-δ系列陶瓷烧结体在中温(450~800 ℃)区的电导率,随Sr掺入量的增大而增大,La0.6Sr0.4FeO3-δ样品的电导率最高,进一步增大Sr含量导电性能变差。在低温段,样品的导电行为符合小极化子导电机制。该系列材料与SDC电解质材料具有良好的化学相容性。  相似文献   

2.
通过溶胶-凝胶法制备出A位Sr掺杂的钙钛矿型氧化物La1-xSrxCoO3x=0,0.2,0.4,0.6,0.8),并将其作为催化剂应用于双功能氧电极中。测试结果表明,A位Sr的掺杂的La1-xSrxCoO3比LaCoO3具有更高的电催化活性,并且La0.6Sr0.4CoO3在氧还原和氧析出反应中均表现出最优的催化性能,最大电流密度分别达到0.244 A·cm-2(-0.6 V vs Hg/HgO)和0.303 A·cm-2(1 V vs Hg/HgO)。为进一步提高催化剂的催化活性,将水热法制备的α-MnO2纳米管与La0.6Sr0.4CoO3复合作为双功能催化剂。当α-MnO2的质量分数为40%时,比起单一的α-MnO2或钙钛矿氧化物,α-MnO2/La0.6Sr0.4CoO3复合材料表现出协同效应,有更好的双功能电催化活性,使双效氧电极具有更好的电化学性能及稳定性。  相似文献   

3.
钙钛矿型LaxSr1-xNi1-yCoyO3光电催化活性研究   总被引:1,自引:0,他引:1  
用甘氨酸-硝酸盐燃烧合成法, 制备LaxSr1-xNi1-yCoyO3复合氧化物的陶瓷粉末, 对钙钛矿氧化物进行了XRD结构分析. 在通氧或不通氧下测试氧还原和氧析出的循环伏安曲线. 结果表明: 该氧电极具有双功能催化特性, 但不完全可逆. 利用汞灯作为激发光源, 进行几种水溶性染料和五种混合染料光解实验, 利用紫外-可见、红外以及人工神经网络光度法研究LaxSr1-xNi1-yCoyO3的催化性能. 结果表明: LaxSr1-xNi1-yCoyO3 (x=0.7, 0.9, 1; y=0.3, 0.75)复合氧化物都具有较强光催化特性; LaxSr1-xNi1-yCoyO3的光催化活性高于LaxSr1-xNiO3, 这与B位离子(Ni2—, Co2-)的电子构型有关; Co2+的加入可使LaxSr1-xNiO3的光催化活性有所提高.  相似文献   

4.
纳米钙钛矿LaxSr1-xFe1-yCoyO3复合氧化物的制备和表征   总被引:1,自引:0,他引:1  
用甘氨酸-硝酸盐燃烧合成法,制备LaxSr1-xFe1-yCoyO3复合氧化物的陶瓷粉末,对该钙钛矿型氧化物进行了XRD、IR、紫外漫反射光谱及循环伏安曲线分析。结果表明:该复合氧化物粉体平均晶粒为15.3~29.8 nm,为立方和正交晶系。该氧电极具有双功能催化特性,但不完全可逆。对水溶液染料进行光解实验,利用紫外-可见、人工神经网络光度法研究LaxSr1-xFe1-yCoyO3的催化性能。结果表明:CO2+的加入可使LaxSr1-xFeO3的光催化活性有所提高,B位离子(Fe3+,CO2+)改变与加入,使LaxSr1-xFe1-yCoyO3(x=0.7,0.3;y=0.3,0.9,1)光催化活性高于LaxSr1-xFeO3。同时,对5种染料进行紫外光解,在0.75 h,脱色率大于91%,并为动力学一级反应。  相似文献   

5.
采用EDTA-柠檬酸法合成了中温固体氧化物燃料电池阴极材料Sr1.5La0.5Mn1-xCoxO4(SLMCOx),并利用粉末X射线衍射(XRD)、X射线光电子能谱(XPS)以及电化学交流阻抗谱(EIS)进行表征。结果表明,该材料与Ce0.9Gd0.1O1.95(CGO)在1 200℃烧结12 h不发生化学反应。随着Co掺入量的增加,氧化物中Mn3+和Co2+含量增多,晶格氧含量降低,晶格畸变率增大。交流阻抗谱(EIS)测试结果显示,钴的掺杂明显降低电极的极化电阻,其中Sr1.5La0.5Mn0.7Co0.3O4阴极在700℃空气中的极化电阻为0.62 Ω·cm2,明显小于Sr1.5La0.5MnO4阴极在750℃的极化电阻(1.5 Ω·cm2),表明钴掺杂的Sr1.5La0.5Mn1-xCoxO4是一种潜在的IT-SOFC阴极材料。  相似文献   

6.
采用甘氨酸-硝酸盐溶液燃烧法制备了钙钛矿型氧化物催化剂La0.8Sr0.2Fe1-xScxO3-δ (LSFS, x=0, 0.3,0.4, 0.5, 0.6, 0.8, 1), 利用X射线衍射(XRD)、H2程序升温还原(H2-TPR)、扫描电子显微镜(SEM)和比表面积测试等手段对催化剂进行了系统表征, 并在常压微型固定床反应器上考察了催化剂对甲烷燃烧的催化性能. 结果表明, 经空气气氛下900 °C煅烧5 h制备的LSFS均具有单一的钙钛矿结构, 在La0.8Sr0.2FeO3-δ (LSF)中掺杂Sc有助于改善催化剂的抗烧结性能, 提高催化剂的比表面积. 当LSF 中的Sc 掺杂量为0.4-0.6 时, 所形成的LSFS表现出良好的甲烷催化燃烧活性, 其中Sc 掺杂量为0.5 时, 其起燃温度(T10)和完全转化温度(T90)分别为406和563 °C, 与La0.8Sr0.2FeO3-δ和La0.8Sr0.2ScO3-δ相比, T10分别降低了14和87 °C; T90分别降低了59和95 °C.  相似文献   

7.
钙钛矿型LaxSr1-xNi1-yCoyO3光电催化活性研究   总被引:8,自引:0,他引:8  
用甘氨酸-硝酸盐燃烧合成法, 制备LaxSr1-xNi1-yCoyO3复合氧化物的陶瓷粉末, 对钙钛矿氧化物进行了XRD结构分析. 在通氧或不通氧下测试氧还原和氧析出的循环伏安曲线. 结果表明: 该氧电极具有双功能催化特性, 但不完全可逆. 利用汞灯作为激发光源, 进行几种水溶性染料和五种混合染料光解实验, 利用紫外-可见、红外以及人工神经网络光度法研究LaxSr1-xNi1-yCoyO3的催化性能. 结果表明: LaxSr1-xNi1-yCoyO3 (x=0.7, 0.9, 1; y=0.3, 0.75)复合氧化物都具有较强光催化特性; LaxSr1-xNi1-yCoyO3的光催化活性高于LaxSr1-xNiO3, 这与B位离子(Ni2—, Co2-)的电子构型有关; Co2+的加入可使LaxSr1-xNiO3的光催化活性有所提高.  相似文献   

8.
利用高温固相反应法制备了Sr掺杂LaNbO4质子导体La1-xSrxNbO4-σ(0≤x≤0.02),并且对其性能进行了表征。XRD分析表明,所有的样品具有单斜结构,晶胞体积随Sr掺杂量的增加而增大;La1-xSrxNbO4-σ样品在沸水中和二氧化碳气氛中具有很好的化学稳定性。SEM分析表明,La1-xSrxNbO4-σ粉体经1500℃烧结8h后均得到致密的、晶粒均匀的样品;Sr的掺杂抑制了陶瓷体裂缝的产生和晶粒的过度增长;随Sr的掺杂量增加,晶粒变小。交流阻抗谱分析表明,Sr掺杂改变了LaNbO4的电导率,其中样品La0.995Sr0.005NbO4-σ具有最高的电导率;样品在25℃水汽饱和的5%H2-Ar气氛下的电导率明显高于干燥空气气氛,在800℃时,La0.995Sr0.005NbO4-σ电导率达到0.003S·cm-1,电导活化能为0.44eV。  相似文献   

9.
我们研究了4种负载型Pt催化剂(1Pt/NiO、1Pt/FeOx、1Pt/Co3O4和Pt/CeO2)上不同反应条件下CO氧化活性及抗H2O和CO2性能.发现反应气氛中CO2的加入与CO形成了竞争吸附,并在催化剂表面形成了碳酸盐物种堵塞了活性位,从而导致催化剂失活.反应气氛中H2O的加入对1Pt/CeO2催化剂的活性有所抑制,但对1Pt/FeOx、1Pt/NiO和1Pt/Co3O4催化剂的活性却有促进作用.在1Pt/FeOx和1Pt/CeO2催化剂上的分步反应实验和动力学研究表明,尽管H2O的加入在两种催化剂上均与CO形成了竞争吸附,但在1Pt/FeOx催化剂上H2O在载体表面解离形成的羟基更易与CO反应,开辟了新的反应途径,从而提高了反应性能.此外,H2O的加入能有效分解该催化剂上的碳酸盐物种,从而保持了其稳定性.  相似文献   

10.
(Zn1-xMnx)C2O4·2H2O在空气中的热分解动力学研究   总被引:1,自引:0,他引:1  
用热分析(TG-DTG/DTA)、X射线衍射(XRD)技术和透射电镜(TEM)研究了固态物质Zn1-xMnxC2O4•2H2O在空气中热分解的过程。热分析结果表明,Zn1-xMnxC2O4•2H2O在空气中分两步分解,其失重率与理论计算失重率相吻合。 XRD和TEM结果表明,Zn1-xMnxC2O4•2H2O分解的最终产物为Zn1-xMnxO,其颗粒大小约为10-13 nm。在非等温条件下对Zn1-xMnxC2O4•2H2O的热分解动力学进行了分析。用Friedman法和Flynn-Wall-Ozawa(FWO)法求取了分解过程的活化能E,并用多元线性回归给出了可能的机理函数。Zn1-xMnxC2O4•2H2O两步热分解的活化能分别为155.7513 kJ/mol 和215.9397 kJ/mol。  相似文献   

11.
The reactivity and mobility of the surface and lattice oxygen in a La1-xCaxFeO3-y system prepared via a ceramic route were studied by using CH4-TPR. While the middle-temperature (400-700oC) oxygen lattice mobility reaches maximum for samples with disordered anion vacancies, the high-temperature lattice oxygen flux appears to be controlled by a rapid transfer along disordered domain walls. In the high-temperature range, a high selectivity to syngas of methane oxidation by the lattice oxygen was achieved both for pure lanthanum ferrite and for samples with a microdomain structure. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

12.
Oxygen species and their reactivity in La1 − x Sr x FeO3 − y perovskites prepared using mechanochemical activation were studied by temperature-programmed reduction (TPR) with hydrogen and methane. The experimental data were compared with data on the catalytic activity in oxidation reactions. It was found that the rates of CO and methane oxidation on the perovskites in the presence of gas-phase oxygen correlated (k = 0.8) with the amount of reactive surface oxygen species that were removed by TPR with hydrogen up to 250°C. Maximum amounts of this oxygen species were released from two-phase samples (x = 0.3, 0.4, and 0.8), which exhibited an enhanced activity in the reaction of CO oxidation. In the absence of oxygen in the gas phase, methane is oxidized by lattice oxygen. In this case, the process activity and selectivity depend on the mobility of lattice oxygen, which is determined by the temperature, the degree of substitution, the degree of reduction, and the microstructure of the oxide. Thus, the high mobility of oxygen, which is reached at high concentrations of point defects or interphase/domain boundaries, is of importance for the process of deep oxidation. However, the process of partial oxidation occurs in single-phase samples at low degrees of substitution (x = 0.1–0.2). __________ Translated from Kinetika i Kataliz, Vol. 46, No. 5, 2005, pp. 773–779. Original Russian Text Copyright ? 2005 by Isupova, Yakovleva, Alikina, Rogov, Sadykov.  相似文献   

13.
李强*  赵辉  江瑞  郭力帆 《物理化学学报》2012,28(9):2065-2070
采用甘氨酸-硝酸盐法合成了中温固体氧化物燃料电池阴极材料La1.6Sr0.4Ni1-xCuxO4 (x=0.2, 0.4, 0.6,0.8), 利用X射线衍射(XRD)和扫描电子显微镜(SEM)对其结构和微观形貌进行了表征. 结果表明, 该阴极材料与固体电解质Ce0.9Gd0.1O1.95(CGO)在1000 °C烧结时不发生化学反应, 且烧结4 h 后, 二者之间可形成良好的接触界面. 利用电化学交流阻抗谱技术对阴极材料的电化学性能进行研究, 结果显示, 当Cu离子掺杂量(x)为0.6 时, La1.6Sr0.4Ni0.4Cu0.6O4阴极具有最小的极化电阻, 在空气中当测试温度为750 °C时, 极化电阻为0.35 Ω·cm2. 在不同氧分压条件下电化学阻抗谱分析结果表明, 电极上的两个氧还原反应主要包含氧离子从三相界面向电解质CGO 转移的过程和电荷的迁移过程, 其中电荷的迁移过程为电极反应的速率控制步骤.La1.6Sr0.4Ni0.4Cu0.6O4电极在空气中700 °C和阴极电流密度为45 mA·cm-2时, 阴极过电位为45 mV. 本研究的初步结果表明La1.6Sr0.4Ni1-xCuxO4材料是一种电化学性能较为优良的新型中温固体氧化物燃料电池(IT-SOFC)阴极材料.  相似文献   

14.
The catalytic oxidation of methane and 1,1-dimethylhydrazine ((CH3)2N–NH2, unsymmetrical dimethylhydrazine (UDMH)) with air on oxide catalysts was studied. Two pairs of perovskites (Ca0.7Sr0.3FeO2.5(3.0) and La0.7Sr0.3CoO2.5(3.0), stoichiometric and superstoichiometric with respect to oxygen) and a supported spinel (20%(Cu x Mg1 – x Cr2O4)/-Al2O3, IC-12-73) were used as catalysts. The experiments were performed using two laboratory flow-type systems: in a catalytic fixed-bed reactor (the oxidation ofCH4) and in a gradientless vibrationally fluidized bed reactor (the oxidation of CH4 and UDMH) at 150–700°C. In the oxidation of CH4, the IC-12-73 catalyst was more active than the perovskite catalysts, although particular perovskite catalysts can exhibit higher activity in the region of low temperatures. In the oxidation of UDMH, the activity of perovskites in the test temperature region was lower than that of IC-12-73; this correlates with the higher activity of IC-12-73 in the oxidation of CH4. The Ca0.7Sr0.3FeO3.0 and La0.7Sr0.3CoO2.5(3.0) perovskites exhibited similar activities in the deep oxidation of UDMH, which were higher than the activity of Ca0.7Sr0.3FeO2.5. A comparison between the selectivities of the conversion of fixed nitrogen, which is a constituent of UDMH, into nitrogen oxides demonstrated that, on all of the perovskites, S N NO was higher and was lower than the corresponding values on IC-12-73. Additional information on the possible mechanisms of intermediate formation in the adsorption and oxidation of UDMH on IC-12-73 was obtained using Fourier transform IR spectroscopy.  相似文献   

15.
Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9CO0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane in the absence of gaseous oxygen was investigated by continuous flow reaction and sequential redox reaction, Methane was oxidized to syngas with high selectivity by oxygen species of perovskite oxides in the absence of gaseous oxygen. The sequential redox reaction revealed that the structural stability and continuous oxygen supply in redox reaction decreased over La0.8Sr0.2Fe0.9Co0. 1O3 oxide, while LaFeO3 and La0.8Sr0.2FeO3 exhibited excellent structural stability and continuous oxygen supply.  相似文献   

16.
Oxygen states in the La1 – x Ca x FeO3 – y perovskites prepared using different procedures are studied by temperature-programmed reduction (TPR). Results are compared to data on the catalytic activity in the oxidation of methane and carbon monoxide. The activity of the samples in the CO and CH4 oxidation over a wide temperature range (200–600°C) is shown to correlate with the amount of reactive surface and subsurface oxygen removable during TPR below 420°C. These oxygen states in the samples of the La1 – x Ca x FeO3 – y series can be associated with the domain or intergrain boundaries. No correlation is found between the amount of lattice oxygen removable during TPR and the activity of the La1 – x Ca x FeO3 – y samples in the complete oxidation of methane at temperatures of 450–600°C. It is suggested that catalytic complete oxidation is determined by the most reactive surface and subsurface oxygen states located at the interphase boundaries, whereas the lattice oxygen does not participate in these reactions.  相似文献   

17.
Studies on the role of oxygen vacancy in structural change of nonstoichiometric perovskites and a property of oxygen-deficient perovskite-related K2NiF4 compounds are reviewed.The structural changes on which the authors focused are cation ordering and lattice distortion. The relationship between the distortion and oxygen vacancy was investigated by comparing the structures of Sr2(Sr1-xMx)TaO6-d (M = Ca2+ and Nd3+) solid solutions. It was found that distortion of a perovskite-type lattice decreased with an increasing amount of oxygen vacancies. In order to investigate the relationship between the cation ordering on octahedral sites and oxygen vacancy, structures of stoichiometric Sr2-xLaxCo1-yTa1+yO6 and oxygen-deficient Sr2-xLaxMg1-yTa1+yO6-d solid solutions were compared. The authors' work reveals that the cation ordering affects the amount of oxygen vacancies in addition to cation charge and size.  相似文献   

18.
Summary A series of Pr2-xSrxCoO4+λmixed oxides were prepared and used successfully for oxidation of CO and C3H8. The results show that Pr2-xSrxCoO4+λdisplay K2NiF4-type structure and their catalytic activities are closely correlated with the concentration of Co3+, mobile lattice oxygen and oxygen vacancy.</o:p>  相似文献   

19.
Dense planar and tubular oxygen separation membranes of La0.5Sr0.5FeO3 −  δ were studied in the partial oxidation of methane to syngas process. The oxygen permeation properties were obtained from the analysis of the outlet gas and compared with the data calculated from conductivity measurements. For the planar reactor, the selectivity achieved 95% and the CH4 conversion was 95–99% at 900 °C with pure methane. For the tubular reactor, the CO selectivity and CH4 conversion were 90% and 100%, respectively, under the same conditions. In both cases, the H2/CO ratio was 1.6–1.9. No degradation of membranes was observed after 250 h of operation.  相似文献   

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