Magnetic specific heat and spin-glass-like ordering in the pyrochlores: RE2Mo2O7 (RE=Y,Sm, Gd,Ho)

The pyrochlores RE₂Mo₂O₇ (RE=Y, Sm, Gd, Ho) display, with the exception of Ho₂Mo₂O₇, magnetic transitions at 18 K, 68 K, 55 K, respectively. No long-range order occurs. The rare-earth atoms remain in the paramagnetic state down to 1.5 K. The magnetic specific heat behaviour is explained by spin-glass-like ordering of Mo⁴⁺ ions, imposing a molecular field of random character on the rare-earth ions, and by crystalline field-splitting effects.     

La0.8Sr0.2Ga0.8Mg0.2O3－α陶瓷的质子导电性能研究

采用溶胶-凝胶法合成了La_0.8Sr_0.2Ga_0.8Mg_0.2O_3－a陶瓷样品, 用XRD, DSC-TGA, SEM, 交流阻抗谱, 气体浓差电池及气体电化学透过等方法对样品的结构和性质进行了表征和测试. 首次对该样品的质子导电性能进行了研究. 该陶瓷样品具有良好的微观结构, 相对密度达95.1%; 氢浓差电池电动势的实测值与理论值吻合, 离子迁移数为1; 在干燥的氧气气氛中是一个纯的氧离子导体; 氢的电化学透过速率的实测值与理论值吻合, 证明该样品在氢气气氛中几乎是一个纯的质子导体, 质子电导率在1000 ℃时高达0.14 S•cm^－1.     

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen cartier 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 re-action decreased over La0.8Sr0.2Fe0.9Co0.1O3 oxide, while LaFeO3 and Lao.sSro.2FeO3 exhibited excellent structural stability and continuous oxygen supply.     

Comparison of LaFeO3, La0.8Sr0.2FeO3, and La0.8Sr0.2Fe0.9Co0.1O3 perovskite oxides as oxygen carrier for partial oxidation of methane

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.     

质子导体(Ce0.8La0.2)1－xCaxO2－δ 在合成氨中的应用

利用溶胶-凝胶法合成了萤石型稀土复合氧化物(Ce_0.8La_0.2)_1－xCa_xO_2－δ, 利用XRD、TEM和SEM对样品进行表征. 电化学方法研究表明, 合成样品在400～800 ℃温度范围内具有质子导电特性. 将(Ce_0.8La_0.2)_1－xCa_xO>_2－δ高温烧结体用于固态质子传导电池, 在常压下以氮气和氢气为原料合成氨气, 并确定了合成氨的适宜条件. 650 ℃时Ce_0.8La_0.2O_2－δ和(Ce_0.8La_0.2)_0.975Ca_0.025O_2－δ对应的氨产率分别达7.2×10^－9和7.5×10^－9 mol•s^－9•cm^－9.     

La0.8Sr0.2-xCaxCo0.9Fe0.1O3-δ的合成与电性能

利用X射线衍射 (XRD)、差热 热重 (DSC/TG)与直流四探针测试分析方法研究了少量Ca取代LaCoO3 中部分La的合成过程及对其电导率的作用。采用固相反应合成的La0 .8Sr0 .2 -xCaxCo0 .9Fe0 .1 O3 -δ(LSCCF ,0≤x≤ 0 1)氧化物为单一钙钛矿相 ,其烧结过程可以分为 3个阶段 :即反应原料的变化 ;LaCoO3 基氧化物的生成 ;LSCCF固溶体的形成。LSCCF复合掺杂材料电导率的最大值都超过了 10 0S·cm- 1 ,其导电机制可以用p型小极子的绝热空隙理论来解释     

低温燃烧合成Ce0.8Y0.2O1.9固溶体及烧结性能的研究

以硝酸盐做氧化剂,柠檬酸为燃料,采用低温燃烧法制备纳米级超细Ce0.8Y0.2O1.9 (YDC)固溶体.利用TG-DSC,XRD,SEM,FT-IR和BET等手段对凝胶前驱体的热分解行为、相转化过程和YDC粉体的性能进行表征.TG-DSC结果表明,柠檬酸-硝酸盐干凝胶的点火温度约为263.3℃;经XRD测试,粉体经600℃焙烧即形成了单相立方萤石型结构的固溶体,晶粒度为16 ～23nm.柠檬酸与硝酸盐摩尔比(CA/N)对粉体的微观形貌、比表面积和烧结活性有显著影响.当CA/N为1.5∶1时,粉体粒子间仅有微弱的软团聚,将素坯在1400℃烧结2h,得到相对密度为95.6％,平均粒径约为0.7 μm的陶瓷烧结体.     

有机燃料对合成大比表面积La0．8Sr0．2CoO3性能的影响

采用溶液燃烧合成法(solution com bustion synthesis,简称SCS)制备了La0.8Sr0.2CoO3钙钛矿复合氧化物,考察了丙氨酸、氨基乙酸和丙三醇等有机燃料对催化剂结构和CH4催化燃烧活性的影响,并运用XRD、FI-TR、BET、TPR等技术进行了表征。结果表明,不同有机燃料所制La0.8Sr0.2CoO3复合氧化物均具有较大比表面积,有机燃料对催化剂的结构和性能有较大的影响,其中以丙氨酸有机燃料制备的复合氧化物活性最好,其T50和T100分别为470℃和550℃。该法所制La0.8Sr0.2CoO3复合氧化物的平均晶粒度较小,比表面积和晶格畸变率较大,表面和氧空穴处的化学吸附氧较易移动,表观活化能较低。     

钙钛矿型La0.8Sr0.2FeO3中的晶格氧用于甲烷选择氧化制取合成气

 用自燃烧法制备了钙钛矿型La0．8Sr0．2FeO3催化剂．用H2－TPR考察了催化剂表面的氧消耗过程，用程序升温表面反应（TPSR）研究了甲烷与催化剂表面氧物种的反应，用在线质谱脉冲反应和甲烷／氧切换反应研究了催化剂的晶格氧选择氧化甲烷制合成气．结果表明，催化剂上存在两种氧物种，无气相氧存在时，强氧化性氧物种首先将甲烷氧化为CO2和H2O；而后提供的氧化性较弱的晶格氧具有良好的甲烷部分氧化选择性，可将甲烷氧化为合成气CO和H2（选择性可达95％以上）．在900℃下的CH4／O2切换反应结果表明，甲烷能与La0．8Sr0．2FeO3中的晶格氧反应选择性地生成CO和H2，失去晶格氧的La0．8－Sr0．2FeO3能与气相氧反应恢复其晶格氧．在合适的反应条件下，用La0．8Sr0．2FeO3催化剂的晶格氧代替分子氧按Redox模式实现甲烷选择氧化制合成气是可能的．     

锂离子蓄电池正极材料LiNi0.8 Co0.2 O2的制备及其电化学性能

用高温固相反应和氧化还原溶胶凝胶法制备了锂离子电池正极材料LiNi0.8Co0.2O2,并对其进行了电化学性能考察。结果显示,氧化还原溶胶凝胶法制备的锂离子电池正极材料的综合性能较高温固相法好。     

NdSr_（1－x）M_xNiO_4（M＝Ca，Ba）的合成，结构和电学磁学性

用固相法首次合成了ＮｄＳｒ＿（１－ｘ）Ｍ＿ｘＮｉＯ＿４（Ｍ＝Ｃａ：０．０≤１．０；Ｍ＝Ｂａ：０．０≤ｘ≤０．６）系列复合氧化物，并研究了其结构，红外光谱，电学性质和磁学性质。除ＮｄＣａＮｉＯ以正交晶系结晶外，其它试样的结构均属于四方晶系。ＩＲ谱显示随Ｃａ￣（２＋）离子含量的增加，ＮｄＳｒ＿（１－ｘ）Ｍ＿ｘＮｉＯ＿４的Ｎｉ－Ｏ键缩短，Ｃａ￣（２＋）和Ｂａ￣（２＋）引入ＮｄＳｒＮｉＯ＿４以取代Ｓｒ￣（２＋），使试样由金属性导电转变为半导体性导电；随Ｃａ￣（２＋）含量增加，试样的室温电阻率增大。７７～３００Ｋ磁化率与温度关系曲线显示，所有试样的Ｎｉ￣（３＋）都以低自旋状态存在。     

Osmium-Nitridtrichlorid,OsNCl3

Osmium Nitridotrichloride, OsNCl₃ OsNCl₃ was prepared by the reaction of (NH₄)₂[OsNCl₅] with chlorine at 300°C, forming a black, X-ray amorphous moisture sensitive, paramagnetic powder which was characterized by IR spectroscopy and measurement of the magnetic susceptibility in the range of 5–300 K.     

Novel Conductive Radical Cation Salts Based on Methylenediselenotetraselenafulvalene (MDSe-TSF): A Sign of Superconductivity in κ-(MDSe-TSF)2Br Below 4 K

Seven conductive radical cation salts based on MDSe-TSF (methylenediselenotetraselenafulvalene) have been synthesized by electrocrystallization in the presence of Cl⁻, Br⁻, I₃⁻, I₂Br⁻, PF₆⁻, ClO₄⁻, and Cu(NCS)₂⁻ counter anions. The crystal appearances of these salts fairly depend on the anions employed. X-ray crystallographic analyses have revealed that the PF₆ and ClO₄ salts in the shape of brown thin plates adopt the θ-type structures characterized by the herringbone arrangement of donor stacks, whereas the Cl and Br salts in the shape of black thick plates favor the κ-type structures with the orthogonal arrangement of donor dimers. Regardless of different crystal appearances or crystal packing patterns, all these salts show high conductivity (>10² S cm⁻¹) at room temperature and retain metallic properties down to 4.2 K. Of them, the Br salt shows a weak but distinct diamagnetic shielding signal below 4 K in the dc magnetization measurement under zero-field-cooled (ZFC) condition, suggesting a sign of superconductivity. The band calculations of both PF₆ and Br salts demonstrate closed Fermi surfaces indicative of two-dimensional molecular conductors.     

Contrasting Magnetic Behaviors in Rhodium‐ and Ruthenium‐Doped Cubic Perovskite SrFeO3: Nearly Ferromagnetic Metal versus Spin‐Glass Insulator

The effects of Rh and Ru doping for SrFeO₃, a helimagnetic metal with a cubic perovskite structure, are studied by magnetic and resistivity measurements. Although SrRhO₃ is a paramagnetic metal and SrRuO₃ is a ferromagnetic one, the Rh doping induces a nearly ferromagnetic metallic state, whereas the Ru doping induces a spin‐glass insulating state. Mössbauer measurements evidence a marked difference between SrFe_0.8Rh_0.2O₃ and SrFe_0.8Ru_0.2O₃ in the formal valences of Fe, which are estimated to be 4+ and 3.75+, respectively. The contrasting magnetic behaviors of Rh‐ and Ru‐doped SrFeO₃ are discussed in terms of the subtle balance between the double‐exchange ferromagnetism and the superexchange antiferromagnetism.     

High dilution of anionic vacancies in Sr(0.8)Ba(0.2)Fe(O,F)(~2.5)

The (Ba,Sr)FeO(3-δ) system is known for its strong tendency for oxygen and vacancies to order into several forms including fully ordered pseudobrownmillerites, hexagonal perovskites with segregation of the vacancies in particular anionic layers and low deficient (pseudo)cubic compounds (generally δ < 0.27, Fe(3/4+)). We show for the first time, using a simple chemical process, the easy access to a large amount of vacancies (δ ≈ 0.5, Fe(3+)) within the room-temperature stable tetragonal (pseudocubic) Sr(0.8)Ba(0.2)FeF(~0.1)(O,F)(~2.5.) The drastic effect of the incorporation of a minor amount of fluoride passes through the repartition of local O/F/□ constraints shifting the tolerance factor into the pseudocubic range for highly deficient compounds. It is stable up to 670 K, where an irreversible reoxidation process occurs, leading to the cubic-form. The comparison with the cubic oxide Sr(0.8)Ba(0.2)FeO(~2.7) shows the increase of the resistivity (3D-VRH model) by two decades due to the almost single valent Fe(3+) of the oxofluoride. In addition, the G-type magnetic ordering shows relatively weak moment for Fe(3+) cations (M(Fe) ≈ 2.64(1) μB at room temperature) attributed to incoherent magnetic components expected from local disorder in such anionic-deficient compounds.     

Ionic Conduction in Ba0.95Ce0.8Ho0.2O3-α

Ba0.95Ce0.8Ho0.2O3-a was prepared by high temperature solid-state reaction. X-ray diffraction （XRD） pattern showed that the material was of a single perovskite-type orthorhombic phase. Using the material as solid electrolyte and porous platinum as electrodes, the measurements of ionic transport number and conductivity of Ba0.95Ce0.8Ho0.2O3-a were performed by gas concentration cell and ac impedance spectroscopy methods in the temperature range of 600---1000 ℃in wet hydrogen, dry and wet air respectively. Ionic conduction of the material was investigated and compared with that of BaCe0.8Ho0.2O3-a. The results indicated that Ba0.95Ce0.8Ho0.2O3-a was a pure protonic conductor with the protonic transport number of 1 during 600---700℃ in wet hydrogen, a mixed conductor of protons and electrons with the protonic transport number of 0.97--0.93 in 800---1000 ℃. But BaCe0.8Ho0.2O3-a was almost a pure protonic conductor with the protonic transport number of 1 in 600---900 ℃ and 0.99 at 1000 ℃ in wet hydrogen. In dry air and in the temperature range of 600---1000 ℃, they were both mixed conductors of oxide ions and electronic holes, and the oxide-ionic transport numbers were 0.24--0.33 and 0.17--0.30 respectively. In wet air and in the temperature range of 600---1000 ℃, they were both mixed conductors of protons, oxide ions and electronic holes, the protonic transport numbers were 0.11--0.00 and 0.09--0.01 respectively, and the oxide-ionic transport numbers were 0.41--0.33 and 0.27--0.30 respectively. Protonic conductivity of Ba0.95Ce0.8Ho0.2O3-a in both wet hydrogen and wet air was higher than that of BaCe0.8Ho0.2O3-a in 600--- 800 ℃, but lower in 900--1000 ℃. Oxide-ionic conductivity of the material was higher than that of BaCe0.8Ho0.2O3-a in both dry air and wet air in 600---1000 ℃.     

Hydrothermal Synthesis and Spectroscopic and Magnetic Behavior of the Mn7(HOXO3)4(XO4)2(X=As, P) Compounds. Crystal Structure of Mn7(HOAsO3)4(AsO4)2

The Mn₇(HOXO₃)₄(XO₄)₂ (X=As, P) compounds have been synthesized by using hydrothermal conditions. The arsenate phase was obtained under autogeneous pressure at 170°C. However, more drastic conditions at both pressure and temperature were necessary in the attainment of the phosphate compound. The crystal structure of Mn₇(HOAsO₃)₄(AsO₄)₂ was solved using single-crystal data. The unit-cell parameters are a=6.810(3) Å, b=8.239(2) Å, c=10.011(4) Å, α=104.31(2)°, β=108.94(3)°, γ=101.25(2)°. Triclinic, P-1 with Z=1. The isostructural Mn₇(HOPO₃)₄(PO₄)₂ phase was characterized from X-ray powder diffraction techniques. The crystal structure of both compounds consists of zig-zag chains constructed by dimeric edge-sharing Mn₂O₁₀ octahedra linked through the MnO₅ trigonal bipyramids. The three-dimensional framework is completed by the connection between isolated MnO₆ entities to the dimers octahedra and trigonal bipyramids. The existence of hydrogenarsenate and hydrogenphosphate anions has been confirmed by IR and Raman spectroscopies. Magnetic measurements indicate the existence of antiferromagnetic interactions in both compounds, which are slightly stronger in the arsenate phase.     

Defect structure and ionic conductivity in Bi3Nb0.8W0.2O7.1

Defect structure and conductivity behavior are discussed in the oxide ion conductor Bi₃Nb_0.8W_0.2O_7.1. Investigations were carried out using a combination of AC impedance spectroscopy and powder X-ray and neutron diffraction. Bi₃Nb_0.8W_0.2O_7.1 shows a defect fluorite type structure with evidence for superlattice ordering in the oxide ion sublattice. A detailed analysis of the diffraction results allow for proposed models for the defect structure and suggest vacancy trapping in the six coordinate environment of Nb⁵⁺/W⁶⁺ cations. The influence of the defect structure on ionic conductivity is discussed.     

XANES Study on the Generation and Distribution of Holes via Ca Substitution and O Doping in Cu(Ba0.8Sr0.2)2(Yb1−xCax)Cu2O6+z

Generation of holes is facilitated in the Cu(Ba_0.8Sr_0.2)₂ (Yb_1−xCa_x)Cu₂O_6+z (Cu-1212) system by two independent ways, i.e., by Ca substitution (0≤x≤0.35) and O doping (0<z<1). The distribution of holes between the CuO₂-(Yb_1−xCa_x)-CuO₂ block containing two identical superconductive CuO₂ planes and the “charge-reservoir” block consisting of a single CuO_z chain has been quantitatively investigated by means of O K-edge and Cu L_2,3-edge X-ray absorption near-edge structure (XANES) spectroscopy. The resultant values for the CuO₂-plane hole concentration are compared with those calculated employing the bond-valence-sum (BVS) method from the neutron powder diffraction (NPD) data previously reported for the same samples. The results of the two methods are in good agreement. The two independent hole-doping ways are found to result in different distributions of holes over the crystal, i.e., different ratios of hole numbers at the CuO₂ plane and the CuO_z chain. With Ca substitution holes are directed efficiently into the CuO₂ plane, while for O doping holes are more homogeneously distributed between the CuO₂ plane and the CuO_z chain. Moreover, the value of T_c at a fixed CuO₂-plane hole concentration is shown to be higher for Ca-substituted than for O-doped samples.