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1.
采用溶胶凝胶及冷压方法, 通过在Ca3Co3.9Cu0.1O9体系中引入不同量的Ag+或Yb3+离子来调控体系的热电性能, 制备了可在300~880 K下稳定存在且热电性能优良的陶瓷材料Ca3-xAgxCo3.9Cu0.1O9(x=0.1, 0.15, 0.2, 0.3)和Ca3-yYbyCo3.9Cu0.1O9(y=0.05, 0.1, 0.2, 0.3). 通过X射线衍射(XRD)和扫描电子显微镜(SEM)等测试手段对产物进行了表征, 结果显示所制备的样品纯度较高, 晶粒均匀, 晶粒间较致密. 适量的Ag+, Yb3+离子取代Ca2+离子固溶到晶体中使制备的双掺杂材料晶胞体积发生了变化, 但并未引起晶体对称结构的变化. 电阻率和Seebeck系数的表征结果说明双掺杂优化了载流子的浓度, 随着温度的升高电阻率不断减小, Seebeck系数不断增大. 经过计算可知Seebeck系数的增大还有电子有效质量的贡献. 热导率表征结果显示双掺杂体系的热导率随着温度的升高而减小, 其中声子热导依然起主要作用, 这与单掺杂体系的结果一致. 随着温度的升高, 双掺杂样品Ca2.7Ag0.3Co3.9Cu0.1O9在880 K下ZT值达到最大, 为0.2.  相似文献   

2.
为解决LiNi0.5Co0.2Mn0.3O2正极材料在高温下循环性能差的问题,本文通过固相法对材料进行锆掺杂改性,研究了不同掺杂量对LiNi0.5Co0.2Mn0.3O2晶体结构和电化学性能的影响。研究表明,当锆掺杂量为1% (x)时,可以降低LiNi0.5Co0.2Mn0.3O2结构中的Li+/Ni2+离子混排,有助于材料电化学性能的提高,尤其是高温循环性能。在25 ℃、3.0-4.3 V下, Li(Ni0.5Co0.2Mn0.3)0.99Zr0.01O2在1C循环95次后容量保持率为92.13%,优于未掺杂样品(87.61%)。在55 ℃下, Li(Ni0.5Co0.2Mn0.3)0.99Zr0.01O2在1C循环115次后容量保持率仍有82.96%,远高于未掺杂样品(67.63%)。因此,少量锆掺杂对提升LiNi0.5Co0.2Mn0.3O2的高温循环性能有积极作用。  相似文献   

3.
Since the discovery of superconductivity in Sr2CuO2F2+δ there has been an increased interest in ternary oxide-fluorides. Sr2CuO2F2+δ is prepared via low temperature (T = 220 °C) reaction routes. Low temperature fluorination induces an interesting structural rearrangement in the parent compound Sr2CuO3, which is a one-dimensional material containing linear chains of vertex sharing CuO4 squares along the crystallographic b axis. Upon fluorination, one oxide is substituted by two fluorides and Cu2+ becomes octahedrally coordinated by four oxides and two fluorides. The fluorinated compound Sr2CuO2F2+δ displays the T-type structure (La2CuO4). Insertion of excess fluorine, δ, also takes place and this fluorine occupies interstitial sites in the T structure. Although the starting material Ca2CuO3 is isostructural to Sr2CuO3, Ca2CuO2F2+δ displays the T′ (Nd2CuO4) structure due to the smaller radius of Ca2+ compared to that of Sr2+.

The alkaline-earth palladates with the general formula A2PdO3 (A = Ba, Sr) are isostructural with the A2CuO3(A = Ca, Sr) materials. We prepared the Ba2xSrxPdO3 (x = 0–2) series and performed low temperature fluorination, which led to the synthesis of the series Ba2xSrxPdO2F2+δ (0 ≤ x ≤ 1.5). All the compounds in the Ba2xSrxPdO2F2+δ series show T′ structure (Ca2CuO2F2+δ). Similarities and differences with Sr2CuO2F2+δ and Ca2CuO2F2+δ will be discussed.  相似文献   


4.
This work aims to study the effect of redox property and surface morphology of perovskite oxides on the catalytic activity of CO oxidation and CO+NO reduction, with the redox property being tuned by doping Fe at the Co site of La0.8Sr0.2Co1-xFexO3 and the surface morphology being modified by supporting La0.8Sr0.2CoO3 on various mesoporous silicas(i.e., SBA-16, SBA-15, MCF). Characteristic results show that the Fe doping improves the match of redox potentials, and SBA-16 is the best support of La0.8Sr0.2CoO3 when referring to the oxidation ability(e.g., the Co3+/Co2+ molar ratio). A mechanism for oxygen desorption from perovskite oxides is proposed based on O2-TPD experiments, showing the evolution process of oxygen released from oxygen vacancy and lattice framework. Catalytic tests indicate that La0.8Sr0.2CoO3 is the best for CO oxidation, and La0.8Sr0.2FeO3 is the best for CO+NO reduction. The mechanism of CO+NO reduction changes as the reaction temperature increases, with XNO/XCO value decreases from 2.4 at 250 ℃ to 1.0 at 400 ℃. As for the surface morphology, La0.8Sr0.2CoO3 supported on SBA-16 possesses the highest surface Co3+/Co2+ molar ratio as compared to the other two, and shows the best activity for CO oxidation.  相似文献   

5.
采用共沉淀法制备了高比表面积的MnxCo3−xO4球形催化剂,研究了NH3选择性催化还原NOx性能。Mn-Co金属氧化物具有尖晶石结构,随着Co含量的增加,晶体结构由四方相转变为立方相。高浓度的表面活性氧物种和变价元素的强有效电子转移(Co3+ + Mn3+ ↔ Co2+ + Mn4+)有利于提高MnxCo3−xO4 (x = 1.0、1.5、2.0)尖晶型石催化剂的氧化还原能力,催化剂表面的Mn富集作用形成了氧缺陷结构和丰富的表面活性位点,进一步促进SCR脱硝反应,呈现出优异的催化性能。Cotet(CoMn)octO4晶体结构中,Mn离子(Mn3+和Mn4+,以三价锰为主)和部分Co离子被配置到八面体中心,这些物种作为活性位点存在着较强的电子转移交互作用,该构型对促进低温脱硝活性和保护活性位点耐受SO2毒害具有重要的意义。Mn-Co尖晶石表面的NH3-SCR脱硝反应过程主要遵循Eley-Rideal反应机理,即吸附态NH3与气态NO (或NO2)的反应路径。随着反应温度的增加,反应生成的NH4NO3中间体很可能转化为NH4NO2物种,进而分解为N2,提高了催化剂的氮气选择性。  相似文献   

6.
The oxygen permeation properties of mixed-conducting ceramics SrFeCo0.5O3−δ (SFCO), Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCFO), La0.2Sr0.8Co0.8Fe0.2O3−δ (LSCFO) and Ba0.95Ca0.05Co0.8Fe0.2O3−δ (BCCFO) were studied by thermogravimetric method in the temperature range 600–900 °C. The results show that the oxygen adsorption rate constants ka of all material are larger than oxygen desorption rate constants kd and both ka and kd are not strongly dependent on temperature in the studied temperature range. The oxygen vacancy contents δ(N2) and δ(O2) in nitrogen and oxygen and their difference Δδ = δ(N2) − δ(O2) play an important role in determining the temperature behavior of oxygen permeation flux JO2.  相似文献   

7.
Single-phase Co-doped TiO2(CoxTi1-xO2) nanoparticles(NPs) synthesized via a simple sol-hydrothermal method were used as surface-enhanced Raman scattering(SERS) substrates. Interestingly, it was found that SERS signals were enhanced greatly compared to those of pure TiO2 nanoparticles when an amount of Co2+ ions were doped into the TiO2 lattice. Detailed results clearly show that Co element as Co2+ was incorporated into the TiO2 lattice and the defects were created due to the substitution of Co2+ ions for the Ti4+ ions. The Co2+ doping increases the defect concentration of CoxTi1-xO2 NPs. An amount of defects is beneficial to the charge-transfer so as to increase the SERS activities. A possible mechanism of charge-transfer from CoxTi1-xO2 NPs to molecules was then briefly discussed.  相似文献   

8.
Cai Y  Jiang G  Liu J 《Talanta》2002,57(6):1438-1180
This paper presents a study of the adsorption characteristics of a commercially available GC stationary phase Chromosorb 105 for Co2+, which can be successfully applied to the preconcentration of Co2+ in water samples followed by GFAAS determination. After reacting with 8-hydroxyquinoline to form a complex at pH 8.0, Co2+ in water can be retained on a minicolumn packed with Chromosorb 105 and eluted with 2.5 ml of a mixture of ethanol and 2 mol l−1 HNO3 (2+1, v/v). The recoveries of Co2+ from 200 ml of tap water, river water and bottled natural mineral water samples are quantitative. Conditions for quantitative and reproducible preconcentration, elution and subsequent GFAAS determination were studied. A highly sensitive, simple method for preconcentration and GFAAS determination of trace amount of cobalt in natural water samples using a Chromosorb 105 packed minicolumn has been proposed. The high retention efficiency (95%) for Co2+ provides a sensitivity enhancement of 80 for a 200 ml sample volume with a detection limit of 13.4 ng l−1 (3σ) and a quantification limit of 44.5 ng l−1 (10σ).  相似文献   

9.
在以往的研究工作中,人们经常关注给定基质具有多个格位所对应多发光中心的光致发射。 取决于所掺杂的基质,多个格位的晶体化合物应该可以提供相应的多发光中心,但某些化合物有时只会表现一个发光中心,由此产生“争议性”发光中心。 据以往研究,以稀土离子掺杂而为人所知的经典镁黄长石(Ca2MgSi2O7)长余辉化合物具有“争议性”Ca格位。 为此,在本文中以非稀土离子(Bi3+)特有的发光特性从侧面来研究Ca2MgSi2O7化合物中的“争议性”Ca格位问题。 结果表明,在250和276 nm激发波长激发下,所有的Bi3+掺杂Ca2MgSi2O7样品均有峰位位于582和350 nm的两个Bi3+特征发射带。结合晶体结构分析,光谱结果表明,Ca2MgSi2O7:Bi3+荧光粉具有对应于六配位和八配位的两个不同Ca2+格位的两个Bi3+发光中心,即,Bi3+(Ⅰ)(~582 nm)和Bi3+(Ⅱ)(~350 nm)发光中心。 此外,光谱分析进一步表明,Bi3+(Ⅰ)与Bi3+(Ⅱ)具有单向的能量传递,而且,发现这两个发光中心所对应的相对发射强度是依赖于激发波长和Bi3+掺杂浓度。 实验证明了Ca2MgSi2O7晶体化合物具有两个Ca格位,而不是有些工作中所讨论的一个Ca格位。 本文工作可以为已知或未知的具有“争议性”格位的晶体化合物的验证提供新的借鉴。  相似文献   

10.
The heat capacities of NaNO3 and KNO3 were determined from 350 to 800 K by differential scanning calorimetry. Solid-solid transitions and melting were observed at 550 and 583 K for NaNO3 and 406 and 612 K for KNO3, respectively. The entropies associated with the solid-solid transitions were measured to be (8.43± 0.25) J K−1 mole−1 for NaNO3 and (13.8±0.4) J K−1 mole−1 for KNO3. At 298.15 K the values of C0P S0P, {H0(T)-H0(0)}/T and -{G0(T)-H0(0)}/T, respectively, are 91.94, 116.3, 57.73, and 58.55 J K−1 mole−1 for NaNO3 and 95.39, 133.0, 62.93, and 70.02 J K−1 mole−1 for KNO3. Values for S0T, {H0(T)-H0(0)}/T, and -{G0(T)-H0(0)}/T were calculated and tabulated from 15 to 800 K for NaNO3 and KNO3.  相似文献   

11.
The thermal decomposition of CaOsO3 by differential thermal analyses, thermogravimetry and X-ray powder diffraction has been studied. In nitrogen CaOsO3 decomposes at 880 ± 10°C into CaO, osmium metal and oxygen due to the reaction CaOsO3 → CaO + Os + O2. In static air the decomposition occurs in three stages: 2CaOsO3 + 1/2O2 → Ca2Os2O7 (in region 775–808°C), Ca2Os2O7 → Ca2Os2O6,5 + 1/4O2 (at a temperature interval of 850–1000°C) and in the third stage Ca2Os2O6,5 → 2CaO + OsO4 ÷ 1/4 O2 (at 1005 ± 5°C). The first intermediate Ca2Os2O7 is isostructural with orthorhombic Ca2Nb2O7 and its cell parameters are: a0 = 3.745 Å, b0 = 25.1 Å, c0 = 5.492 Å, Z = 4, space group Cmcm or Cmc2. Ca2Os2O7 exhibits metallic conductivity and its electrical resistivity is 4.6 × 10−2 ohm-cm at 296K.  相似文献   

12.
采用密度泛函理论B3LYP方法计算了吡啶取代的Lindqvist型多酸(POMs)的线性(最大吸收波长, λmax)和非线性光学(NLO)[超瑞利散射(HRS)的第一超极化率, βHRS]性质, 探讨了其作为潜在阳离子检测剂的可能性. 金属离子吸附能计算结果表明, 吡啶取代的Lindqvist型多酸配体与金属离子之间均有较强的相互作用, 相互作用强度大小顺序为Ni2+>Cu2+>Co2+>Fe2+>Zn2+>Mg2+>Ca2+. 电子光谱和βHRS计算结果表明, 引入适当的供、 受电子基团对该多酸配体进行修饰可有效调节线性和二阶NLO性质; 同时, 吡啶取代的Lindqvist型多酸对7种金属离子(Cu2+, Zn2+, Ca2+, Mg2+, Ni2+, Co2+, Fe2+)表现出了不同的检测行为.  相似文献   

13.
A series of modified ferrites were prepared by doping iron oxide with various transition/non-transition/inner-transition metal ions [M = Cr, Mn, Co, Ni, Cu, Zn and Ce] in situ during synthesis. All the modified ferrites thus obtained exhibit remarkably high surface areas, greater than that of pure iron oxide (Fe2O3) sample. The efficacy of the dopant ions in modifying the resultant specific surface area, could be directly related to variations in the rate of crystal growth. The nature and concentration of the foreign cations present in the system govern this variation. Interestingly all the modified ferrites, exhibit a narrow pore size distribution in the range of 4.9–25 nm. XRD analysis revealed the existence of hematite (Fe2O3) phase in all the as-prepared samples. The X-ray diffraction experiments performed on activated catalysts, confirmed the existence of magnetite (Fe3O4) phase with a nominal composition of Fe2.73M0.27O4. These inverse or mixed spinels with general formula A(1−δ)Bδ[AδB(2−δ)]O4, possess highly facile Fe3+  Fe2+ redox couple, the degree of facileness depends on the extent of synergistic interaction between iron and the other substitutent metal ion. The rapid electron hopping between Fe3+  Fe2+ in the Fe3O4 lattice system is essential to catalyze WGS reaction. From TPR it was observed that, incorporation of metal cations into the hematite (-Fe2O3) crystal structure alters the reducibility of the hematite particles, which in turn depends on the nature of the incorporated metal cation. A plausible explanation for the WGS activity over various modified ferrites has been attempted with the help of TPR analysis.  相似文献   

14.
采用无皂乳液聚合法制备聚苯乙烯(PS)微球,通过自组装得到排列均匀有序的聚苯乙烯(PS)胶晶模板,然后经过浸渍和煅烧得到三维有序大孔(3DOM)钙钛矿型氧化物LaFe_(0.7)Co_(0.3)O_3。通过扫描电镜、透射电镜和X射线衍射等手段对制备的3DOM钙钛矿型氧化物LaFe_(0.7)Co_(0.3)O_3的物理化学性能进行表征。在固定床反应器上考察3DOM LaFe_(0.7)Co_(0.3)O_3的甲烷化学链水蒸气重整性能。结果表明,聚苯乙烯(PS)微球粒径受苯乙烯单体使用量的影响,随着苯乙烯单体使用量的增加聚苯乙烯(PS)微球粒径呈增大的趋势;煅烧温度对三维有序大孔结构有显著影响,浸渍后模板在500℃煅烧下即能形成三维有序大孔结构比表面积达到19.820 m2/g,随着煅烧温度的升高三维有序大孔结构遭到部分破坏,在900℃煅烧下三维有序大孔结构遭到完全破坏。在氧载体与甲烷的反应前期,气体产物中CO2含量较高,是表面吸附氧将甲烷完全氧化所致,在表面吸附氧消耗完后体相晶格氧将甲烷部分氧化生成H2与CO。在水蒸气氧化阶段,水蒸气与还原态的氧载体发生反应生成氢气,产氢率为4.0-5.0 mmol/g。同时水蒸气氧化阶段气相产物中CO和CO2含量很低,说明3DOM LaFe_(0.7)Co_(0.3)O_3具有优秀的抗积炭性能。  相似文献   

15.
Shamsipur M  Esmaeili A  Amini MK 《Talanta》1989,36(12):1300-1302
The complexation reactions between murexide and Co2+, Ni2+ and Cu2+ in C2H5OH-H2O mixtures have been investigated spectrophotometrically. The formation constants of the 1:1 complexes formed increase in the order Co2+ < Ni2+ < Cu2+ for all solvent mixtures studied, and log Kf is a linear function of the mole fraction of ethanol. The heat of complexation was determined calorimetrically for the nickel and copper complexes. The values of ΔH° and ΔS° are solvent-dependent, and all three complexes have negative ΔH° and positive ΔS° values.  相似文献   

16.
Cobalt(II) and copper(II) complexes with 1-allyl-2-methylimidazole (L), of general formula [ML2(NO3)2], have been prepared in the solid state. The compounds were characterised by structural, spectroscopic and magnetic measurements. The metal ions in both six coordinate complexes are surrounded by two nitrogen atoms of the imidazole rings and four oxygen atoms of the chelating nitrato group (the CoN2O4 and CuN2O4 chromophores). The structure of both chromophores is described by a very distorted tetragonal bipyramid. The formation of successive complexes of the azole with Co2+, Ni2+, Cu2+, Zn2+ and Cd2+ in aqueous solution was followed potentiometrically. An irregularity in the Kn constants of successive Co2+ and Zn2+ complexes suggests a change in the coordination sphere of the central ions from octahedral to tetrahedral. With the Co2+–1-allyl-2-methylimidazole system, the change has been proven by inspection of the visible absorption spectra.  相似文献   

17.
The praseodymium and europium dichloroacetates were obtained in the form of monocrystals. Crystal structures of the Ln(HCl2CCOO)3·2H2O (Ln=Pr, Eu) compounds were determined by X-ray analysis. Both crystals proved to be isomorphous. They are monoclinic, space group P21/n with: a=9.747(6), b=13.857(7), and c=23.595(9) Å, β=95.03(4)°, U=3175(3) Å3, Z=8 for C6H7Cl6O8Pr and a=9.634(7), b=13.757(11), and c=23.524(14) Å, β=94.84(4)°, U=3107(4) Å3, Z=8 for C6H7Cl6O8Eu. There are two symmetry independent lanthanide cations, which adopt a nine-coordinate geometry with seven oxygen atoms from carboxylate groups and two oxygen atoms from water molecules. Absorption (Pr3+, Eu3+), emission and emission excitation (Eu3+) spectra of single crystals of Ln(HCl2CCOO)3·2H2O were recorded at room temperature and low temperatures down to 4.2 K. Spectral intensities of the investigated systems are parametrized in terms of the Judd–Ofelt theory and compared to those of lanthanide trichloroacetates and acetates crystals. The relationship between the hypersensitivity and covalency is discussed. The nephelauxetic ratio β and Sinha's parameter δ are calculated based on the absorption spectra. The variation of these parameters and their correlation with the nature of metal–ligand bond is discussed. The bond polarity and bond strength of coordination complex determine the activity and stereospecifity of the catalyst thus the study of these properties are very important because of the application of lanthanide carboxylates as precursors of catalysts. The spectroscopic results are correlated with those from the crystal structure studies, especially with Ln–O distances and the co-ordinating forms of the carboxylate ions. The vibronic coupling in the f–f transitions were analysed. In order to determine the vibronic coupling quantitatively, calculations of the R=IVIB./I0-phonon rates were performed from the low temperature absorption spectra. The correlation between the vibronic coupling and covalency is analysed.  相似文献   

18.
Synthesis, structure, spectroscopy and thermal properties of complex [Co(NCS)2(hmt)2(H2O)2][Co(NCS)2(H2O)4] (H2O) (I), assembled by hexamethylenetetramine and octahedral Co(II) metal ions, are reported. Crystal data for I: Fw 387.34, a=9.020(8), b=12.887(9), c=7.95(1) Å, =96.73(4), β=115.36(5), γ=94.16(4)°, V=820(1) Å3, Z=2, space group=P−1, T=173 K, λ(Mo-K)=0.71070 Å, ρcalc=1.718567 g cm−3, μ=17.44 cm−1, R=0.088, Rw=0.148. An interesting two-dimensional network is assembled via hydrogen bonds through coordinated and free water molecules. The d–d transition energy levels of Co(II) ion are determined by UV–vis spectroscopy and calculated by ligand field theory. The calculated results agree well with experiment ones.  相似文献   

19.
Peroxymonosulfate(PMS) has received increasing attention as viable technology for recalcitrant organics removal from polluted waters. Although promising, alternative heterogeneous catalysts with stable structure, strong hydrophilicity, environmental friendliness and excellent catalytic performance are highly desirable to facilitate the wide industrialization of PMS. In this work, Ni doped CoOOH catalyst was employed as PMS activator. Ni dopant had a significant influence on the morphology, structure and catalytic performance of CoOOH. NiojCoo.gOOH exhibited the best catalytic performance. Reaction rate ofNio.2Coo.8OOH was 2, 4, and 4.4 times that of CoOOH, CoFe2O4 and CO3O4, respectively. Moreover, Ni。2C00.8OOH/PMS system had potential application to organic pollutants and displayed a great catalytic activity over a broader pH value(e.g., 4-10). More importantly, Ni doping accelerated the transfonnation of Co(Ⅲ) and Co(Ⅱ) and formed active species CoOH^+ and NiOH^+ which were responsible to the enhancement of PMS activation.OH, SO4^-:O2^- and 1^O2 were detected, indicating both non-radical and radical processes in the Nio.2Coo.8OOH/PMS system. These findings provide a promising alternative to mixed-metal oxyhydroxides catalysts for PMS activation, demonstrating a great potential in environmental remediation and wastewater treatment.  相似文献   

20.
A 1D supramolecular compound [dmbbbi](1) and a 2D cobalt coordination polymer [Co(dmbbbi)(ox)]2(2) [dmbbbi=1,1-(1,4-butanediyl)bis(5,6-dimethylbenzimidazole), ox=oxalate], C48H52Co2N8O8, were obtained under hydrothermal conditions by tuning the molar ratio of the reactants. The crystal structure analysis reveals that in compound 1, the adjacent dmbbbi molecules connect with each other via hydrogen bonds to form a 1D supramolecular chain. In compound 2, two crystallographically independent Co2+ ions show the same six-coordination mode. Each Co2+ ion is coordinated by four oxygen atoms from two ox anions and two nitrogen atoms from two cis-dmbbbi ligands. The adjacent Co2+ ions are bridged by ox anions to generate an infinite 1D zigzag chain, which is extended by pairs of dmbbbi ligands to form a 2D honeycomb-like (6,3) network. Moreover, the thermal stability and the electrochemical property of compound 2 were studied.  相似文献   

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