The effect of element substitution on high-temperature thermoelectric properties of Ca3Co2O6 compounds

Polycrystalline Ca₃Co_1.8M_0.2O₆ (M=Mn, Fe, Co, Ni, Cu) and Ca_2.7Na_0.3Co₂O₆ were synthesized by solid-state reaction to evaluate the effect of substitution on the thermoelectric properties of Ca₃Co₂O₆. Substitution by Mn, Cu and Na appears to increase carrier density, given that electrical resistivity (ρ) and the Seebeck coefficient (S) were simultaneously reduced. Conversely, Fe substitution seems to reduce carrier density, resulting in a simultaneous increase in S and ρ. Cu and Na substitution resulted in a significant decrease in ρ due to enhancement of grain size and grain boundary connectivity, which could have a strong impact on ρ. Not only the intrinsic substitution effect on the electronic state but also this modification of the microstructure plays an important role in improvement of the thermoelectric power factor, particularly in the case of the Na-substituted sample.     

Facile synthesis of Co3O4 and Ag/Co3O4 nanosheets and their electrocatalytic properties

The precursors of Co₃O₄ and Ag/Co₃O₄ composites with different Ag contents were synthesized with assistance of (NH₄)₂CO₃ via a facile hydrothermal process. The final samples were fabricated by calcining each precursor at 400 °C according to TG experiment. The as-prepared samples were identified and characterized by thermogravimetric analysis, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and field emission scanning electron microscopy, respectively. The results showed that the morphology of Co₃O₄ and Ag/Co₃O₄ composites were sheet-like. Ag nanoparticles were dispersed well in the nanosheets. The samples were used as electrocatalysts modified directly on a glassy carbon electrode for p-nitrophenol reduction in a basic solution. The results showed that p-nitrophenol could be reduced at a large peak current but a higher peak potential with Co₃O₄, at lower potentials with Ag/Co₃O₄ composites. Ag/Co₃O₄ composite with 3 % Ag showed more efficiently electrocatalytic activity than other composites. The present method suggested the potential application of Ag/Co₃O₄ composites in electrocatalysis.     

Enhancement of thermoelectric performance of Na<Subscript>x</Subscript>Co<Subscript>2</Subscript>O<Subscript>4</Subscript> with Ag dispersion by precipitation from Ag<Superscript>+</Superscript> aqueous solution

Thermoelectric Na_xCo₂O₄/Ag composites were synthesized by citric acid complex (CAC) method and Ag precipitation from CH₃COOAg aqueous solution on the Na_xCo₂O₄ powders. Effects of the synthesis process on microstructure and thermoelectric performance of Na_xCo₂O₄/Ag composites were investigated. When the Na_xCo₂O₄ CAC powders were dipped in CH₃COOAg aqueous solution and dried, fine Ag particles less than around 300 nm in size were precipitated on the surface of Na_xCo₂O₄ powders. After the subsequent sintering process, the flaky Ag phase, the length and thickness of which were up to 5 and 1 μm, respectively, existed along interfaces between Na_xCo₂O₄ grains. The sizes of Ag particles obtained in this study were found to be smaller than those of the conventionally prepared Na_xCo₂O₄/Ag composites. The fine dispersion of Ag grains was effective for suppressing the increase in thermal conductivity due to the addition of metallic phase, Ag, and for improving the thermoelectric performance of Na_xCo₂O₄/Ag composites, suggesting that the synthesis technique composed of the CAC method and Ag precipitation from CH₃COOAg aqueous solution is significantly important process for thermoelectric Na_xCo₂O₄/Ag composites.     

Synthesis of Hexagonal Co3O4 and Ag/Co3O4 Composite Nanosheets and their Electrocatalytic Performances

Sheet-like precursors of Co₃O₄ and Ag/Co₃O₄ composites with different Ag contents were synthesized with assistance of triethylamine via a hydrothermal process. The final samples were fabricated by calcing each precursor at 400 °C. The as-prepared samples were identified and characterized by thermogravimetric analysis and differential thermal analysis, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, and field emission scanning electron microscopy, respectively. The Co₃O₄ and Ag/Co₃O₄ composite samples were used as electrocatalysts modified on a glassy carbon electrode for p-nitrophenol reduction in a basic solution. The electrocatalytic results indicated that all the samples showed enhanced electrocatalytic performance for p-nitrophenol by comparing a bare glass carbon electrode, and p-nitrophenol could be reduced by Co₃O₄ at a high peak current but a rather higher peak potential but be reduced effectively by Ag/Co₃O₄ composites at lower potential. Ag/Co₃O₄ composites with 4 % Ag displayed the highest electrocatalytic activity.     

Phase diagram of SrO-InO1.5-CoOx and a new compound Sr3In0.9Co1.1O6

Sr₃In_0.9Co_1.1O₆, isostructural to Ca₃Co₂O₆, is revealed by the study of the phase relations in the system SrO-InO_1.5-CoO_x (1000 °C). The structure of Sr₃In_0.9Co_1.1O₆ is refined by the combination of powder X-ray and neutron diffraction. Sr₃In_0.9Co_1.1O₆ crystallizes in a trigonal lattice with the cell parameters a=b=9.59438(3) Å, c=11.02172(4) Å with the space group R-3c. Its structure possesses 1D (In/Co)O₃ chains running along the c-axis constructed by alternating face-sharing CoO₆ octahedra and (In_0.9Co_0.1)O₆ trigonal prisms. The co-occupation of In³⁺ and Co³⁺ at the trigonal prismatic site is evidenced by elementary analysis and determined by the structure refinement. Sr₃In_0.9Co_1.1O₆ is paramagnetic, and the susceptibility is consistent with the occupation of Co³⁺ at 10% of the trigonal prismatic positions in a high spin state (HS, S=2). The HS Co³⁺ is well separated by diamagnetic CoO₆ octahedra and InO₆ trigonal prisms and shows a g factor of 2.0 in the magnetic measurements.     

片状Co9S8/ZnS/C复合材料的制备及电催化产氧性能

以六水合硝酸钴[Co(NO_3)_2·6H_2O]为钴源、六水合硝酸锌[Zn(NO_3)_2·6H_2O]为锌源、2,2′-硫代二乙酸(C4H6O4S)为硫源,采用溶剂热法制备出了片状的Co_9S_8/ZnS/C复合材料。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)和N_2吸附/脱附测试等手段对于片状Co_9S_8/ZnS/C复合材料结构和形貌等进行表征,同时对片状Co_9S_8/ZnS/C复合材料进行了电催化产氧性能测试。结果表明:片状Co_9S_8/ZnS/C复合材料的起始过电位为390 mV,塔菲尔斜率为144 mV·dec~(-1),具有高的电催化产氧性能。     

Phase diagram, crystal chemistry and thermoelectric properties of compounds in the Ca-Co-Zn-O system

In the Ca-Co-Zn-O system, we have determined the tie-line relationships and the thermoelectric properties, solid solution limits, and structures of two low-dimensional cobaltite series, Ca₃(Co, Zn)₄O_9−z and Ca₃(Co,Zn)₂O_6−z at 885 °C in air. In Ca₃(Co,Zn)₄O_9−z, which has a misfit layered structure, Zn was found to substitute in the Co site to a limit of Ca₃(Co_3.8Zn_0.2)O_9−z. The compound Ca₃(Co,Zn)₂O_6−z (n=1 member of the homologous series, Ca_n+2(Co,Z_n)_n(Co,Zn)′O_3n+3−z) consists of one-dimensional parallel (Co,Zn)₂O₆⁶⁻ chains that are built from successive alternating face-sharing (Co,Zn)O₆ trigonal prisms and ‘n’ units of (Co,Zn)O₆ octahedra along the hexagonal c-axis. Zn substitutes in the Co site of Ca₃Co₂O₆ to a small amount of approximately Ca₃(Co_1.95Zn_0.05)O_6−z. In the ZnO-CoO_z system, Zn substitutes in the tetrahedral Co site of Co₃O₄ to the maximum amount of (Co_2.49Zn_0.51)O_4−z and Co substitutes in the Zn site of ZnO to (Zn_0.94Co_0.06)O. The crystal structures of (Co_2.7Zn_0.3)O_4−z, (Zn_0.94Co_0.06)O, and Ca₃(Co_1.95 Zn_0.05)O_6−z are described. Despite the Ca₃(Co, Zn)₂O_6−z series having reasonably high Seebeck coefficients and relatively low thermal conductivity, the electrical resistivity values of its members are too high to achieve high figure of merit, ZT.     

Crystal growth, structural characterization and magnetic properties of Ca3CuRhO6, Ca3Co1.34Rh0.66O6 and Ca3FeRhO6

Single crystals of Ca₃CuRhO₆, Ca₃Co_1.34Rh_0.66O₆ and Ca₃FeRhO₆ were synthesized by high temperature flux growth in molten K₂CO₃ and structurally characterized by single crystal X-ray diffraction. While Ca₃Co_1.34Rh_0.66O₆ and Ca₃FeRhO₆ crystallize with trigonal (rhombohedral) symmetry in the space group , Z=6: Ca₃Co_1.34Rh_0.66O₆a=9.161(1) Å, c=10.601(2) Å; Ca₃FeRhO₆a=9.1884(3) Å, c=10.7750(4) Å; Ca₃CuRhO₆ adopts a monoclinic distortion of the K₄CdCl₆ structure in the space group C2/c, Z=4: a=9.004(2) Å, b=9.218(2) Å, c=6.453(1) Å, β=91.672(5). All crystals of Ca₃CuRhO₆ examined were twinned by pseudo-merohedry. Ca₃CuRhO₆, Ca₃Co_1.34Rh_0.66O₆, and Ca₃FeRhO₆ are structurally related and contain infinite one-dimensional chains of alternating face-sharing RhO₆ octahedra and MO₆ trigonal prisms. In the monoclinic modification, the copper atoms are displaced from the center of the trigonal prism toward one of the rectangular faces adopting a pseudo-square planar configuration. The magnetic properties of Ca₃CuRhO₆, Ca₃Co_1.34Rh_0.66O₆, and Ca₃FeRhO₆ are discussed.     

Crystal structure and magnetic properties of the solid-solution phase Ca3Co2−vScvO6

The two crystallographically non-equivalent Co atoms of the quasi-one-dimensional crystal structure of Ca₃Co₂O₆ form chains with alternating, face-sharing polyhedra of Co2O₆ trigonal prisms and Co1O₆ octahedra. This compound forms a substitutional solid-solution phase with Sc, in which the Sc atoms enter the Co2 sublattice exclusively. The homogeneity range of Ca₃Co_2−vSc_vO₆ (more specifically Ca₃Co1Co2_1−vSc_vO₆) extends up to v≈0.55. The crystal structure belongs to space group R3¯c with lattice parameters (in hexagonal setting): 9.0846(3)?a?9.1300(2) Å and 10.3885(4)?c?10.4677(4) Å. The magnetic moment decreases rapidly with increasing amount of the non-magnetic Sc solute in the lattice.     

Structure and properties of the CaFe2O4-type cobalt oxide CaCo2O4

The calcium cobalt oxide CaCo₂O₄ was synthesized for the first time and characterized from a powder X-ray diffraction study, measuring magnetic susceptibility, specific heat, electrical resistivity, and thermoelectric power. CaCo₂O₄ crystallizes in the CaFe₂O₄ (calcium ferrite)-type structure, consisting of an edge- and corner-shared CoO₆ octahedral network. The structure of CaCo₂O₄ belongs to an orthorhombic system (space group: Pnma) with lattice parameters, a=8.789(2) Å, b=2.9006(7) Å and c=10.282(3) Å. Curie-Weiss-like behavior in magnetic susceptibility with the nearly trivalent cobalt low-spin state (Co³⁺, 3d, S=0), semiconductor-like temperature dependence of resistivity (ρ=3×10⁻¹ Ω cm at 380 K) with dominant hopping conduction at low temperature, metallic-temperature-dependent large thermoelectric power (Seebeck coefficient: S=+147 μV/K at 380 K), and Schottky-type specific heat with a small Sommerfeld constant (γ=4.48(7) mJ/Co mol K²), were observed. These results suggest that the compound possesses a metallic electronic state with a small density of states at the Fermi level. The doped holes are localized at low temperatures due to disorder in the crystal. The carriers probably originate from slight off-stoichiometry of the phase. It was also found that S tends to increase even more beyond 380 K. The large S is possibly attributed to residual spin entropy and orbital degeneracy coupled with charges by strong electron correlation in the cobalt oxides.     

Improvement on Electrical Properties and Magnetoresistance Induced by Pd or Ag Addition in La0.67(Ca0.65Ba0.35)0.33MnO3 Manganites

Electrical properties and magnetoresistance have been studied in two series of xAg-La_0.67(Ca_0.65Ba_0.35)_0.33MnO₃ and xPd-La_0.67(Ca_0.65Ba_0.35)_0.33MnO₃ (abbreviated by xAg-LCBMO and xPd-LCBMO) composites. Both Pd and Ag addition induce a decrease in resistivity and an increase in temperature at which the resistivity reaches its maximum. This is mainly due to the improvement of grain boundaries caused by the segregation of good conductive metal grains on the grain boundaries/surfaces. In addition, both Pd and Ag addition induce a large enhancement of room temperature magnetoresistance (RTMR). Note that 27% molar ratio of Ag addition induces a large RTMR of about 70%, about ten times larger than pure LCBMO, whereas 27% molar ratio Pd addition brings a much larger RTMR of about 170%. The large enhancements of MR can be attributed to the decrease in resistivity of the samples caused by the good conductive metal. On the other hand, the polarization of Pd atoms near the Mn ions on the grain surfaces/boundaries plays a very im-portant role in the increase in MR, which induces a large number of spin clusters in Pd-added samples.     

The disordered cubic structure of Ca7Co3Ga5O18

The new mixed oxide having composition close to Ca₇Co₃Ga₅O₁₈ was synthesized from CaCO₃, Co₃O₄ and Ga₂O₃ at 1150 °C in air and studied by neutron and synchrotron X-ray powder diffraction, selected-area electron diffraction and high-resolution electron microscopy. The structure was refined, using time-of-flight (TOF) neutron powder diffraction data, in space group F432, with and Z=8, to R_F=0.7%. It is considerably disordered, with four different tetrahedral sites randomly occupied by Co and Ga atoms at a ratio of 1:2. The tetrahedra form a disordered (Co_1/3Ga_2/3)O₂ 3D-framework inside which isolated CoO₆ octahedra, surrounded by 8 Ca atoms, are located. The structure is related to the ordered structure of Ca₁₄Al₁₀Zn₆O₃₅. Electron diffraction patterns confirmed the symmetry and unit cell and revealed no diffuse scattering. High-resolution electron microscopy images showed the absence of extended structural defects.     

A Novel Complex Cobalt Gallium Oxide Ca2Co0.8Ga1.2O4.8: Synthesis and High-Temperature Electron Transport Properties

A new complex oxide with the cation ratio Ca:Co: Ga=2:0.8:1.2 has been synthesized in air at 1150^oC. The cobalt atoms adopt oxidation states 2+ and 3+ in equal amounts giving an oxygen content corresponding to the composition Ca₂Co_0.8Ga_1.2O_4.8. It crystallizes in F-centered cubic structure with a=15.0558 Å. Conductivity measurements performed at high temperatures revealed that the temperature increase gives a charge disproportionation of Co³⁺ species resulting in a small concentration of Co⁴⁺ species and thus a small p-type conductivity in the oxide. A decrease of the oxygen pressure promotes oxygen depletion from the oxide and a deterioration of the conductivity. The electric properties are interpreted within a small polaron conduction mechanism. An unusually large mobility activation energy of 0.45 eV can be explained by a large spatial separation of cobalt cations in the structure.     

Ag/PANI/Fe_2O_3复合纳米粒子的合成与催化性能

借助于PANI的还原性质,PANI/Fe2O3复合载体与AgNO3发生表面氧化还原反应,合成了Ag/PANI/Fe2O3复合纳米粒子。TEM和XRD结果表明,立方晶系纳米银的平均粒径10nm。FTIR结果表明,Ag与PANI及Fe2O3复合载体之间不存在化学键合作用,但由于PANI与Ag之间的电子相互作用,Ag/PANI/Fe2O3复合纳米粒子的FTIR吸收峰发生蓝移。Ag/PANI/Fe2O3复合纳米粒子对于间硝基苯磺酸钠的硼氢化钠还原反应表现出良好的催化活性,30min内间硝基苯磺酸钠的转化率达到86.77%。     

Thermal behaviour of cobalt oxides doped with ZrO2 and ThO2 and the possible cubic phase stabilization of zirconia

The effects of doping cobalt oxides with different amounts of ZrO₂ and ThO₂ (1.5–9 mol%) on the thermal stability of Co₃O₄ and the re-oxidation of CoO by O₂ to Co₃O₄ were investigated. The techniques employed were DTA, with a controlled rate of heating and cooling, X-ray diffraction, and IR spectrometry.The results obtained by DTA revealed that the addition of both Th⁴⁺ and Zr⁴⁺ (up to 6 mol%) exerted no appreciable effect on the thermal stability of Co₃O₄. Increasing the amount of the dopant ions to 9% resulted in no further change in the thermal stability of Co₃O₄ in the case of Th⁴⁺, and an increase of 16% in case of Zr⁴⁺-doping. However, ThO₂-doping of cobalt oxide was accompanied by an enhancement in the reactivity of CoO towards re-oxidation by O₂ to Co₃O₄ to an extent proportional to the amount of dopant oxide.The X-ray investigation of ZrO₂-doped cobalt oxides calcined in air at 1000°C revealed the presence of highly crystalline and stable zirconia in the cubic form. Such a stable phase could not be obtained at temperatures below 2370°C in the absence of stabilizing agents.X-ray and IR investigations of different solids showed the presence of free thoria and zirconia together with new thorium—cobalt and zirconium—cobalt compounds. However, the slow cooling of Zr-treated cobalt oxides from 1000°C to room temperature led to the decomposition of the newly formed compound. The d-spacings and absorption bands of the newly formed compounds were determined.     

Electromagnetic transport properties and magnetoresistance of La0.7Ca0.2Sr0.1MnO3-Ag composites prepared by electroless process

A series of bulk polycrystalline La_0.7Ca_0.2Sr_0.1MnO₃ (LCSMO)-Ag composites were prepared by electroless plating process and several kinds of physical properties have been studied systemically. According to the results of X-ray diffraction (XRD), scanning electron microscopy (SEM), and electromagnetic transport properties, we can see that Ag-added segregated at the surfaces or interfaces of LCSMO grains. The metal-insulator transition temperature (T_P) and Curie temperature (T_c) were almost unchanged but ρ decreased with increasing plating time. We also observed Ag-added can significantly enhance the magnetoresistance (MR) near T_P under a low applied field (3000 Oe) and the room temperature MR reached to 35% under 20 kOe, which is encouraging for practical applications. We can suggest that improved grain boundary effect by Ag-added is responsible for the enhancement.     

Electrochemical deposition and properties of PbO2 + Co3O4 composites

Electrolysis of suspensions of Co₃O₄ particles in Pb²⁺-containing electrolytes has been used for depositing PbO₂ + Co₃O₄ composite layers on Ni rotating dise anodes. A sufficiently high angular speed of the electrode is necessary to obtain layers of homogeneous thickness and Co₃O₄ concentration. The volume fraction of Co₃O₄ particles in the deposit α reaches a limiting value of ca. 0.1 when the volume fraction of particles in suspension C exceeds 0.008. The current density j has little effect on α as long as it is in the range 1 to 20 mA cm⁻²; if j increases further, α decreases.PbO₂ + Co₃O₄ composite layers have been studied as electrode materials for the oxygen evolution reaction (mainly in NaOH solution). The overpotential and Tafel slope decrease upon increasing α. At a fixed potential, j is roughly proportional to OH⁻ concentration. The PbO₂ + Co₃O₄ electrode performance is fairly stable at 25°C but declines with time at higher temperature.     

Enhanced ferromagnetic transition and magnetoresistance in granular Ag-added La0.7Ca0.3MnO3

Granular Ag-added La_0.7Ca_0.3MnO₃ (LCMO) samples were prepared by a sol-gel chemical route. Significant enhancements in Curie temperature (T_C), metal−insulator transition (T_p) and magnetoresistance (MR) effects near room temperature are observed in as-obtained samples. 10 wt% addition of Ag in LCMO causes T_C shift from 272 to 290 K, T_p boost up for more than 100 K and resistivity decrease by more than 3 orders of magnitude. X-ray diffraction patterns, thermal analysis and energy dispersive analysis of X-rays evidently show the existence of metal silver in LCMO matrices. High-resolution electron microscopy illustrates a well crystallization for LCMO grains in existence of Ag. It is argued that improved grain boundary effect and better crystallization caused by Ag addition are responsible for the enhancements.     

Lithium-substituted cobalt oxide spinels LixM1−xCo2O4 (M = Co2+, Zn2+; 0 ≤ x ≤ 0.4)

Substitution of Li⁺ into Co₃O₄ and ZnCo₂O₄ gives rise to the solid solution series Li_xM_1?xCo₂O₄ (M = Co²⁺ or Zn²⁺) having the spinel structure upto x = 0.4. X-Ray diffraction intensities show that the spinel solid solutions are likely to have the following cation distributions: (Co²⁺)_t[Li⁺_xCo³⁺_2?3xCo⁴⁺_2x]₀O₄ and (Zn²⁺_1?xCo²⁺_x)_t[Li⁺_xCo³⁺_2?3xCo⁴⁺_2x]₀O₄. Electrical resistivity and Seebeck coefficient data indicate that the electron transport in these systems occurs by a small-polaron hopping mechanism.     

Synthesis, crystal structure and electrical characterization of two new potassium uranyl molybdates K2(UO2)2(MoO4)O2 and K8(UO2)8(MoO5)3O6

Two new potassium uranyl molybdates K₂(UO₂)₂(MoO₄)O₂ and K₈(UO₂)₈(MoO₅)₃O₆ have been obtained by solid state chemistry . The crystal structures were determined by single crystal X-ray diffraction data, collected with MoKα radiation and a charge coupled device (CCD) detector. Their structures were solved using direct methods and Fourier difference techniques and refined by a least square method on the basis of F² for all unique reflections, with R₁=0.046 for 136 parameters and 1412 reflections with I?2σ(I) for K₂(UO₂)₂(MoO₄)O₂ and R₁=0.055 for 257 parameters and 2585 reflections with I?2σ(I) for K₈(UO₂)₈(MoO₅)₃O₆. The first compound crystallizes in the monoclinic symmetry, space group P2₁/c with a=8.250(1) Å, b=15.337(2) Å, c=8.351(1) Å, β=104.75(1)°, ρ_mes=5.22(2) g/cm³, ρ_cal=5.27(2) g/cm³ and Z=4. The second material adopts a tetragonal unit cell with a=b=23.488(3) Å, c=6.7857(11) Å, ρ_mes=5.44(3) g/cm³, ρ_cal=5.49(2) g/cm³, Z=4 and space group P4/n.In both structures, the uranium atoms adopt a UO₇ pentagonal bipyramid environment, molybdenum atoms are in a MoO₄ tetrahedral environment for K₂(UO₂)₂(MoO₄)O₂ and MoO₅ square pyramid coordination in K₈(UO₂)₈(MoO₅)₃O₆. These compounds are characterized by layered structures. The association of uranyl ions (UO₇) and molybdate oxoanions MoO₄ or MoO₅, give infinite layers [(UO₂)₂(MoO₄)O₂]²⁻ and [(UO₂)₈(MoO₅)₃O₆]⁸⁻ in K₂(UO₂)₂(MoO₄)O₂ and K₈(UO₂)₈(MoO₅)₃O₆, respectively. Conductivity properties of alkali metal within the interlayer spaces have been measured and show an Arrhenius type evolution.