Effect of the calcination temperature on the cation distribution and optical properties of Mg0.5Co0.5CrAlO4 spinel pigment

In this study, a blue-green pigment has been prepared by partially replace Co²⁺ and Cr³⁺ in CoCr₂O₄ spinel structure with Mg²⁺ and Al³⁺ using a gel casting method The gel precursor was calcined at various temperatures (900–1400 °C) to obtain Mg_0.5Co_0.5CrAlO₄ spinel pigment. Combining the Rietveld refinement method of XRD and peak fitting of XPS high-resolution spectra, the relationships between the cation distributions (Co²⁺, Mg²⁺, Al³⁺, and Cr³⁺) in the tetrahedron and octahedron of the spinel structure and the calcination temperature were examined. In the octahedron, the contents of Co²⁺ and Al³⁺ decreased with increasing calcination temperature, and the Mg²⁺ and Cr³⁺ contents exhibited the opposite trend. The bond lengths of A-O and B–O change with increasing calcination temperature, thereby leading to a change in the unit cell. The optical performance of the pigments was investigated via UV–vis and CIE L*a*b* spectrophotometry, and the study shows that the blue-green hue of the pigment powder is caused by the absorption at υ3～υ8 (370 nm–640 nm) in the visible light region. The varied contents of Co²⁺ and Cr³⁺ in the spinel structure among calcination temperatures cause the absorption spectrum intensity change, thereby resulting in various blue-green tones. This study lays the foundations for subsequent investigations of colour modification in Mg_xCo_1-xAl_yCr_2-yO₄ spinel.     

A new binuclear Cr(III) citrate anion: Synthesis,characterization and crystal structure of [Cr(CO(NH2)2)6]2[Cr2(CO(NH2)2)2(C6H4O7)2]3

The new anion [Cr₂(CO(NH₂)₂)₂(C₆H₄O₇)₂]^2 − has been isolated in the complex [Cr(CO(NH₂)₂)₆]₂[Cr₂(CO(NH₂)₂)₂(C₆H₄O₇)₂]₃. The crystals of this complex were obtained by a one-pot synthetic method using 1:1 molar ratio of hexaureachromium(III) chloride and trisodium citrate in aqueous medium. It was characterized by elemental analysis, IR spectroscopy and single crystal X-ray diffraction analysis. The compound crystallizes in space group R‾3 of the trigonal system with three formula units in a cell of dimensions a = b = 24.7461(4) Å, c = 13.7204(3) Å and γ = 120°. The crystal structure comprises the columns consisting of [Cr(CO(NH₂)₂)₆]^3 + cations surrounded by a cylinder of complex anions, [Cr₂(CO(NH₂)₂)₂(C₆H₄O₇)₂]^2 − which are packed in a honeycomb-like manner. This supramolecular architecture is formed and stabilized by inter- and intramolecular NH⋯O hydrogen bonds.     

Blue-violet ceramic pigments based on Co and Mg Co2−xMgxP2O7 diphosphates

Solid solutions of Co and Mg diphosphates with compositions Co_2?xMg_xP₂O₇ (x = 0, 0.1, 0.2, 0.3, 0.5, 0.7, 1.0, 1.5 and 1.8) have been prepared and characterized for the first time as alternative low-toxicity blue ceramic pigments. The compositions were prepared through the conventional coprecipitation route and calcined up to 1000 °C/2 h. Samples were characterized by thermal analysis, XRD, SEM/EDX, UV–vis-NIR spectroscopy and colour measurements (CIE-L^*a^*b^*). Isostructural Co_2?xMg_xP₂O₇ diphosphate solid solutions (monoclinic system and P21/c spatial group) formed successfully within the studied range of compositions, accompanied only by a minor quantity of residual Co or Mg orthophosphates (M₃(PO₄)₂). Interestingly, the obtained solid solutions developed nice blue-violet colourations even with high Mg doping after enamelling within double-firing (x = 1.5–1.8) and single-firing (x = 1.0–1.5) ceramic glasses. These optimal compositions containing a minimized Co amount (measured values around 7–16 wt%) could be therefore less toxic alternatives to the conventional Co₃(PO₄)₂ blue ceramic pigment.     

Role of Ni2+ substituent on the structural,optical and magnetic properties of chromium oxide (Cr2-xNixO3) nanoparticles

Pristine chromium oxide (Cr₂O₃) and nickel ions (Ni²⁺) substituted Cr₂O₃ nanoparticles were synthesized using a simple co-precipitation technique. The main objective of this work is to investigate Ni²⁺ substituent's role at different concentrations on the structural, morphological, optical, and magnetic properties of Cr₂O₃ nanoparticles. Structural analyses based on X-ray diffraction (XRD), Raman and Fourier transform infra-red (FTIR) data confirmed the successful incorporation of Ni²⁺ into Cr₂O₃ nanoparticles up to x = 0.05 of Ni²⁺ content, without affecting the rhombohedral crystal structure of Cr₂O₃ nanoparticles. Rietveld refinement results showed the variation in lattice parameters and cell volumes alongwith the substitution of Ni²⁺ into Cr₂O₃ nanoparticles. Raman and FTIR spectra also depicted a considerable shift in the characteristic vibration modes of Cr₂O₃ nanoparticles due to strain-induced by Ni²⁺ substitution. Beyond x = 0.05, the structural transformation took place from rhombohedral to cubic crystal structure. Subsequently, new peaks (apart from Cr₂O₃ phase modes) have been observed at x = 0.1 of Ni²⁺ content due to the formation of secondary phase i.e., nickel chromate (NiCr₂O₄). Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) illustrated the changes in the morphology of Cr₂O₃ nanoparticles with Ni²⁺ substitution. UV–Vis analysis revealed a narrowing of optical band energy (E_g) of Ni²⁺ substituted Cr₂O₃ nanoparticles from 3 to 1.85 eV as Ni²⁺ content varies from x = 0 to 0.2, respectively. Afterward, there is an increase in optical band gap energy (E_g) when Ni²⁺ content increased from x = 0.3 to 0.5, as NiCr₂O₄ started dominating the Cr₂O₃ phase. Single-phase Ni²⁺ substituted Cr₂O₃ nanoparticles exhibited a superparamagnetic behavior, whereas the multi-phase compound ascribed to both superparamagnetic and paramagnetic. These changes in optical and magnetic properties can lead to novel strategies to render applications in the field of optoelectronics and optomagnetic devices.     

Two inorganic–organic hybrid compounds based on [Ni2(V3O9)2]2− cluster and {Co2V2} cage subunits

Two novel inorganic-organic hybrid compounds (Ni₃(Hfcz)₄(V₃O₉)₂? 2H₂O) (1) and Co₅(H₂O)₄(fcz)₂(V₄O₁₂)₂ (2) have been successfully constructed, based on [Ni₂(V₃O₉)₂]^2? “bow tie” clusters and {Co₂V₂} pure inorganic cages. Structural analysis reveals that the clusters and cages are expanded to a 2D network and 3D framework via Ni^II and Co^II, respectively. In addition, we investigated the optical band gaps of the two compounds: 2.92 eV and 2.23 eV.     

Investigation on phase structure,spectral characteristics,microstructure and microwave dielectric properties of Li2Zn[Ti1-x(Co1/3Nb2/3)x]3O8 (0.0 ≤ x ≤ 0.4) ceramics

In this paper, a series of Li₂Zn[Ti_1-x(Co_1/3Nb_2/3)_x]₃O₈ (0.0 ≤ x ≤ 0.4) ceramics were prepared via the conventional solid-state method. The influences of (Co_1/3Nb_2/3)⁴⁺ complex ions on the phase composition, spectral characteristics, microstructure, and microwave dielectric properties of Li₂Zn[Ti_1-x(Co_1/3Nb_2/3)_x]₃O₈ ceramics were studied systematically. XRD analysis accompanied with Rietveld refinements showed that pure Li₂ZnTi₃O₈ solid solution ceramics with the cubic spinel structure were obtained at x = 0.2–0.4. New Raman-active mode of about 858 cm⁻¹ should be attributed to the vibrations of NbO₆ due to the high bond energy of Nb–O bonds, exerting a certain impact on the structure and performance of Li₂Zn[Ti_1-x(Co_1/3Nb_2/3)_x]₃O₈ ceramics. XPS results indicated that Nb⁵⁺ ion donor suppressed the deoxidation process and therefore resulted in the disappearance of Ti³⁺ ion and oxygen vacancy. The downward trend variation in the ε_r value with the increase of (Co_1/3Nb_2/3)⁴⁺ content could be explained by the presence of “compressed” cations and “rattling” cations effect. In addition, the Q × f of the current ceramics was closely dependent on relative density, grain size, FWHM, and oxygen vacancy. Good combined microwave dielectric properties of ε_r = 24.5, Q × f = 91,250 GHz, and τ_f = −16.8 ppm/°C were achieved for the Li₂Zn[Ti_0.8(Co_1/3Nb_2/3)_0.2]₃O₈ ceramic sintered at 1120 °C. High quality factor gives evidence that the Li₂Zn[Ti_0.8(Co_1/3Nb_2/3)_0.2]₃O₈ ceramic is an appealing candidate for highly selective microwave devices.     

Development of La(CrCoFeNi)O3 system perovskites as interconnect and cathode materials for solid oxide fuel cells

The purpose of this research is to develop interconnect and cathode materials for use in solid oxide fuel cells (SOFCs) which demonstrate desired properties of outstanding sintering properties, high electrical conductivity, and excellent chemical stability at high temperatures. Five different perovskite oxides of lanthanum in combination with chromium, iron, cobalt and nickel oxides powders, i.e. LaCr_0.7Co_0.1Fe_0.1Ni_0.1O₃(LCr7CFN), LaCo_0.7Cr_0.1Fe_0.1 Ni_0.1O₃(LCo7CFN), LaFe_0.7Cr_0.1Co_0.1Ni_0.1O₃(LFe7CCN), LaNi_0.7Cr_0.1Co_0.1Fe_0.1O₃(LNi7CCF), and LaCr_0.25Co_0.25Fe_0.25Ni_0.25O₃(LCCFN), were synthesized through the Pechini method. XRD results show that all materials are in single phase, either rhombohedral or orthorhombic crystal structure. The resulting powders were able to be sintered to a high relative density at a temperature of 1400 °C for 2 h in air. The electrical conductivity of the sintered sample was measured and evaluated from 300 °C to 800 °C. The LCCFN sample appears to have the best combination of sintering property (approximate 94% relative density) and electrical conductivity (88.13 Scm⁻¹ at 800 °C).     

Fabrication and in vitro studies on bioactive borate glasses containing dopant chromium sulfate

This research aims to assess the bioactive properties of the modified borate glasses containing extremely low concentrations (≤5 mol.%) from chromium sulfate (Cr₂(SO₄)₃). The glasses in the system xCr₂(SO₄)₃.(60–x)B₂O₃.15CaO.15Na₂O.10P₂O₅, where x = 0, 1, 2, and 5 mol.% were prepared by the melt quenching technique. All glass samples have been treated thermally at 600 °C for 6 h. Fourier Transform Infrared (FTIR) spectroscopy, Scanning Electron Microscopy (SEM), and X-ray Diffraction (XRD) measurements were carried out to differentiate between the structural changes before and after soaking in the simulated body fluid (SBF) at about 37 °C for 1, 2, and 3 weeks. Glass-ceramic samples have showed sharper peaks that are identified using X-ray diffraction data. These crystalline phases are indexed to crystalline calcium borate (Ca₂B₂O₃) and calcium phosphate (Ca₃(PO₄)₂). In vitro tests, FTIR spectra revealed two small bands in the 560-610 cm⁻¹ range which might be assigned to the formation of a hydroxyapatite layer (HA). The formation of HA was also confirmed by XRD results, particularly after immersion in SBF for 21 days. The study suggests that the presently studied glasses containing Cr₂(SO₄)₃ can possess good bioactivity which might be considered to be suitable for some bio and medical applications.     

Photocatalytic reduction of Ag2SO4 by the Dawson anion α-[P2W18O62] and tetracobalt sandwich complexes

The photocatalytic behaviours of the Dawson salt α-K₆[P₂W₁₈O₆₂] and two isomers of the tetracobalt Dawson-derived sandwich complexes, αββα-Na₁₇[Co₄(H₂O)(OH)(P₂W₁₅O₅₆)₂]·51H₂O·2NaCl and ααβα-Na₁₆[Co₄(H₂O)₂(P₂W₁₅O₅₆)₂]·51H₂O (abbreviated ββ-{Co₄P₄W₃₀} and αβ-{Co₄P₄W₃₀}, respectively), are described and compared.The direct photochemical excitation of the polyoxometalates (POM) in the presence of propan-2-ol as electron donor leads to their reduction. With polyoxometalates as photocatalyst and propan-2-ol as sacrificial electron donor, the reduction of Ag^I₂SO₄ from aqueous solutions is observed leading to metallic Ag_n⁰ clusters and colloidal metal nanoparticles stabilized by POM.In the case of both {Co₄P₄W₃₀}, TEM experiments reveal that most of the Ag_n particles obtained with a slight excess of Ag⁺ are spherical with a quite large distribution in size between 10 and 100 nm.     

Weak ferroelectricity and low-permittivity microwave dielectric properties of Ba2Zn(1+x)Si2O(7+x) ceramics

Ba₂Zn_(1+x)Si₂O_(7+x) ceramics were prepared using the conventional solid-state method at 1200 °C for 3 h in air. Apart from the previously reported Ba₂Zn_(1+x)Si₂O_(7+x) (x = 0) with a monoclinic structure (C 2/c), the end-member compositions at x = −1 and 1 exhibit single-phase β-BaSiO₃ with an orthorhombic structure (P2₁2₁2₁) and BaZnSiO₄ with a hexagonal structure (P6₃), and possess a coexistence of weak ferroelectricity and low-permittivity microwave dielectric properties. A reduction in Zn²⁺ content mainly decreases the intensity of the ε_r anomaly peak at lower temperature and increases the ε_r (or frequency) stability against temperature. The Zn²⁺-rich BaZnSiO₄ phase has a τ_f value of −181 ppm/°C, whereas the τ_f value of Zn²⁺-free BaSiO₃ phase decreases to −35.4 ppm/°C. The Zn²⁺ deficiency in Ba₂ZnSi₂O₇ composition could inhibit the presence of BaZnSiO₄ phase and improve the τ_f value, whereas excessive Zn²⁺ cations prompt the formation of the BaZnSiO₄ phase to deteriorate significantly the τ_f value.     

Design of a narrow-band blue-emitting Rb2Ba3(P2O7)2:Eu2+ phosphor with low thermal quenching for plant growth LEDs

Phosphor-converted light-emitting diodes (pc-LEDs) are commonly used to regulate the light environment to control the growth rates and improve the production efficiency of plant. Among them, the exploration of blue-emitting phosphors with high efficiency, low thermal quenching and excellent spectrum resemblance matching with the plant response spectrum is still challenging. Herein, a narrow-band blue-emitting Rb₂Ba₃(P₂O₇)₂:Eu²⁺ phosphor with high color purity of 93.4% has been developed. Under 345 nm excitation, it exhibits a blue emission band centered at 413 nm with a full width at half-maximum (FWHM) of 36 nm, and the emission spectrum of Rb₂Ba₃(P₂O₇)₂:0.060Eu²⁺ sample shows 85.7% spectrum resemblance with the absorption spectrum of chlorophyll-a in the blue region from 400 to 500 nm. In addition, the temperature-dependent emission spectra demonstrate that the Rb₂Ba₃(P₂O₇)₂:0.060Eu²⁺ phosphor has good thermal stability and small chromaticity shift, with the emission intensity dropping to 72.5% at 423 K of the initial intensity at 298 K and a chromaticity shift of 38 × 10^-3 at 498 K. All results suggest that the blue-emitting Rb₂Ba₃(P₂O₇)₂:Eu²⁺ phosphor has potential application in plant growth LEDs.     

A new ternary phase in the system CaO–Al2O3–Cr2O3: Crystal structure and thermal expansion of CaAl2Cr2O7

Polycrystalline material of a novel phase in the system CaO–Al₂O₃–Cr₂O₃ has been obtained by solid-state reactions. Chemical analysis indicated the composition CaAl₂Cr₂O₇. Single-crystal growth of the new compound using borax as a mineralizer was successful. Diffraction experiments at ambient conditions on a crystal with composition CaAl_2.13Cr_1.87O₇ yielded the following basic crystallographic data: space group P 3, a = 7.7690(5) Å, c = 7.6463(5) Å, V = 399.68(6) ų, Z = 3. Structure determination and subsequent least-squares refinements resulted in a residual of R(|F|) = 2.3% for 1440 independent observed reflections and 113 parameters. To the best of our knowledge, the structure of CaAl_2.13Cr_1.87O₇ or CaAl₂Cr₂O₇ represents a new structure type. It belongs to the group of double layer structures where individual double layers contain octahedrally and tetrahedrally coordinated cation positions. Linkage between neighboring sheet packages is provided by additional calcium cations. Furthermore, thermal expansion has been studied in the interval between 29 and 790°C using in situ high-temperature single-crystal diffraction. No indications for a structural phase transition were observed. From the evolution of the lattice parameters the thermal expansion tensor has been obtained. A pronounced anisotropy is evident. The response of structural building units to variable temperature has been discussed.     

Microwave dielectric properties,microstructure, and bond energy of Zn3-xCoxB2O6 low temperature fired ceramics

Low temperature co-fired ceramics (LTCCs) technology plays an important role in modern wireless communication. Zn_3-xCo_xB₂O₆ (x = 0–0.25) low temperature fired ceramics were synthesized via traditional solid-state reaction method. Influences of Co²⁺ substitution on crystal phase composition, grain size, grain morphology, microwave dielectric properties, bond energy, and bond valence were investigated in detail. X-ray diffraction analysis indicated that the major phase of the ceramics was monoclinic Zn₃(BO₃)₂. Solid solution was formed with Co²⁺ substituted for Zn²⁺ because no individual phase that contained Co was observed. An increase in the amount of Co²⁺ substitution changed average grain sizes, and regrowth of grains were observed with Co²⁺ substitution. Appropriate amount of Co²⁺ substitution improved densification. With changes in Co²⁺ substitution, bond energy of major phase and average bond valence of B–O were positively correlated to temperature coefficient of resonant frequency. The Zn_2.927Co_0.075B₂O₆ ceramic sintered at 875 °C for 4 h exhibited excellent microwave properties with ε_r = 6.79, Q × f = 140,402 GHz, and τ_f = −87.42 ppm/°C. This ceramic is regarded as candidate for LTCC applications.     

Methane Combustion Over Copper Chromites Catalysts Prepared by the Sol–Gel Process

Abstract  

Methane combustion was performed over a series of copper chromites (CuCr₂O₄) catalysts prepared by the sol–gel process (SG). The results were compared with those obtained over commercial CuCr₂O₄. The samples were characterised by elemental analysis, thermal analysis, X-ray diffraction and X-ray photoelectron spectroscopy (XPS). The as-synthesised CuCr₂O₄ sample exhibited higher specific surface area (248 m² g⁻¹) with respect to commercial solids (42 m² g⁻¹). The surface properties were established using XPS. Simultaneously, an increase in the atomic Cr⁶⁺/Cr³⁺ ratio (0.56 for SG catalyst vs. 0.39 for commercial sample) and a decreasing surface copper concentration (8.3%, for SG specimen vs. 17.6% for commercial catalyst) are observed. XPS study revealed also that Cu²⁺/(Cu° + Cu⁺) ratio of copper species remained constant (ca. 5) in both catalysts. Structure transformations of CuCr₂O₄ under reduction-reoxidation conditions showed that the reduction of copper and/or chromium cations from the CuCr₂O₄ and from delafossite (CuCrO₂) structure (CuCr₂O₄↔CuCrO₂ + Cu + Cr₂O₃↔Cu + Cr₂O₃) were different. This has lead to a difference in catalytic properties of the catalysts. Catalytic activity of SG catalysts was superior to that of commercial CuCr₂O₄ tested under the same conditions. Complex hysteresis behaviour for CuCr₂O₄ catalysts ramped over a temperature range of 220–850 °C where the stables active phases were obtained only after the first ramp of heating under reactants. No catalysts deactivation was further observed after several cycles of heating and cooling. The stabilisation of catalytic activity was attributed to the formation of mixed crystalline phases containing both copper and chromium species.     

Thermal and chemical stability of Cu–Zn–Cr-LDHs prepared by accelerated carbonation

Layered double hydroxides Cu_xZn_6 − xCr₂(OH)₁₆(CO₃)·4H₂O with different molar ratios of Cu/Zn/Cr were synthesized by accelerated carbonation. The products were characterized by XRD, SEM, FT-IR and TG-DTG-DSC-MS. The chemical stability was tested by the modified Toxicity Characteristic Leaching Procedure (TCLP). The results showed that the products were the mixture of Cu_xZn_6 − xCr₂(OH)₁₆(CO₃)·4H₂O and (CuZn)₂(CO₃)(OH)₂, with similar thermal behavior. All products were chemically stable with reduced leaching at pH > 6 (Cu²⁺, Zn²⁺) or > 5 (Cr³⁺).     

Preparation and electrochemical properties of Cr-doped Li9V3(P2O7)3(PO4)2 as cathode materials for lithium-ion batteries

Cr-doped Li₉V_3−xCr_x(P₂O₇)₃(PO₄)₂ (x = 0.0–0.5) compounds have been prepared using sol–gel method. The Rietveld refinement results indicate that single-phase Li₉V_3−xCr_x(P₂O₇)₃(PO₄)₂ (x = 0.0–0.5) with trigonal structure can be obtained. Although the initial specific capacity decreased with Cr content at a lower current rate, both cycle performance and rate capability have excited improvement with moderate Cr-doping content. Li₉V_2.8Cr_0.2(P₂O₇)₃(PO₄)₂ compound presents the good electrochemical rate and cyclic ability. The enhancement of rate and cyclic capability may be attributed to the optimizing particle size, morphologies, and structural stability during the proper amount of Cr-doping (x = 0.2) in V sites.     

A rapid synthesis of cobalt cyclotetraphosphate Co2P4O12 at low temperature

The cobalt cyclotetraphosphate, Co₂P₄O_12, was synthesized by evaporating a mixture of cobalt chloride hexahydrate, phosphoric acid and water at 70 °C, with further calcinations at 400 °C, 500 °C and 600 °C for 3 h. XRD results indicated that the Co₂P₄O₁₂ compounds obtained had only monoclinic phase with space group C_2h⁶ (Z=4). From FT-IR spectra, vibrational modes corresponding to internal vibrations of the P₄O₁₂^4? anion were identified. The morphologies and crystallite sizes for the Co₂P₄O₁₂ obtained from SEM data and X-ray line broadening showed non-uniform particles and 37–68 nm, respectively. All characterization methods showed that the monoclinic phase of Co₂P₄O₁₂ could be synthesized at the low temperature of 400 °C with short time consumption. The temperature was about 400 °C lower than that used in the previous synthesis method with CoCl₂ as reactant, and resulted in a cost-, energy-, and time-saving method.     

(Sb2O3/Sb2O5)-doped SnO2–Co3O4–Cr2O3 varistors: The Sb2O4 in-situ formation and its influence over the electrical and microstructural properties

The present study aimed to systematically study the transitions and consequential effects of antimony oxide (Sb₂O₃ or Sb₂O₅) additions over the properties of a SnO₂-based varistor system. High energy ball-milling and conventional sintering were used to obtain the samples with the following molar composition: (98.95-X)% SnO₂ - 1% Co₃O₄ - 0.05% Cr₂O₃ - X% Sb₂O₃/Sb₂O₅ where X = 0, 0.05, 0.1, 0.2 and 0.4 mol%. The thermal analysis suggested the in-situ formation of Sb₂O₄ at ~450 °C from Sb₂O₃ or Sb₂O₅ during the sintering of mixed oxides. SEM, XRD, and electrical analysis revealed similar results by using Sb₂O₃ or Sb₂O₅; the addition of 0.05 mol% antimony oxide provides the foremost properties. The transition equations from Sb₂O₃ or Sb₂O₅ to Sb₂O₄ demonstrate equivalency in the amount of Sb₂O₄ formed. That fact, besides the results obtained, were used to discuss a reasonable route for Sb³⁺ and Sb⁵⁺ incorporation within the SnO₂ lattice.     

Hydrothermal synthesis,characterization and magnetic properties of a new 2D arsenic–vanadate layers supported cobalt coordination complex: [Co(en)2(H2O)]{[Co(en)2]2As8V14O42(SO4)} · 3H2O

The title compound [Co(en)₂(H₂O)]{[Co(en)₂]₂As₈V₁₄O₄₂(SO₄)} · 3H₂O (1) (en = ethylenediamine) has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, IR spectrum and thermogravimetric analysis. The single crystal diffraction analysis shows that compound 1 exhibits {[Co(en)₂]₂As₈V₁₄O₄₂(SO₄)}n²ⁿ⁻ layers act as ligand of coordination cations [Co(en)₂]²⁺, and water molecules are inserted in the layers. The magnetic measurement indicates a weak antiferromagnetic exchange coupling within the molecular unit, which is deemed to attribute to the contribution of V^iv and Co²⁺.     

Valence state of europium and samarium in Ln2Hf2O7 (Ln = Eu,Sm) based oxygen ion conductors

Ln₂(Hf_2-xLn_x)O_7-x/2 (Ln = Sm, Eu; x = 0.1) pyrochlores have been prepared via mechanical activation of oxide mixtures, followed by heat treatment for 4h at 1450 and 1600 °C, respectively. According to the ESR data, the Eu cations on the Hf site in the Hf_1-xEu_xO₆ octahedra in pyrochlore Eu₂(Hf_2-xEu_x)O_7-x/2 (x = 0.1) are most readily oxidized and reduced. Oxidation at 840 °C for 24h in air reduces the total conductivity of the Ln₂(Hf_2-xLn_x)O_7-x/2 (Ln = Sm, Eu; x = 0.1) by a factor of 2.5–6, due to the decrease in the concentrations of oxygen vacancies and Ln²⁺ ions as a result of the oxidation. The anomalous low-frequency behavior of the permittivity of the Eu₂(Hf_2-xEu_x)O_7-x/2 (x = 0.1) at ~800 °C can be understood in terms of the changes in the oxygen sublattice of the pyrochlore structure as a result of the oxidation of divalent europium and partial filling of oxygen vacancies at this temperature.