Kinetics of reduction of iron oxides by H2: Part II. Low temperature reduction of magnetite

This study deals with the reduction of Fe₃O₄ by H₂ in the temperature range of 210-950 °C. Two samples of Fe₃O₄ produced at 600 and 1200 °C, designated as Fe₃O₄₍₆₀₀₎ and Fe₃O_4(1200), have been used as starting material.Reduction of Fe₃O₄₍₆₀₀₎ by H₂ is characterized by an apparent activation energy ‘E_a’ of 200, 71 and 44 kJ/mol at T < 250 °C, 250 °C < T < 390 °C and T > 390 °C, respectively. The important change of E_a at 250 °C could be attributed to the removal of hydroxyl group and/or point defects of magnetite. This is confirmed during the reduction of Fe₃O_4(1200). While transition at T ≈ 390 °C is probably due to sintering of the reaction products as revealed by SEM.In situ X-rays diffraction reduction experiments confirm the formation of stoichiometric FeO between 390 and 570 °C. At higher temperatures, non-stoichiometric wüstite is the intermediate product of the reduction of Fe₃O₄ to Fe.The physical and chemical modifications of the reduction products at about 400 °C, had been confirmed by the reduction of Fe₃O₄₍₆₀₀₎ by CO and that of Fe₃O_4(1200) by H₂. A minimum reaction rate had been observed during the reduction of Fe₃O_4(1200) at about 760 °C. Mathematical modeling of experimental data suggests that the reaction rate is controlled by diffusion and SEM observations confirm the sintering of the reaction products.Finally, one may underline that the rate of reduction of Fe₃O₄ with H₂ is systematically higher than that obtained by CO in the explored temperature range.     

Hydrogen production from water decomposition by redox of Fe2O3 modified with single- or double-metal additives

Iron oxide modified with single- or double-metal additives (Cr, Ni, Zr, Ag, Mo, Mo-Cr, Mo-Ni, Mo-Zr and Mo-Ag), which can store and supply pure hydrogen by reduction of iron oxide with hydrogen and subsequent oxidation of reduced iron oxide with steam (Fe₃O₄ (initial Fe₂O₃)+4H₂↔3Fe+4H₂O), were prepared by impregnation. Effects of various metal additives in the samples on hydrogen production were investigated by the above-repeated redox. All the samples with Mo additive exhibited a better redox performance than those without Mo, and the Mo-Zr additive in iron oxide was the best effective one enhancing hydrogen production from water decomposition. For Fe₂O₃-Mo-Zr, the average H₂ production temperature could be significantly decreased to 276 °C, the average H₂ formation rate could be increased to 360.9-461.1 μmol min⁻¹ Fe-g⁻¹ at operating temperature of 300 °C and the average storage capacity was up to 4.73 wt% in four cycles, an amount close to the IEA target.     

Crystal structure, microstructure and reducibility of LaNixCo1−xO3 and LaFexCo1−xO3 Perovskites (0<x≤0.5)

Nickel and iron substituted LaCoO₃ with rhombohedrally distorted perovskite structure were obtained in the temperature range of 600-900 °C by thermal decomposition of freeze-dried citrates and by the Pechini method. The crystal structure, morphology and defective structure of LaCo_1−xNi_xO₃ and LaCo_1−xFe_xO₃ were characterized by X-ray diffraction and neutron powder diffraction, TEM and SEM analyses and electron paramagnetic resonance spectroscopy. The reducibility was tested by temperature programmed reduction with hydrogen. The products of the partial and complete reduction were determined by ex-situ XRD experiments. The replacement of Co by Ni and Fe led to lattice expansion of the perovskite structure. For perovskites annealed at 900 °C, there was a random Ni, Fe and Co distribution. The morphology of the perovskites does not depend on the Ni and Fe content, nor does it depend on the type of the precursor used. LaCo_1−xNi_xO₃ perovskites (x>0.1) annealed at 900 °C are reduced to Co/Ni transition metal and La₂O₃ via the formation of oxygen deficient Brownmillerite-type compositions. For LaCo_1−xNi_xO₃ annealed at 600 °C, Co/Ni metal, in addition to oxygen-deficient perovskites, was formed as an intermediate product at the initial stage of the reduction. The interaction of LaCo_1−xFe_xO₃ with H₂ occurs by reduction of Co³⁺ to Co²⁺ prior to the Fe³⁺ ions. The reducibility of Fe-substituted perovskites is less sensitive towards the synthesis procedure in comparison with that of Ni substituted perovskites.     

Peculiarities of the iron reduction mechanism in Fe-Al-K system

Temperature-programmed reduction was used in combination with measurements of magnetization to determine the peculiarities of iron reduction in the Fe-K-Al system. It was found that reduction by hydrogen proceeds with the formation of metallic iron through the stage of magnetite formation (Fe₃O₄); the effective activation energies are 63 and 39 kJ/mol for the I and II stages, respectively. It was shown that substituting carbon oxide for hydrogen leads to iron reduction proceeding only to the stage of magnetite formation (E _{Fe 3}O₄ = 94 kJ/mol). The magnetite interacts with CO to produce carbide (presumably Hegge carbide Fe₂C). Iron reduction in the synthesis gas occurs with the preferential participation of hydrogen or carbon dioxide, depending on the rate of temperature rise.     

Hexaferrites and phase relations in the iron-rich part of the system Sr-La-Co-Fe-O

The iron rich part of the system was examined in the temperature range of 1200-1380 °C in air, with focus on the solid solutions of M-type hexaferrites. Samples of suitable compositions were studied by electronprobe microanalysis (EPMA). Substituted Sr-hexaferrites in the system Sr-La-Co-Fe-O do not follow the 1:1 substitution mechanism of La/Co in M-type ferrites. Due to the presence and limited Co²⁺-incorporation Fe³⁺-ions are reduced to Fe²⁺ within the crystal lattice to obtain charge balance. In all examined M-type ferrites divalent iron is formed, even at 1200 °C. The substitution principle Sr²⁺+Fe³⁺↔La³⁺+(Fe²⁺, Co²⁺) yields to the general substitution formula for the M-type hexaferrite Sr²⁺_1-xLa³⁺_xFe²⁺_x-yCo²⁺_yFe³⁺_12-xO¹⁹ (0≤x≤1 and 0≤y≤x). In addition Sr/La-perovskite_SS (_SS=solid solution), Co/Fe-spinel_SS, hematite and magnetite are formed. Sr-hexaferrite exhibits at 1200 °C a limited solid solution with small amounts of Fe²⁺ (SrFe₁₂O₁₉↔Sr_0.3La_0.7Co_0.5Fe²⁺_0.2Fe_11.3O₁₉). At 1300 and 1380 °C a continuous solid solution series of the M-type hexaferrite is stable. SrFe₁₂O₁₉ and LaCo_0.4Fe²⁺_0.6Fe₁₁O₁₉ are the end members at 1300 °C. The maximum Fe²⁺O content is about 13 mol% in the M-type ferrite at 1380 °C (LaCo_0.1Fe²⁺_0.9Fe₁₁O₁₉).     

Mild hydrothermal synthesis and ferrimagnetism of Pr3Fe5O12 and Nd3Fe5O12 garnets

Two pure light rare earth iron garnets Pr₃Fe₅O₁₂ and Nd₃Fe₅O₁₂ single crystals were synthesized under mild hydrothermal conditions and structurally characterized by single crystal and powder X-ray diffraction methods. Both compounds crystallize in cubic space group Ia3?d with lattice parameters a=12.670(2) Å for Pr₃Fe₅O₁₂ and a=12.633(2) Å for Nd₃Fe₅O₁₂, respectively. The synthesis of compounds was studied with regard to phase evolution and morphology development with hydrothermal conditions. We proposed the formation mechanisms and formulated a reasonable explanation for their growth habits. Ferrimagnetic Curie temperatures which have been inferred from thermo-magnetization curves were 580 K for Pr₃Fe₅O₁₂ and 565 K for Nd₃Fe₅O₁₂, and the transitions of long range order were also evidenced by differential scanning calorimetry method. The result of magnetic properties has shown that moments of the large radius Pr³⁺ and Nd³⁺ ions are parallelly coupled with net moments of iron ions.     

The formation and physicochemical characterization of Al2O3-doped manganese ferrites

Mn/Fe mixed oxide solids doped with Al₂O₃ (0.32-1.27 wt.%) were prepared by impregnation of manganese nitrate with finely powdered ferric oxide, then treated with different amounts of aluminum nitrate. The obtained samples were calcined in air at 700-1000 °C for 6 h. The specific surface area (S_BET) and the catalytic activity of pure and doped precalcined at 700-1000 °C have been measured by using N₂ adsorption isotherms and CO oxidation by O₂. The structure and the phase changes were characterized by DTA and XRD techniques. The obtained results revealed that Mn₂O₃ interacted readily with Fe₂O₃ to produce well-crystallized manganese ferrite (MnFe₂O₄) at temperatures of 800 °C and above. The degree of propagation of this reaction increased by Al₂O₃-doping and also by increasing the heating temperature. The treatment with 1.27 wt.% Al₂O₃ followed by heating at 1000 °C resulted in complete conversion of Mn/Fe oxides into the corresponding ferrite phase. The catalytic activity and S_BET of pure and doped solids were found to decrease, by increasing both the calcination temperature and the amount of Al₂O₃ added, due to the enhanced formation of MnFe₂O₄ phase which is less reactive than the free oxides (Mn₂O₃ and Fe₂O₃). The activation energy of formation (ΔE) of MnFe₂O₄ was determined for pure and doped solids. The promotion effect of aluminum in formation of MnFe₂O₄ was attributed to an effective increase in the mobility of reacting cations.     

Ferroelectric perovskite-type barium copper niobate: BaCu1/3Nb2/3O3

A perovskite-type BaCu_1/3Nb_2/3O₃ was prepared by high temperature reaction using BaCO₃, CuO and Nb₂O₅. The X-ray powder diffraction pattern of this compound was indexed with the tetragonal cell with the lattice parameters of a=4.0464(4) and c=4.1807(4) Å (c/a=1.033). This compound had the tetragonal perovskite-type structure in which the B site was occupied statistically by Nb and Cu atoms. From high temperature X-ray powder diffraction patterns this compound had a phase transition from the tetragonal to cubic symmetry in the temperature range of 500-600 °C. The P-E and S-E hysteresis loops occurred at room temperature and the apparent maximum in the temperature dependence of the dielectric constant was observed at 520 °C. The temperature dependence of the inverse of magnetic susceptibility exhibited paramagnetic behavior.     

Thermal and rheological behaviours of some random aromatic amino-ended polyethersulfone/polyetherethersulfone copolymers

The thermal and rheological characterizations of seven random, low molecular weight (M_n ≅ 9500 g mol⁻¹), H₂N-ended polyethersulfone/polyetherethersulfone (PES/PEES) copolymers, at various PES/PEES ratios, were performed. The glass transition temperatures (T_g) were determined by DSC. Degradations were carried out in a thermobalance, under flowing nitrogen, in dynamic heating conditions from 35 °C to 650 °C. The initial decomposition temperatures (T_i) and the half decomposition temperatures (T_1/2) were directly determined by TG curves, while the apparent activation energies of degradation (E_a) were obtained by the Kissinger method. In addition, the complex viscosities (η^∗) of the molten polymers were determined in experimental conditions of linear viscoelasticity. T_g, E_a and η^∗ values increased linearly with PES% content, while T_i and T_1/2 values showed opposite behaviour. In every case both PES and PEES homopolymers felt outside linearity. The results obtained are discussed and interpreted, and compared with those of corresponding Cl-ended copolymers previously studied.     

Reduction kinetics of mechanically activated hematite concentrate with hydrogen gas using nonisothermal methods

The reduction kinetics of both non-activated and mechanically activated hematite concentrate in a vibratory mill for different grinding periods have been studied using themogravimetry (TG). Changes in the structure of hematite were studied using X-ray diffraction analysis. The isoconversional method of Kissinger-Akahira-Sunose (KAS) was used to determine the activation energy of the different reactions. The Vyazovkin model-free kinetic method was also used for prediction of kinetic behavior of the samples for a given temperature.Fe₂O₃ was found to reduce to Fe in a two-step via Fe₃O₄. Intensive grinding resulted in improved resolution of overlapping reduction events. It was also established that the mechanical activation had a positive effect on the first step of reduction. With increasing the grinding time, the activation energy at lower extent of conversion (α ≤ 0.11) decreased from 166 to 106 kJ mol⁻¹ range in the initial sample to about 102-70 kJ mol⁻¹ in the sample ground for 9 h. The complexity of the reduction of hematite to magnetite and magnetite to iron was illustrated by the dependence of E on the extent of conversion, α(0.02 ≤ α ≤ 0.95). The values of E decreased sharply with α for 0.02 ≤ α ≤ 0.11 range in the initial sample and mechanically activated samples, followed by a slight decrease in the values of E during further reduction by α ≤ 0.85 in the ground samples up to 3 h. A slight increasing dependence of E on α for mechanically activated sample within 9 h in the second step of reduction was observed due to the finely agglomerated particles during intensive milling and subsequently the formation of a dense layer during the reduction processes. In addition, the dependence of ln A_α on α was detected and it was found that the ln A_α shows the same dependence on α as the apparent activation energies.     

Synthesis and characterization of Zn1−xNixFe2O4 spinels prepared by a citrate precursor

Nanocrystalline single-phase samples of Zn_1−xNi_xFe₂O₄ ferrites (0<x<1) have been obtained via a soft-chemistry method based on citrate-ethylene glycol precursors, at a relatively low temperature (650 °C). The influence of the nickel and zinc contents as well as that of heat treatments were investigated by means of X-ray powder diffraction, Brunauer-Emmett-Teller (BET) surface area, scanning electron microscopy (SEM) and Fourier Transform Infrared (FTIR) Spectroscopy. Higher Ni content increases the surface areas, the largest one (∼20 m²/g) being obtained for NiFe₂O₄ annealed at 650 °C for 15 h. For all compositions, the surface area decreases for prolonged annealing at 650 °C and for higher annealing temperatures. Those results were correlated to the particle size evolution; the smallest particles (∼50 nm) observed in the NiFe₂O₄ sample (650 °C, 15 h) steadily increase as Ni ions were replaced by Zn, reaching ∼100 nm in the ZnFe₂O₄ sample (650 °C, 15 h). For all the Zn_1−xNi_xFe₂O₄ samples and, whatever the heat treatments was, the FTIR spectra show two fundamental absorption bands in the range 650-400 cm⁻¹, characteristics of metal vibrations, without any superstructure stating for cation ordering. The highest ν₁-tetrahedral stretching, observed at ∼615 cm⁻¹ in NiFe₂O₄, shifts towards lower values with increasing Zn, whereas the ν₂-octahedral vibration, observed at 408 cm⁻¹ in NiFe₂O₄, moves towards higher wavenumbers, reaching 453 cm⁻¹ in ZnFe₂O₄.     

Nanocrystalline Ni0.6Zn0.4Fe2O4: A novel semiconducting material for ethanol detection

The structure and crystal phase of the nanocrystalline powders of Ni_1−xZn_xFe₂O₄ (0 ≤ x ≤ 0.5) mixed ferrite, synthesized by ethylene glycol mediated citrate sol-gel method, were characterized by X-ray diffraction and microstructure by transmission electron microscopy. Further studies by Fourier transform infrared spectroscopy were also conducted. Moreover, DC electrical properties of the prepared nanoparticles were studied by DC conductivity measurements. The response of prepared Ni_1−xZn_xFe₂O₄ mixed ferrites to different reducing gases (ethanol, hydrogen sulfide, ammonia, hydrogen and liquefied petroleum gas) was investigated. In particular, Ni_0.6Zn_0.4Fe₂O₄ composition exhibited high response to 100 ppm ethanol gas at 300 °C. Incorporation of palladium further improved the response, selectivity and response time of Ni_0.6Zn_0.4Fe₂O₄ to ethanol gas with the blue shift in the operating temperature by 25 °C.     

Reduction properties of phases in the system La0.5Sr0.5MO3 (M=Fe, Co)

Phases formed by the reduction of compounds of the type La_0.5Sr_0.5MO₃ (M=Fe, Co) have been characterized by means of temperature programmed reduction, X-ray powder diffraction, ⁵⁷Fe Mössbauer spectroscopy and Fe K-, Co K-, Sr K-, and La L_III-edge X-ray absorption spectroscopy. The results show that treatment of the material of composition La_0.5Sr_0.5FeO₃ (which contains 50% Fe⁴⁺ and 50% Fe³⁺) at 650 °C in a flowing 90% hydrogen/10% nitrogen atmosphere results in the formation of an oxygen-deficient perovskite-related phase containing only trivalent iron. Further heating in the gaseous reducing environment at 1150 °C results in the formation of the Fe³⁺-containing phase SrLaFeO₄, which has a K₂NiF₄-type structure, and metallic iron. The material of composition La_0.5Sr_0.5CoO₃ is more susceptible to reduction than the compound La_0.5Sr_0.5FeO₃ since, after heating at 520 °C in the hydrogen/nitrogen mixture, all the Co⁴⁺ and Co³⁺ are reduced to metallic cobalt with the concomitant formation of strontium- and lanthanum-oxides.     

New binuclear vanadium(III) and (IV) squarate species: synthesis, structure and characterization of [V(OH)(H2O)2(C4O4)]2·2H2O and (NH4)[(VO)2(OH)(C4O4)2(H2O)3]·3H2O

Two new vanadium squarates have been synthesized, characterized by infrared and thermal behavior and their structures determined by single crystal X-ray diffraction. Both structures are made of discrete, binuclear vanadium entity but in 1, [V(OH)(H₂O)₂(C₄O₄)]₂·2H₂O the vanadium atom is trivalent and the entity is neutral while in 2, (NH₄)[(VO)₂(OH)(C₄O₄)₂(H₂O)₃]·3H₂O, the vanadium atom is tetravalent and the entity is negatively charged, balanced by the presence of one ammonium ion. Both molecular anions are bridged by two terminal μ₂ squarate ligands. 1 crystallizes in the triclinic system, space group P-1, with lattice constants a=7.5112(10) Å, b=7.5603(8) Å, c=8.2185(8) Å, α=106.904(8)°, β=94.510(10)°, γ=113.984(9)° while 2 crystallizes in the monoclinic system, space group C2/c, with a=14.9340(15) Å, b=6.4900(9) Å, c=17.9590(19) Å and β=97.927(12)°. From the magnetic point of view, V(III) binuclear species show ferromagnetic interactions at low temperatures. However, no anomalies pointing to magnetic ordering are observed down to 2 K.     

Thermodynamic studies on SrFe12O19(s), SrFe2O4(s), Sr2Fe2O5(s) and Sr3Fe2O6(s)

The citrate-nitrate gel combustion route was used to prepare SrFe₂O₄(s), Sr₂Fe₂O₅(s) and Sr₃Fe₂O₆(s) powders and the compounds were characterized by X-ray diffraction analysis. Different solid-state electrochemical cells were used for the measurement of emf as a function of temperature from 970 to 1151 K. The standard molar Gibbs energies of formation of these ternary oxides were calculated as a function of temperature from the emf data and are represented as (SrFe₂O₄, s, T)/kJ mol⁻¹ (±1.7)=−1494.8+0.3754 (T/K) (970?T/K?1151). (Sr₂Fe₂O₅, s, T)/kJ mol⁻¹ (±3.0)=−2119.3+0.4461 (T/K) (970?T/K?1149). (Sr₃Fe₂O₆, s, T)/kJ mol⁻¹ (±7.3)=−2719.8+0.4974 (T/K) (969?T/K?1150).Standard molar heat capacities of these ternary oxides were determined from 310 to 820 K using a heat flux type differential scanning calorimeter (DSC). Based on second law analysis and using the thermodynamic database FactSage software, thermodynamic functions such as Δ_fH°(298.15 K), S°(298.15 K) S°(T), C_p°(T), H°(T), {H°(T)-H°(298.15 K)}, G°(T), free energy function (fef), Δ_fH°(T) and Δ_fG°(T) for these ternary oxides were also calculated from 298 to 1000 K.     

Synthesis, characterization and magnetic property of a new 3D iron phosphite: |C4N3H14|[Fe3(HPO3)4F2(H2O)2] with intersecting channels

A new open-framework iron (III) phosphite |C₄N₃H₁₄|[Fe₃(HPO₃)₄F₂(H₂O)₂] has been solvothermally synthesized by using diethylenetriamine (DETA) as the structure-directing agent. Single-crystal X-ray diffraction analysis reveals that the compound crystallizes in the monoclinic space group C2/c having unit cell parameters a=12.877(3) Å, b=12.170(2) Å, c=12.159(2) Å, β=93.99(3)°, V=1900.9(7) Å³, and Z=4 with R₁=0.0447, wR₂=0.0958. The complex structure consists of HPO₃ pseudo-tetrahedra and {Fe₃O₁₄F₂} trimer building units. The assembly of these building units generates 3D inorganic framework with intersecting 6-, 8-, and 10-ring channels. The DETA cations are located in the 10-ring channels linked by hydrogen bonds. The Mössbauer spectrum shows that there exhibit two crystallographically independent iron (III) atoms. And the magnetic investigation shows the presence of antiferromagnetic interactions. Further characterization of the title compound was performed using X-ray powder diffraction (XRD), infrared (IR) spectra, thermal gravimetric analyses (TGA), inductively coupled plasma (ICP) and elemental analyses.     

Morphological and magnetic study of CaMnO3−x oxides obtained from different routes

The CaMnO_3−x (x=0 and 0.02) mixed oxide was synthesized from both thermal treatment of the [CaMn(C₃H₂O₄)₂(H₂O)₄] metallo-organic precursor and ceramic method. In the case of the latter method, temperatures of 1350 °C and 50 h were necessary; however, lower temperatures, 800 °C, and shorter reaction times, 15 h, were utilized in the attainment of the mixed oxide from the precursor. As a consequence, the morphology of the different products is clearly different. The samples exhibit three-dimensional antiferromagnetic ordering with T_N near 120 K, and a low-dimensional antiferromagnetic ordering at high temperatures. The presence of a ferromagnetic component above T_N was also observed in both compounds, it is slightly stronger in the phase prepared by the ceramic route.     

Conservation of [(C2H4NH3)3N]2·(ZrF7)2·H2O layers during the topotactic dehydration of [(C2H4NH3)3N]2·(ZrF7)2·9H2O

Tren amine cations [(C₂H₄NH₃)₃N]³⁺ and zirconate or tantalate anions adopt a ternary symmetry in two hydrates, [H₃tren]₂·(ZrF₇)₂·9H₂O and [H₃tren]₆·(ZrF₇)₂·(TaOF₆)₄·3H₂O, which crystallise in R32 space group with a_H = 8.871 (2) Å, c_H = 38.16 (1) Å and a_H = 8.758 (2) Å, c_H = 30.112 (9) Å, respectively. Similar [H₃tren]₂·(MX₇)₂·H₂O (M = Zr, Ta; X = F, O) sheets are found in both structures; they are separated by a water layer (O_w(2)-O_w(3)) in [H₃tren]₂·(ZrF₇)₂·9H₂O. Dehydration of [H₃tren]₂·(ZrF₇)₂·9H₂O starts at room temperature and ends at 90 °C to give [H₃tren]₂·(ZrF₇)₂·H₂O. [H₃tren]₂·(ZrF₇)₂·H₂O layers remain probably unchanged during this dehydration and the existence of one intermediate [H₃tren]₂·(ZrF₇)₂·3H₂O hydrate is assumed. O_w(1) molecules are tightly hydrogen bonded with -NH₃⁺ groups and decomposition of [H₃tren]₂·(ZrF₇)₂·H₂O occurs from 210 °C to 500 °C to give successively [H₃tren]₂·(ZrF₆)·(Zr₂F₁₂) (285 °C), an intermediate unknown phase (320 °C) and ZrF₄.     

Synthesis, structure, and characterization of hybrid materials: [Ce(H2O)]2[O2C(CH2)2CO2]3 and [Sm(H2O)]2[O2C(CH2)2CO2]3·H2O

The rare-earth dicarboxylate hybrid materials [Ce(H₂O)]₂[O₂C(CH₂)₂CO₂]₃ ([Ce(Suc)]) and [Sm(H₂O)]₂[O₂C(CH₂)₂CO₂]₃·H₂O ([Sm(Suc)]) have been hydrothermally synthesized (200°C, 3 days) under autogenus pressure. [Ce(Suc)] is triclinic, a=7.961 (3) Å, b=8.176 (5) Å, c=14.32 (2) Å, α=97.07° (7), β=96.75° (8), γ=103.73° (6), and z=2. The crystal structure of this compound has been determined using 3120 unique single crystal data. The final refinements let the agreement factors R₁ and wR₂(F²) converge to 0.0138 and 0.0363, respectively. [Ce(Suc)] is built up from infinite chains of edge-sharing nine-fold coordinated cerium atoms running along [100]. These chains are interconnected by the carbon atoms of the succinate anions, leading to a three-dimensional hybrid framework. The cell constants of [Sm(Suc)], isotypic with monoclinic C2/c [Pr(H₂O)]₂[O₂C(CH₂)₂CO₂]₃·H₂O ([Pr(Suc)]), were refined starting from X-ray powder data: a=20.275 (3) Å, b=7.919 (6) Å, c=14.130 (3) Å, and β=121.45° (1). Despite its lower symmetry, [Ce(Suc)] presents an important structural filiation with [Sm(Suc)]     

Synthesis and structure of BaKFeO3: a new quaternary oxide with 1-D ferrate chains

Amber-colored single crystals of the quaternary oxide BaKFeO₃ were synthesized from a mixture of Fe₂O₃, KOH and Ba(OH)₂ heated at 750°C for 5 h then cooled slowly. The structure was determined by single-crystal X-ray diffraction (space group Cmca; a=5.804(1) Å, b=11.528(1) Å, c=12.776(1) Å; Z=8, R₁=0.0376, wR₂=0.0996). The structure is comprised of [FeO₃³⁻]^∞ chains of corner-sharing iron-oxo tetrahedra that are isolated from one another by interspersed Ba and K cations. The iron coordination environment is moderately distorted from perfect tetrahedral symmetry and the Fe-O-Fe bond angles are 152.8°. Magnetic susceptibility data show a pronounced zero-field cooling effect that suggests strong coupling from 5 K to above room temperature.