Über hexagonale Perowskite mit Kationenfehlstellen. XXVII. Die Systeme Ba4−xSrxBIIRe2□O12′, Ba4BCaxRe2□O12 und Ba4−xLaxBIIRe2−xWx□O12 mit BII = Co,Ni

On Hexagonal Perovskites with Cationic Vacancies. XXVII. Systems Ba_4?xSr_xB^IIRe₂□O₁₂, Ba₄B Ca_xRe₂□O₁₂, and Ba_4?xLa_xB^IIRe_2?xW_x□O₁₂ with B^II = Co, Ni In the systems Ba_4?xSr_xB^IIRe₂□O₁₂, Ba₄BCa_xRe₂□O₁₂ and Ba_4?xLa_xB^IIRe_2?xW_x□O₁₂ (B^II = Co, Ni) hexagonal perovskites with a rhombohedral 12 L structure (general composition A₄BM₂□O₁₂; sequence (hhcc)₃; space group R&3macr;m) are observed. With the exception of Ba₄NiRe₂□O₁₂ the octahedral net consists of BO₆ single octahedra and M₂□O₁₂ face connected blocks (type 1). In type 2 (Ba₄NiRe₂□O₁₂) the M ions are located in the single octahedra and in the center of the groups of three face connected octahedra. The two outer positions of the latter are occupied by B ions and vacancies in the ratio 1:1. The difference between type 1 and 2 are discussed by means of the vibrational and diffuse reflectance spectra.     

Perovskite-like La1−xKxMnO3 and related compounds: Solid state chemistry and the catalysis of the reduction of NO by CO and H2

The new compounds La_1?xM_xMnO₃ (0.05 ? x ? 0.4 for M = K; x = 0.2 for M = Na, Rb) have been prepared. La_1?xK_xMnO₃ (0.05 ? x ? 0.4), LaMnO_3.01, LaMnO_3.15, La_0.8Na_0.2MnO₃, and La_0.8Rb_0.2MnO₃ have been used as catalysts in the reduction of NO. La_0.8K_0.2MnO₃ has also been used in the catalytic decomposition of NO. The activity of these catalysts is related to the presence of a Mn³⁺/Mn⁴⁺ mixed valence and to the relative ease of forming oxygen vacancies in the solid. The presence of cation vacancies in LaMnO_3.15 and the substitution of La³⁺ by alkali ions in LaMnO₃ increases the catalytic activity. The reduction of NO involves both molecular and dissociative adsorption of NO.     

Electrode performance and X-ray absorption spectroscopy of La0.8Sr0.2Mn1−x Cu x O3 (0 ≤ x ≤ 0.2)–GDC composite cathodes for SOFCs

Electrochemical properties of composite cathodes consisting of La_0.8Sr_0.2Mn_1?x Cu _x O₃ (LSMCu, 0?≤?x?≤?0.2) and Ce_0.8Gd_0.2O_2?x (GDC) were determined by impedance spectroscopy, and conduction mechanism for the composite cathodes was investigated by a near-edge X-ray absorption fine-structure analysis (NEXAFS). LSMCu–GDC cathodes showed lower polarization resistance (R _p) than LSM–GDC up to 750 °C, whereas they exhibited better performance at higher temperature (≥800 °C). The best performance was achieved with the LSMCu10–GDC cathode: 0.27 and 0.08?Ω cm² at 800 °C and 850 °C, respectively. NEXAFS and refinement results confirmed that Cu doping caused the oxidation of Mn³⁺ to Mn⁴⁺ and lattice contraction. This additional Mn⁴⁺ can lead to the formation of oxygen vacancies when Mn⁴⁺ is converted to Mn³⁺ at relatively high temperatures (above 600 °C). This in turn contributes to improved oxygen ion transport in LSM. The LSMCu–GDC composite cathode can thus be considered a suitable potential cathode for SOFC applications.     

Strain correlated effect on structural,magnetic, and dielectric properties in Ti4+ substituted Bi0.8Ba0.2Fe1−xTixO3

Ti⁴⁺ substituted Bi_0.8Ba_0.2Fe_1−xTi_xO₃ for x = 0.0, 0.1 and 0.2 are prepared by modified solid state reaction method. The prepared samples sintered at 850 °C for 1 h show a single phase nature. A structural change was observed on Ti⁴⁺ substitutions are confirmed through X-ray Diffraction, Fourier Transform Infrared spectroscopy and Raman spectra. An anomalous phase transition is observed in Bi_0.8Ba_0.2FeO₃ at 1173 K. The absence of ferroelectric transition and enhancement of decomposition temperature is observed in the substituted samples from the thermal analysis. A dielectric spectroscopic measurement shows that on Ti⁴⁺ substitutions, the magnitude of dielectric constant and loss tangent (tan δ) value is decreased. Vibrating Sample Magnetometer (VSM) study shows both antiferromagnetic and ferromagnetic phases coexist in the M−H curve. On Ti⁴⁺ substitutions in Bi_0.8Ba_0.2FeO₃, the antiferromagnetism dominates over the ferromagnetic phase. In corroboration to magnetisation process, ZFC–FC measurement confirms it that on Ti⁴⁺ substitution, the antiferromagnetic behaviour gets dominated. The report suggests that the interplay of strain upon Ti⁴⁺ substitution causes the structural and magnetic phase transition.     

Effects of vacancy concentration on the magnetic and transport properties of (La1−xPbx)1−y□yMnO3

(La_1−xPb_x)_1−y□_yMnO₃ with x=0.05-0.5 and y=0, 0.05, 0.1 (where □ is a vacancy) was studied to evaluate the effects of A-site vacancies on the physical properties. In this system manganese perovskites form with tolerance factors close to 1 and low A-site cation size mismatch due to similarities in the effective ionic radii of La³⁺ and Pb²⁺. Increasing vacancy concentration indicates no significant effect on the lattice parameters or volume. However, the vacancies introduce a greater A-site cation size mismatch, which leads to a lowering of the ferromagnetic and metal-insulator transition temperatures, although the transitions are not broadened with increasing vacancy content. Due to the vacancies a distribution of Mn-O-Mn angles and Mn-O distances are created, and long range order in (La_1−xPb_x)_1−y□_yMnO₃ appears to be determined by Mn-O-Mn angles and Mn-O distances which most distort from 180° and are the longest, respectively, in the structure.     

Synthesis and structural characterization of LaxSr1−xMnO2.6+δ (0.1<x<0.4) compounds displaying compressed octahedral coordination of Mn

La_xSr_1−xMnO_2.6+δ (x=0.1-0.4) compounds have been obtained by low-temperature annealing of stoichiometric materials in hydrogen. La_0.1Sr_0.9MnO_2.6+δ (δ=0.15) and La_0.3Sr_0.7MnO_2.6, tetragonal (P4/m), and La_0.2Sr_0.8MnO_2.6, pseudo-tetragonal monoclinic (P2/m), structures are isostructural with oxygen-vacancy-ordered Sr₅Mn₅O₁₃ (, c≈a_P). La_0.4Sr_0.6MnO_2.6 shows cubic perovskite structure with disordered oxygen vacancies. In the vacancy-ordered (La_xSr_1−x)₅Mn₅O₁₃ phases four out of five Mn cations are Mn³⁺ and show a typical Jahn-Teller elongated pyramidal coordination while the fifth one Mn^(4−5x)+, in octahedral environment, shows decreasing formal charge from Mn⁴⁺ (x=0) to Mn^2.5+x=0.3. This unusual selective doping of the octahedral site produces structural strain due to increasing size of the Mn^(4−5x)+ and, in the case of (La_0.2Sr_0.8)₅Mn₅O₁₃, the unusual compressed octahedral arrangement of oxygen atoms around it. The coordination geometry implies that either the d_x²-y² orbital is occupied, which would be a rare example of inverted occupancy of e_g orbitals in manganites, or that disordered Mn³⁺ apically elongated MnO₆ octahedra are present with normal electronic configuration , and the observed bond distances are the average of the long and intermediate in-plane Mn-O bonds. Several structural features favor the second case.     

Electrical, electrochemical, and thermomechanical properties of perovskite-type (La1?x Sr x )1?y Mn0.5Ti0.5O3?δ (x?=?0.15–0.75, y?=?0–0.05)

Strontium additions in (La_1?x Sr _x )_1?y Mn_0.5Ti_0.5O_3?δ (x?=?0.15–0.75, y?=?0–0.05) having a rhombohedrally distorted perovskite structure under oxidizing conditions lead to the unit cell volume contraction, whilst the total conductivity, thermal and chemical expansion, and steady-state oxygen permeation limited by surface exchange increase with increasing x. The oxygen partial pressure dependencies of the conductivity and Seebeck coefficient studied at 973–1223?K in the p(O₂) range from 10^?19 to 0.5?atm suggest a dominant role of electron hole hopping and relatively stable Mn³⁺ and Ti⁴⁺ states. Due to low oxygen nonstoichiometry essentially constant in oxidizing and moderately reducing environments and to strong coulombic interaction between Ti⁴⁺ cations and oxygen anions, the tracer diffusion coefficients measured by the ¹⁸O/¹⁶O isotopic exchange depth profile method with time-of-flight secondary-ion mass spectrometric analysis are lower compared to lanthanum–strontium manganites. The average thermal expansion coefficients determined by controlled-atmosphere dilatometry vary in the range 9.8–15.0?×?10^?6?K^?1 at 300–1370?K and oxygen pressures from 10^?21 to 0.21?atm. The anodic overpotentials of porous La_0.5Sr_0.5Mn_0.5Ti_0.5O_3?δ electrodes with Ce_0.8Gd_0.2O_2-δ interlayers, applied onto LaGaO₃-based solid electrolyte, are lower compared to (La_0.75Sr_0.25)_0.95Cr_0.5Mn_0.5O_3?δ when no metallic current-collecting layers are introduced. However, the polarization resistance is still high, ~2 Ω?×?cm² in humidified 10?% H₂–90?% N₂ atmosphere at 1073?K, in correlation with relatively low electronic conduction and isotopic exchange rates. The presence of H₂S traces in H₂-containing gas mixtures did not result in detectable decomposition of the perovskite phases.     

Influence of the structure on electric and magnetic properties of La0.8Na0.2Mn1−xCoxO3 perovskites

The influence of the cobalt substitution for manganese ions in the mixed valence perovskites La_0.8Na_0.2Mn_1−xCo_xO₃ (0?x?0.2) was investigated by X-ray, electric transport and magnetic measurements. The study carried out on sintered polycrystalline samples revealed the rhombohedral () structure and the insulator-metal transition connected with a ferromagnetic arrangement in the whole concentration range. Increasing concentration of cobalt ions leads to a gradual decrease of PM-FM and I-M transition temperatures. An influence of the cobalt ions on the observed behavior is attributed to charge compensation Mn³⁺→Mn⁴⁺ leading to the formation of stable couples Mn⁴⁺-Co²⁺. Therefore the double-exchange interactions Mn³⁺-O²⁻-Mn⁴⁺ partly vanish and they are replaced by positive superexchange interactions Mn⁴⁺-O²⁻-Co²⁺, but of a semiconducting character.     

Synthesis and characterization of La0.8Sr1.2Co0.5M0.5O4−δ (M=Fe, Mn)

The M⁴⁺-containing K₂NiF₄-type phases La_0.8Sr_1.2Co_0.5Fe_0.5O₄ and La_0.8Sr_1.2Co_0.5Mn_0.5O₄ have been synthesized by a sol–gel procedure and characterized by X-ray powder diffraction, thermal analysis, neutron powder diffraction and Mössbauer spectroscopy. Oxide ion vacancies are created in these materials via reduction of M⁴⁺ to M³⁺ and of Co³⁺ to Co²⁺. The vacancies are confined to the equatorial planes of the K₂NiF₄-type structure. A partial reduction of Mn³⁺ to Mn²⁺ also occurs to achieve the oxygen stoichiometry in La_0.8Sr_1.2Co_0.5Mn_0.5O_3.6. La_0.8Sr_1.2Co_0.5Fe_0.5O_3.65 contains Co²⁺ and Fe³⁺ ions which interact antiferromagnetically and result in noncollinear magnetic order consistent with the tetragonal symmetry. Competing ferromagnetic and antiferromagnetic interactions in La_0.8Sr_1.2Co_0.5Fe_0.5O₄, La_0.8Sr_1.2Co_0.5Mn_0.5O₄ and La_0.8Sr_1.2Co_0.5Mn_0.5O_3.6 induce spin glass properties in these phases.     

Synthesis and characterization of La0.8Sr1.2Co0.5M0.5O4−δ (M=Fe, Mn)

The M⁴⁺-containing K₂NiF₄-type phases La_0.8Sr_1.2Co_0.5Fe_0.5O₄ and La_0.8Sr_1.2Co_0.5Mn_0.5O₄ have been synthesized by a sol-gel procedure and characterized by X-ray powder diffraction, thermal analysis, neutron powder diffraction and Mössbauer spectroscopy. Oxide ion vacancies are created in these materials via reduction of M⁴⁺ to M³⁺ and of Co³⁺ to Co²⁺. The vacancies are confined to the equatorial planes of the K₂NiF₄-type structure. A partial reduction of Mn³⁺ to Mn²⁺ also occurs to achieve the oxygen stoichiometry in La_0.8Sr_1.2Co_0.5Mn_0.5O_3.6. La_0.8Sr_1.2Co_0.5Fe_0.5O_3.65 contains Co²⁺ and Fe³⁺ ions which interact antiferromagnetically and result in noncollinear magnetic order consistent with the tetragonal symmetry. Competing ferromagnetic and antiferromagnetic interactions in La_0.8Sr_1.2Co_0.5Fe_0.5O₄, La_0.8Sr_1.2Co_0.5Mn_0.5O₄ and La_0.8Sr_1.2Co_0.5Mn_0.5O_3.6 induce spin glass properties in these phases.     

X-ray photoelectron spectroscopy investigation of perovskites La1−x Sr x FeO3−y (0 ≤x < 1.0), prepared via a mechanochemical route

Perovskite-structure oxides La_1?x Sr _x FeO_3?y (x = 0, 0.2, 0.6, 1) were synthesized by the mechanochemical method. In order to refine the stoichiometric composition and the charge state of ions, these samples were studied by X-ray photoelectron spectroscopy (XPS). An investigation of perovskites with x = 0, 0.2, and 0.6 in air at room temperature showed that these samples do not contain oxygen vacancies (y = 0), i.e., they are fully oxidized. Hence, to produce electrical neutrality, these samples should contain iron(4+) cations in an amount proportional to the degree of substitution (x) of strontium(2+) for lanthanum(3+). However, no Fe⁴⁺ cations were found in the oxides. All perovskites contain only Fe³⁺ cations, oxygen ions O^2? along with oxygen ions with reduced electron density (O^?). These data provid evidence of the possible electron density redistribution from oxygen ions to iron cations. The fact that the oxides contain oxygen ions with reduced electron density suggests that weakly bound lattice oxygen in substituted perovskites is represented by O^? ions.     

Aurivillius phases of PbBi4Ti4O15 doped with Mn synthesized by molten salt technique: Structure, dielectric, and magnetic properties

Doping of manganese (Mn³⁺/Mn⁴⁺) into the Aurivillius phase Pb_1−xBi_4+xTi_4−xMn_xO₁₅ was carried out using the molten salt technique for various Mn concentrations (x=0, 0.2, 0.4, 0.6, 0.8, and 1). Single phase samples could be obtained in the composition range with x up to 0.6 as confirmed by X-ray and neutron diffraction analysis. Dielectric measurements show a peak at 801, 803, 813 and 850 K for samples with x=0, 0.2, 0.4, and 0.6, respectively, related to the ferroelectric transition temperature (T_c). The main contribution of the in-plane polarization for x≤0.2 which was calculated from the atomic positions obtained by the structure analysis is the dipole moment in the Ti(1)O₆ layer; however, for x≥0.4 the polarization originates from the dipole moment in the Ti(2)O₆ layer. Mn doping in the Pb_1−xBi_4+xTi_4−xMn_xO₁₅ does not show any long range magnetic ordering.     

Die Photolumineszenz der dreiwertigen Seltenen Erden in den Perowskitstapelvarianten Ba2La2−xSE MgW2□O12, Ba6Y2−xSEW3□O18 und Sr8SrGd2−x SEW4□O24

Photoluminescence of Trivalent Rare Earths in Perovskite Stacking Polytypes Ba₂La_2?x RE MgW₂□O₁₂, Ba₆Y_2?x RE W₃□O₁₈, and Sr₈SrGd_2?xRE W₄□O₂₄ Rhombohedral 12 L stacking polytypes Ba₂La_2?xREMgW₂□O₁₂ show with RE³⁺ = Pr, Sm, Eu, Tb, Dy, Ho, Er, Tm; the 18 L stacking polytypes Ba₆Y_2?xREW₃□O₁₈ and the polymorphic perovskites Sr₈SrGd_2?xREW₄□O₂₄ with RE³⁺ = Sm, Eu, Dy, Ho, Er visible photoluminescence. The concentration dependence and the influence of the coordination number of the rare earth are reported.     

Über hexagonale Perowskite mit Kationenfehlstellen. XXXII. Die Photolumineszenz der dreiwertigen Seltenen Erden in den Systemen Ba2−ySryLa2−xSExMgW2□O12

On Hexagonal Perovskites with Cationic Vacancies. XXXII. Photoluminescence of Trivalent Rare Earth in the Systems Ba_2?ySr_yLa_2?xRE_xMgW₂□O₁₂ In the series Ba_2?ySr_yLa_2?xRE_xMgW₂□O₁₂ the Ba²⁺ can be completely substituted by Sr²⁺. All compounds crystallize in the rhombohedral 12 L-type (space group R3 m; sequence (hhcc)₃). By doping the stacking polytypes with some of the trivalent rare earths efficient visible photoluminescence is obtained. The simultaneous incorporation of two different rare earth ions leads to two-color-phosphors, which, according to the excitation energy used, emit either mainly the typical spectrum from one or the other activator; the corresponding luminescence mechanism are discussed.     

Synthesis and characterization of A-site deficient rare-earth doped BaZrxTi1−xO3 perovskite-type compounds

A-site deficient rare-earth doped BaZr_xTi_1?xO₃ (BZT) ceramics were prepared from a soft-chemistry route and by solid-state reaction (SSR). Perovskite-like single-phase diagrams for the BaTiO₃–La_2/3TiO₃–BaZrO₃ system were constructed for each method of synthesis. Infrared spectroscopy on (Ba_1?yLa_2y/3)Zr_xTi_1?xO₃ solid solution revealed a dramatic stress on the M–O (M = Ti, Zr) bonds due to the combined effect of A-site vacancies and the lower ionic radius of La³⁺ than that of Ba²⁺. A relationship between the M–O stretching vibration (υ) and the tolerance factor (t) was determined. (Ba_1?yLn_2y/3)Zr_0.09Ti_0.91O₃ (Ln = La, Pr, Nd) samples synthesized by SSR were selected for detailed studies. X-ray diffraction data were refined by the Rietveld method. Scanning electron microscopy on sintered compacts detected abnormal crystal growth and grain sizes in the range of about 1 μm up to 10 μm when the dopant concentration is 6.7 at. %. Impedance measurements exhibited that ferroelectric to paraelectric phase-transition temperature shifted to lower values as increasing rare-earth content. (Ba_1?yLn_2y/3)Zr_0.09Ti_0.91O₃ system showed a diffuse phase transition with a relaxor-like ferroelectric behaviour. Furthermore, the dielectric constant was enhanced with respect to non-doped BZT system.     

Crystal structure and electrical conductivity of lanthanum-calcium chromites-titanates La1−xCaxCr1−yTiyO3−δ (x=0-1, y=0-1)

Five series of perovskite-type compounds in the system La_1−xCa_xCr_1−yTi_yO₃ with the nominal compositions y=0, x=0-0.5; y=0.2, x=0.2-0.8; y=0.5, x=0.5-1.0; y=0.8, x=0.6-1.0 and y=1, x=0.8-1 were synthesized by a ceramic technique in air (final heating 1350 °C). On the basis of the X-ray analysis of the samples with (Ca/Ti)?1, the phase diagram of the CaTiO₃-LaCr^IIIO₃-CaCr^IVO₃ quasi-ternary system was constructed. Extended solid solution with a wide homogeneity range is formed in the quasi-ternary system CaCr^IVO₃-CaTiO₃-LaCr^IIIO₃. The solid solution La_{(1−x′−y)}Ca_(x′+y)Cr^IV_x′Cr^III_{(1−x′−y)}Ti_yO₃ exists by up to 0.6-0.7 mol fractions of CaCr^IVO₃ (x^′<0.6-0.7) at the experimental conditions. The crystal structure of the compounds is orthorhombic in the space group Pbnm at room temperature. The lattice parameters and the average interatomic distances of the samples within the solid solution ranges decrease uniformly with increasing Ca content. Outside the quasi-ternary system, the nominal compositions La_0.1Ca_0.9TiO₃, La_0.2Ca_0.8TiO₃, La_0.4Ca_0.6Cr_0.2Ti_0.8O₃ and La_0.3Ca_0.7Cr_0.2Ti_0.8O₃ in the system La_1−xCa_xCr_1−yTi_yO₃ were found as single phases with an orthorhombic structure. In the temperature range between 850 and 1000 °C, the synthesized single-phase compositions are stable at pO₂=6×10⁻¹⁶-0.21×10⁵ Pa. Oxygen stoichiometry and electrical conductivity of the separate compounds were investigated as functions of temperature and oxygen partial pressure. The chemical stability of these oxides with respect to oxygen release during thermal dissociation decreases with increasing Ca-content. At 900 °C and oxygen partial pressure 1×10⁻¹⁵-0.21×10⁵ Pa, the compounds with x>y (acceptor doped) are p-type semiconductors and those with x<y (donor doped) and x=y are n-type semiconductors. The type and level of electrical conductivity are functions of the concentration ratios of cations occupying the B-sites of the perovskite structures: [Cr³⁺]/[Cr⁴⁺] and [Ti⁴⁺]/[Ti³⁺]. The maximum electrical conductivity at 900 °C and pO₂=10⁻¹⁵ Pa was found for the composition La_0.1Ca_0.9TiO₃ (near 50 S/cm) and in air at 900 °C for La_0.5Ca_0.5CrO₃ (close to 100 S/cm).     

Magnetic interactions in ternary cobalt oxides with cubic perovskite structure

Magnetic properties were measured on the cubic perovskite systems SrCoO_3?δ, (La_1?xSr_x)CoO₃ (0.5 ≦ x ≦ 1.0), and Sr(Co_1?xMn_x)O₃ (0 ≦ x ≦ 1.0). It is found that S²⁺ and La³⁺ ions strongly affect the spin state of the Co²⁺ ion and that the Mn⁴⁺ ion located at the octahedral site affects the spin state of Co⁴⁺ ion. The magnetic properties (T_c, T_θ, and σ) are explained by the magnetic interaction Co³⁺OCo³⁺, Co³⁺OCo⁴⁺, Co⁴⁺OCo⁴⁺, Mn⁴⁺OMn⁴⁺, and Mn⁴⁺OCo⁴⁺ in these systems.     

The reduction of alkali substituted LaMnO3

In order to determine the stability of some potential NO_x reduction catalysts (La_0.8M_0.2MnO₃, M  Na, K, Rb) the accelerated reduction of these catalysts in H₂, N₂ atmospheres was studied. La_0.8K_0.2MnO₃ goes through a reversible oxygen loss at about 350°C corresponding to the reduction of the available Mn⁴⁺ to Mn³⁺ in H₂, N₂ atmospheres. By reduction at higher temperatures a previously unreported phase La₂MnO₄ is formed. The most reducing conditions (10% H₂ in N₂, >940°C) formed only La₂O₃ and MnO. Between 700 and 880°C in 10% H₂ in N₂ potassium was eliminated from the sample by reduction to the metal and evaporation. Analogous results were found for Na and Rb substituted LaMnO₃ except that the intermediate phase La₂MnO₄ was not observed in the reduction of La_0.8Rb_0.2MnO₃.     

Structural,Magnetic and Catalytic Properties of a New Vacancy Ordered Perovskite Type Barium Cobaltate BaCoO2.67

A new vacancy ordered, anion deficient perovskite modification with composition of BaCoO_2.67 (Ba₃Co₃O₈□₁) has been prepared via a two-step heating process. Combined Rietveld analysis of neutron and X-ray powder diffraction data shows a novel ordering of oxygen vacancies not known before for barium cobaltates. A combination of neutron powder diffraction, magnetic measurements, and density functional theory (DFT) studies confirms G-type antiferromagnetic ordering. From impedance measurements, the electronic conductivity of the order of 10⁻⁴ S cm⁻¹ is determined. Remarkably, the bifunctional catalytic activity for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is found to be comparable to that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3–y, confirming that charge-ordered anion deficient non-cubic perovskites can be highly efficient catalysts.     

First principles study of structure and properties of La- and Mn-modified BiFeO3

First principles calculations have been performed to study the effects of the La³⁺ and Mn³⁺ substitutions in the multiferroic BiFeO₃. The real compositions Bi_1−xLa_xFeO₃ and BiFe_1−xMn_xO₃ with x = 0.0, 0.1, 0.2, 0.3 were modeled by substitution of one, two and three Bi³⁺ or Fe³⁺ by La³⁺ or Mn³⁺ in the orthorhombic BiFeO₃ structure, respectively. Density functional theory within the generalized gradient approximation with Hubbard correction of Dudarev (GGA + U) and plane wave pseudo-potential approach has been used to track the changes that occur in the structural parameters, electronic structure, magnetic, optical and polarization properties of the modified BiFeO₃. The substitution of one Bi³⁺ with La³⁺ increases the band gap energy whereas the augmentation of La³⁺ substitutes decreases it. The substitutions of Fe³⁺ with Mn³⁺ do not change the band gap energy. The calculations predicted larger polarization of the modified BiFeO₃, antiferromagnetism for Bi_1−xLa_xFeO₃ and small ferrimagnetism for BiFe_1−xMn_xO₃. Better multiferroic properties are expected for BiFe_1−xMn_xO₃ materials (x = 0.1, 0.2) due to the increasing polarization and ferrimagnetic behavior. The optical properties were estimated by the calculated imaginary and real parts of the dielectric function. The increase of La³⁺ and Mn³⁺ substitutes lead to lower absorption intensity at energy range 2–7 eV.