Structural studies of TcO2 by neutron powder diffraction and first-principles calculations

Crystalline technetium dioxide was prepared and for the first time its crystal structure determined by neutron powder diffraction. In addition, electronic structure calculations using density functional theory were performed to further elucidate the bonding mechanisms in TcO2. The crystal structure determined by Rietveld analysis with the NPD data is of a distorted rutile type, similar to that of MoO2; space group P21/c, a = 5.6891(1), b = 4.7546(1), c = 5.5195(1) A, and beta = 121.453(1) degrees . The NPD analysis also establishes a new neutron scattering length of 6.00(3) fm for 99Tc. Our results clearly show metal-metal bonding between Tc pairs along the edge-sharing chains of TcO6 octahedra. The Tc-Tc bond was found to be 2.622(1) A from NPD profile analysis and 2.59 A from first-principles DFT calculations. The bond is somewhat longer than expected from earlier predictions, suggesting that the nature of the Tc-Tc interaction is weaker than anticipated for the Tc(IV) cation with three outer electrons. The NPD results supported by the DFT calculations suggest that the filling of antibonding orbitals and the influence of the crystal field stabilization of the d3 Tc cations lead to more regular TcO6 octahedra and diminish the metal-metal bond strength compared with closely related oxides such MoO2 and WO2.     

Fabrication and Properties of Technetium-bearing Pyrochlores and Perovskites as Potential Waste Forms

Technetium-99 is one of the most abundant, long-lived radiotoxic isotopes in used nuclear fuel (UNF). As such, it is targeted in UNF separation strategies such as UREX+, for isolation and encapsulation in solid waste forms for storage in a nuclear repository. We report here results regarding the incorporation of Tc-99 into ternary oxides of different structure types: pyrochlore (Nd2Tc2O7), perovskite (SrTcO3), and layered perovskite (Sr2TcO4). The goal was to determine synthesis conditions of these potential waste forms to immobilize Tc-99 and to harvest crystallographic, thermophysical and hydrodynamic data. Within these studies, Rietveld structure refinement was applied to allow for crystallographic characterization, while a physical property measurement system (PPMS) was used to determine thermophysical properties. The ternary oxides exhibited good crystallinity and their lattice parameters and atomic coordinates could be refined to high accuracy. Low refinement residuals (RBragg) of 2.0, 2.4, and 3.9% were achieved for Nd2Tc2O7, SrTcO3, and Sr2TcO4, respectively. The strontium technetates, SrTcO3 and Sr2TcO4, show superconductivity at rather high critical temperatures of Tc = 7.8 K and 7 K, respectively. Nd2Tc2O7 did not show any changes in magnetic properties above 3 K.     

Electronic and molecular structures of trans-dioxotechnetium(V) polypyridyl complexes in the solid state

The structures of novel Tc(V) complexes trans-[TcO(2)(py)(4)]Cl·2H(2)O (1a), trans-[TcO(2)(pic)(4)]Cl·2H(2)O (2a), and trans-[TcO(2)(pic)(4)]BPh(4) (2b) were determined by X-ray crystallography, and their spectroscopic characteristics were investigated by emission spectroscopy and atomic scale calculations. The cations adopt a tetragonally distorted octahedral geometry, with a trans orientation of the apical oxo groups. trans-[TcO(2)(pic)(4)]BPh(4) has an inversion center located on technetium; however, for trans-[TcO(2)(py)(4)]Cl·2H(2)O and trans-[TcO(2)(pic)(4)]Cl·2H(2)O, a strong H bond formed by only one of the oxo substituents introduces an asymmetry in the structure, resulting in inequivalent trans Tc-N and Tc═O distances. Upon 415 nm excitation at room temperature, the complexes exhibited broad, structureless luminescences with emission maxima at approximately 710 nm (1a) and 750 nm (2a, 2b). Like the Re(V) analogs, the Tc(V) complexes luminesce from a (3)E(g) excited state. Upon cooling the samples from 278 to 8 K, distinct vibronic features appear in the spectra of the complexes along with increases in emission intensities. The low temperature emission spectra display the characteristic progressions of the symmetric O═Tc═O and the Tc-L stretching modes. Lowest-energy, triplet excited-state distortions calculated using a time-dependent theoretical approach are in good agreement with the experimental spectra. The discovery of luminescence from the trans-dioxotechnetium(V) complexes provides the first opportunity to directly compare fundamental luminescence properties of second- and third-row d(2) metal-oxo congeners.     

Bismuth(Ⅲ) Complexes with N,N-Di(2-hydroxylethyl)amino-dithiocarboxylate: Synthesis and Crystal Structure of {Bi[S_2CN(C_2H_4OH)_2]_2[1,10-Phen]_2(NO_3)}·3H_2O and {Bi[S_2CN(C_2H_4OH)_2]_3}_2

Introduction The chemistry of organotin(IV) dithiocarbamate complexes was extensively studied due to their biological activities.1-5 To date, a large number of transition-metal complexes with dithiocarbamate have been synthesized and structurally characterized,6-9 including Ni(S2CNC4H8O)2, Cu(S2CNC4H8)2, Zn(S2CNC4H8O)2 and Fe(S2CNC4H8O)2(DMF). However, the chemistry of main-group metal complexes with dithiocarbamate has been scarcely studied, and few reports have appeared on the s…     

Remarkable rare-earth metal silicide oxides with planar Si6 rings

New rare-earth silicide oxides, La10Si8O3 (1) and Ce10Si8O3 (2), were synthesized through high-temperature reactions of the pure elements under controlled oxygen atmosphere conditions. The remarkable silicides crystallize in a unique crystal structure (space group P6/mmm; a = 10.975(3) A (La) and 10.844(1) A (Ce); c = 4.680(1) A (La) and 4.561(1) A (Ce)) that features a 3-D framework of corner-shared O-centered (La/Ce)6 octahedra, reminiscent of hexagonal tungsten bronzes, with planar Si6 rings enclosed within its hexagonal channels. Band structure calculations indicate the compounds are metallic, with optimized La-Si bonds, and a benzene-like [Si6]6- anion. Compound 1 exhibits temperature independent paramagnetism. Compound 2 exhibits Curie-Weiss paramagnetism, and an antiferromagnetic ordering below 7 K.     

Technetium(VII)-oxid: Ein Übergangsmetalloxid mit Molekülstruktur im festen Zustand

Tc₂O₇ crystallizes in the orthorhombic space group Pbca with a = 13.756, b = 7.439, c = 5.617 Å, Z = 4. The single crystal structure analysis shows the crystals to contain isolated centrosymmetric Tc₂O₇ molecules with a linear central Tc? O? Tc bridge and with, tetrahedral coordination of the Tc atoms. Tc? O bond lengths: 1.840 (bridge), 1.658, 1.684 and 1.706 Å. The structure is more closely related to CrO₃, RuO₄ and OsO₄ than to Re₂O₇. Structural properties of the d° transition metal oxides are briefly discussed.     

Polynuclear bismuth-oxo clusters: insight into the formation process of a metal oxide

The reaction of the bismuth silanolates [Bi(OSiR2R')3] (R = R' = Me, Et, iPr; R = Me, R' = tBu) with water has been studied. Partial hydrolysis gave polynuclear bismuth-oxo clusters whereas amorphous bismuth-oxo(hydroxy) silanolates were obtained when an excess of water was used in the hydrolysis reaction. The metathesis reaction of BiCl3 with NaOSiMe3 provided mixtures of heterobimetallic silanolates. The molecular structures of [Bi18Na4O20(OSiMe3)18] (2), [Bi33NaO38(OSiMe3)24].3 C7H8 (3.3 C7H8), [Bi50Na2O64(OH)2(OSiMe3)22].2 C7H8.2H2O (4.2 C7H8.2 H2O), [Bi4O2(OSiEt3)8] (5), [Bi9O7(OSiMe3)13].0.5 C7H8 (6. 0.5C7H8), [Bi18O18(OSiMe3)18)].2C7H8 (7. 2C7H8) and [Bi20O18(OSiMe3)24].3C7H8 (8.3C7H8) are presented and compared with the solid-state structures of [Bi22O26(OSiMe2tBu)14] (9) and beta-Bi2O3. Compound 2 crystallises in the triclinic space group P1 with the lattice constants a = 17.0337(9), b = 19.5750(14), c = 26.6799(16) A, alpha = 72.691(4), beta = 73.113(4) and gamma = 70.985(4) degrees ; compound 3.3C7H8 crystallises in the monoclinic space group P2(1)/n with the lattice constants a = 20.488(4), b = 22.539(5), c = 26.154(5) A and beta = 100.79(3) degrees ; compound 4.2C7H82 H2O crystallises in the monoclinic space group P2(1)/n with the lattice constants a = 20.0518(12), b = 24.1010(15), c = 27.4976(14) A and beta = 103.973(3) degrees ; compound 5 crystallises in the monoclinic space group P2(1)/c with the lattice constants a = 25.256(5), b = 15.372(3), c = 21.306(4) A and beta = 113.96(3) degrees ; compound 6.0.5C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 15.1916(9), b = 15.2439(13), c = 22.487(5) A, alpha = 79.686(3), beta = 74.540(5) and gamma = 66.020(4) degrees ; compound 7.2C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 14.8295(12), b = 16.1523(13), c = 18.4166(17) A, alpha = 75.960(4), beta = 79.112(4) and gamma = 63.789(4) degrees ; and compound 8.3C7H8 crystallises in the triclinic space group P1 with the lattice constants a = 17.2915(14), b = 18.383(2), c = 18.4014(18) A, alpha = 95.120(5), beta = 115.995(5) and gamma = 106.813(5) degrees . The molecular structures of the bismuth-rich compounds are related to the CaF2-type structure. Formally, the hexanuclear [Bi6O8]2+ fragment might be described as the central building unit, which is composed of bismuth atoms placed at the vertices of an octahedron and oxygen atoms capping the trigonal faces. Depending on the reaction conditions and the identity of R, the thermal decomposition of the hydrolysis products [Bi(n)O(l)(OH)(m-)(OSiR3)(3n-(2l-m))] gives alpha-Bi2O3, beta-Bi2O3, Bi12SiO20 or Bi4Si3O12.     

Syntheses，Structures and Properties of Some New Composition Perovskite Compounds：Sr_（0．6）Bi_（0．4）FeO_（2．7），Sr_（1－x）Bi_xFeO_（3－y） and Ba_（1．5）Pt_（0．5）Mn_2O_6

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Photoreduction of 99Tc pertechnetate by nanometer-sized metal oxides: new strategies for formation and sequestration of low-valent technetium

Technetium-99 ((99)Tc) (β(-)(max): 293.7 keV; t(1/2): 2.1 × 10(5) years) is a byproduct of uranium-235 fission and comprises a large component of radioactive waste. Under aerobic conditions and in a neutral-basic environment, the pertechnetate anion ((99)TcO(4)(-)) is stable. (99)TcO(4)(-) is very soluble, migrates easily through the environment and does not sorb well onto mineral surfaces, soils, or sediments. This study moves forward a new strategy for the reduction of (99)TcO(4)(-) and the chemical incorporation of the reduced (99)Tc into a metal oxide material. This strategy employs a single material, a polyoxometalate (POM), α(2)-[P(2)W(17)O(61)](10-), that can be photoactivated in the presence of 2-propanol to transfer electrons to (99)TcO(4)(-) and incorporate the reduced (99)Tc covalently into the α(2)-framework to form the (99)Tc(V)O species, (99)Tc(V)O(α(2)-P(2)W(17)O(61))(7-). This occurs via the formation of an intermediate species that slowly converts to (99)Tc(V)O(α(2)-P(2)W(17)O(61))(7-). Extended X-ray absorption fine structure and X-ray absorption near-edge spectroscopy analysis suggests that the intermediate consists of a (99)Tc(IV) α(2)- species where the (99)Tc is likely bound to two of the four W-O oxygen atoms in the α(2)-[P(2)W(17)O(61)](10-) defect. This intermediate then oxidizes and converts to the (99)Tc(V)O(α(2)-P(2)W(17)O(61))(7-) product. The reduction and incorporation of (99)TcO(4)(-) was accomplished in a "one pot" reaction using both sunlight and UV irradiation and monitored as a function of time using multinuclear nuclear magnetic resonance and radio thin-layer chromatography. The process was further probed by the "step-wise" generation of reduced α(2)-P(2)W(17)O(61)(12-) through bulk electrolysis followed by the addition of (99)TcO(4)(-). The reduction and incorporation of ReO(4)(-), as a nonradioactive surrogate for (99)Tc, does not proceed through the intermediate species, and Re(V)O is incorporated quickly into the α(2)-[P(2)W(17)O(61)](10-) defect. These observations are consistent with the periodic trends of (99)Tc and Re. Specifically, (99)Tc is more easily reduced compared to Re. In addition to serving as models for metal oxides, POMs may also provide a suitable platform to study the molecular level dynamics and the mechanisms of the reduction and incorporation of (99)Tc into a material.     

Synthesis and structural investigation of a unique columnar phase in the Bi2O3–TeO2–V2O5 System

A new columnar phase Bi(11.65)Te(1.35)V(5)O(34-δ) (δ ～ 1.3) containing VO(4) tetrahedra has been identified for the first time in the Bi(2)O(3)-TeO(2)-V(2)O(5) system. The phase formation and the extent of substitution of Te(4+) for Bi(3+) ions in order to stabilize V(5+) in this composition have been confirmed by the single crystal analysis, combined with the powder X-ray diffraction of the solid state synthesized bulk crystalline samples. The oxide crystallizes in a monoclinic crystal system, space group P2/c, with unit cell parameters a = 11.4616(7) ?, b = 5.7131(3) ?, c = 23.5090(18) ?, β = 101.071° (6) (Z = 2). The structure retains the basic features of the columnar oxides with the presence of [Bi(10.65)Te(1.35)O(14)](n)(9.35n+) columns along the (010) direction, surrounded by (VO(4)) tetrahedra placed in the planes parallel to (100) and (001), with an isolated bismuth atom in between the columns. The composition with a limited Te(4+) substitution, Bi(11.65)Te(1.35)V(5)O(34-δ) (δ ～ 1.3), exists with a surprisingly high oxygen deficiency as compared to the stoichiometrically known columnar oxides such as Bi(13)Mo(4)VO(34), Bi(12)Te(1)Mo(3)V(2)O(34), and Bi(11)Te(2)Mo(2)V(3)O(34). The structure of this interesting member of the columnar family of oxides based on the single crystal X-ray diffraction and the Raman spectroscopic studies indicates the possibility of the distribution of the oxygen vacancies among the VO(4) tetrahedral units. Further confirmation for the formation of vanadium stabilized columnar structures has been provided by the successful preparation of Bi(11.65)Te(1.35)V(4)CrO(34-δ) (δ ～ 0.83) and Bi(11.65)Te(1.35)V(4)WO(34-δ) (δ ～ 0.83) phases. Preliminary investigation of the photocatalytic efficiencies of the oxides Bi(11.65)Te(1.35)V(5)O(34-δ), Bi(11.65)Te(1.35)V(4)CrO(34-δ), and Bi(11.65)Te(1.35)V(4)WO(34-δ) revealed moderate photocatalytic activities for the decomposition of the dyes such as Rhodamine B under UV-vis light irradiation.     

Ba11Cd8Bi14: bismuth zigzag chains in a ternary alkaline-earth transition-metal Zintl phase

A new transition-metal-containing Zintl phase, Ba11Cd8Bi14, has been synthesized by a Cd-flux reaction, and its structure has been determined by a single-crystal X-ray diffraction. Ba11Cd8Bi14 crystallizes in the monoclinic space group C2/m (No. 12, Z = 2) with a = 28.193(8) A, b = 4.8932(14) A, c = 16.823(5) A, and beta = 90.836(4) degrees , taken at -150 degrees C (R1 = 0.0407, wR2 = 0.1016). The structure can be described as being built of complex polyanionic [Cd8Bi14]22- layers running along the b axis, which are separated by the Ba2+ cations. An interesting feature of these layers is that they are composed of novel centrosymmetric chains of corner- and edge-shared CdBi4 tetrahedra, interconnected through exo-Bi-Bi bonds. These bonds connect terminal Bi atoms from adjacent chains in such a way that infinite zigzag chains of bismuth parallel to the same direction are formed. Electronic band structure calculations performed using the TB-LMTO-ASA method show a very small band gap, suggesting a narrow-gap semiconducting or poor metallic behavior for Ba11Cd8Bi14. The crystal orbital Hamilton population (COHP) analysis on the homo- and heteroatomic interactions in this structure is reported as well.     

Hydrothermal Synthesis and Structure of a Novel Binuclear Molybdenum Complex with Oxalate Ligand,(enH2){NH4[Co(en)3][Mo2O7(C2O4)]}2·2H2O

The title complex (enH2){NH4[Co(en)3][Mo2O7(C2O4)]}2·2H2O (C18H70Co2Mo4- N16O24, Mr = 1396.52) was obtained under hydrothermal conditions and its crystal structure has been determined by single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c with a = 17.8023(8), b = 7.7527(4), c = 16.9781(4)A,β= 103.878(7)°, V = 2274.8(2) A3, Dc = 2.039 g/cm3, Z = 2,μ(MoKα) = 1.878 mm-1 and F(000) = 1408. The final R = 0.0410 and Wr = 0.1070 for 4065 observed reflections with I≥2σ(I). The crystal structure is composed of bi- nuclear [Mo2O7(C2O4)]4- anions, complex [Co(en)3]2+ cations, protonated ethylenediamine cations, ammonium cations and crystal water molecules, which are held together into a three-dimensional network via hydrogen-bonding interactions. The binuclear structure of [Mo2O7(C2O4)]4- consist of one MoO4 and one MoO6 octahedra through sharing a bridging oxygen atom, where the oxalate ligand acts as a bidentate ligand coordinating to the octahedral molybdenum atom though two deprotonated corboxylate groups.     

Luminescence from the trans-dioxotechnetium(V) chromophore

The luminescence of trans-[TcO2(L)4]+ (L = pyridine (py) or picoline (pic)) and trans-[TcO2(CN)4]3- at room and low temperature is described and represents the first example of room temperature excited-state luminescence observed for Tc complexes. At room temperature, the complexes exhibited broad luminescence with emission maxima ranging from 745 to 780 nm. Analogous to the Re complexes (emission at 635-655 nm), the low-temperature emission spectra of microcrystalline samples of [TcO2(py)4]BPh4 and [TcO2(pic)4]BPh4 display the characteristic progressions of the symmetric O=Tc=O and Tc-L stretching modes. DFT/TDDFT calculations were performed on the trans-[MO2(L)4]+ (M = Re, Tc) congeners and predicted the dioxotechnetium emission to be 0.41 eV lower in energy than its Re analogue. Low-temperature lifetimes (8 K) ranging from 15 to 1926 mus for the series of Tc complexes are consistent with the Re analogues.     

极性金属间化合物MgIn2的合成、晶体结构及能带特征

在惰性气氛氩气保护下,通过高温固相反应合成得到了一个二元极性金属间化合物MgIn2。经X-射线单晶衍射与元素分析等方法确定了其晶体结构。MgIn2属立方体系,空间群为Fd3m(No.227),晶体学参数a=0.956 13(16)nm,V=0.874 1(3)nm3,Z=8,R1=0.035 3,wR2=0.082 8。MgIn2属于CaAl2结构类型,其结构特征为[In4]四面体通过共用顶点In原子链接而成的三维框架结构,Mg原子填充在三维框架的空隙中。能带结构计算表明MgIn2属于金属性的化合物。     

The coordination of perrhenate and pertechnetate to thorium(IV) in the presence of phosphine oxide or phosphate ligands

A series of thorium(IV) perrhenato- and pertechnetato-complexes with P[double bond, length as m-dash]O donor ligands have been prepared and characterised both in the solid state and in solution. Isostructural complexes of general formula [Th(MO(4))(4)(L)(4)], where M = Re or Tc and L = triethylphosphate (TEP) (2 and 7), tri-iso-butylphosphate (TiBP) (3 and 8) and tri-n-butylphosphine oxide (TBPO) (4 and 9) have been prepared from the novel starting materials [Th(ReO(4))(4)] x 4H(2)O (1) and [Th(TcO(4))(4)] x 4H(2)O (6). The reaction of or with triphenylphosphine oxide (TPPO) in MeOH has also led to the synthesis of [Th(MO(4))(3)(TPPO)(3)(OCH(3))(HOCH(3))] (M = Re (5) or Tc (10)). While the structural characterisation of 4 and 9 has been previously described, we report for the first time the structural characterisation of 2 and 5, with a partial structural refinement of 3. Vibrational spectroscopic analysis confirms that the Tc complexes not characterised by single crystal X-ray diffraction are indeed isostructural with the perrhenate complexes with the same P[double bond, length as m-dash]O donor ligand. In all cases, monodentate coordination of the Group 7 tetraoxo anion is observed. (31)P NMR spectroscopy indicates that in all the phosphine oxide-based complexes there is one dominant solution species. For the phosphate based systems, the presence of pertechnetate appears to inhibit P[double bond, length as m-dash]O donor ligand complexation in solution, whereas a significant proportion of each phosphate remains coordinated to Th(IV) when perrhenate is present as the counter ligand. These results give some indication as to the mechanism of pertechnetate co-extraction with tetravalent cations in the presence of tri-n-butyl phosphate in the Plutonium and Uranium Recovery by Extraction (PUREX) process.     

Synthesis and Crystal Structure of 2-Chloromethyl-1H-benzimidazole Nitrate, [ClCH_2(C_7H_6N_2)]NO_3

1 INTRODUCTION Benzimidazole is an interesting heterocyclic compound because it is found in various naturally occurring drugs, such as omeprazole, astemizole and emedastine difumarate[1]. The efficacy of sub- stituted benzimidazoles in the treatment of parasitic infections is well known[2～4]. Substituted benzimid- azole moieties are established pharmacophores in parasitic chemotherapy. Bis(2-benzimidazole) and some substituted bis(benzimidazol-2-yl)alkanes have attracted much interest …     

Octachloro- and octabromoditechnetate(III) and their rhenium(III) congeners

The compound (n-Bu4N)2Tc2Br8 was prepared by the metathesis of (n-Bu4N)2Tc2Cl8 with HBr (g) in dichloromethane and characterized by X-ray absorption fine structure spectroscopy and UV-vis spectroscopy. Analysis of the data gives a Tc-Tc distance of 2.16(1) A and a Tc-Br distance of 2.48(1) A. The Tc(III) oxidation state was inferred by the position of the edge absorption, which reveals a shift of 12 eV between (n-Bu4N)2Tc2Br8 and NH4TcO4. The analogous shift between (n-Bu4N)2Tc2Cl8 and NH4TcO4 is 11 eV. The UV-vis spectrum of Tc2Br8(2-) in dichloromethane exhibits the characteristic delta --> delta* transition at 13,717 cm(-1). The M2X8(2-) (M = Re, Tc; X = Cl, Br) UV-vis spectra are compared, and the position of the delta --> delta* transition discussed.     

Syntheses of new ionic technetium(III) complexes containing four monodentate phosphine ligands. Crystal structures of trans-[Tc(PMe2Ph)4Cl2]PF6, trans-[Tc(PMe3)4Cl2]BPh4, and trans-[Tc(PMe3)4Cl2]PF6

New ionic technetium complexes of the type trans-[Tc(PR3)4Cl2]+ are synthesized by various methods. The simplest method is the reaction of [TcO4]- with the phosphine in methanol in the presence of a chloride salt. Compounds containing PMe2Ph and PMe3 are synthesized and characterized by crystallographic methods. The complexes containing the less bulky phosphine can be prepared from complexes containing the bulker phosphine. The compounds are paramagnetic, with two unpaired electrons. The complexes studied by X-ray diffraction methods are the trans isomers. [Tc(PMe2Ph)4Cl2]PF6 crystallizes in the monoclinic space group P2(1)/c, with a = 11.511(2) A, b = 26.713(7) A, c = 12.688(3) A, beta = 92.79(1) degrees, Z = 4, and R1 = 0.0574. [Tc(PMe3)4Cl2]BPh4 (II) crystallizes in the orthorhombic space group Pbcn, with a = 18.213(5) A, b = 22.950(5) A, c = 19.428(6) A, Z = 8, and R1 = 0.0691. [Tc(PMe3)4Cl2]PF6 crystallizes in the monoclinic space group P2(1)/c, with a = 18.152(7) A, b = 16.838(9) A, c = 18.090(6) A, beta = 106.63(1) degrees, Z = 8, and R1 = 0.0670. The compounds all have octahedral coordination, but an important tetrahedral deformation of the plane containing the Tc and the four P atoms is observed in each case. In II, the two independent Tc atoms are both located on 2-fold axes.     

Stability and structural evolution of Ce(IV)(1-x)Ln(III)(x)O(2-x/2) solid solutions: a coupled μ-Raman/XRD approach

Several CeO(2)-based mixed oxides with general composition Ce(1-x)Ln(x)O(2-x/2) (for 0 ≤ x ≤ 1 and Ln = La, Nd, Sm, Eu, Gd, Dy, Er, or Yb) were prepared using an initial oxalic precipitation leading to a homogeneous distribution of cations in the oxides. After characterization of the Ce/Nd oxalate precursors and then thermal conversion to oxides at T = 1000 °C, investigation of the crystalline structure of these oxides was carried out by XRD and μ-Raman spectroscopy. Typical fluorite Fm ?3m structure was obtained for relatively low Ln(III) contents, while a cubic Ia ?3? superstructure was evidenced above x ≈ 0.4. Moreover, since Nd(2)O(3) does not crystallize with the Ia ?3?-type structure, two-phase systems composed with additional hexagonal Nd(2)O(3) were obtained for x(Nd) ≥ 0.73 in the Ce(1-x)Nd(x)O(2-x/2) series. The effect of heat treatment temperature on these limits was explored through μ-Raman spectroscopy, which allowed determining the presence of small amounts of the different crystal structures observed. In addition, the variation of the Ce(1-x)Ln(x)O(2-x/2) unit cell parameter was found to follow a quadratic relation as a result of the combination between increasing cationic radius, modifications of cation coordination, and decreasing O-O repulsion caused by oxygen vacancies.     

Layered perovskite-like Pb2Fe2O5 structure as a parent matrix for the nucleation and growth of crystallographic shear planes

The Pb(2)Fe(2)O(5) compound with a layered intergrowth structure has been prepared by a solid-state reaction at 700 °C. The incommensurate compound crystallizes in a tetragonal system with a = 3.9037(2) ?, c = 3.9996(4) ?, and q = 0.1186(4)c*, or when treated as a commensurate approximant, a = 3.9047(2) ?, c = 36.000(3) ?, space group I4/mmm. The crystal structure of Pb(2)Fe(2)O(5) was resolved from transmission electron microscopy data. Atomic coordinates and occupancies of the cation positions were estimated from high-angle annular dark-field scanning transmission electron microscopy data. Direct visualization of the positions of the oxygen atoms was possible using annular bright-field scanning transmission electron microscopy. The structure can be represented as an intergrowth of perovskite blocks and partially disordered blocks with a structure similar to that of the Bi(2)O(2) blocks in Aurivillius-type phases. The A-cation positions at the border of the perovskite block and the cation positions in the Aurivillius-type blocks are jointly occupied by Pb(2+) and Fe(3+) cations, resulting in a layer sequence along the c axis: -PbO-FeO(2)-PbO-FeO(2)-Pb(7/8)Fe(1/8)-O(1-x)-Fe(5/8)Pb(3/8)-O(2)-Fe(5/8)Pb(3/8)-. Upon heating, the layered Pb(2)Fe(2)O(5) structure transforms into an anion-deficient perovskite modulated by periodically spaced crystallographic shear (CS) planes. Considering the layered Pb(2)Fe(2)O(5) structure as a parent matrix for the nucleation and growth of CS planes allows an explanation of the specific microstructure observed for the CS structures in the Pb-Fe-O system.