Relative Stabilities of Layered Perovskite and Pyrochlore Structures in Transition Metal-Oxides Containing Trivalent Bismuth

In order to investigate the factors determining the relative stabilities of layered perovskite and pyrochlore structures of transition metal oxides containing trivalent bismuth, several ternary and quaternary oxides have been investigated. While d0 cations stabilize the layered perovskite structure, cations containing partially-filled d orbitals (which suppress ferroelectric distortion of MO6 octahedra) seem to favor pyrochlore-related structures. Thus, the vanadium analogue of the layered perovskite Bi4Ti3O12 cannot be prepared; instead the composition consists of a mixture of pyrochlore-type Bi1.33V2O6, Bi2O3, and Bi metal. The distortion of Bi1.33V2O6 to orthorhombic symmetry is probably due to an ordering of anion vacancies in the pyrochlore structure. None of the other pyrochlores investigated, Bi2NbCrO7, Bi2NbFeO7, TlBiM2O7 (M = Nb, Ta), shows evidence for cation ordering in the X-Ray diffraction patterns, as indeed established by structure refinement of TlBiNb2O7.

Hydrothermal phase equilibria in Ln2O3-H2O-CO2 systems : I. The lighter lanthanides

Phase diagrams for Nd2O3-H2O-CO2 and Gd2O3-H2O-CO2 systems at 1500 atm are given along with the results of selected runs in La, Sm and Eu systems. The stable phases in systems of La and Nd, are Ln(OH)CO3-B, Ln2O2CO3-II and LnOOH, in addition to the Ln(OH)3 phase at extremely low partial pressures of CO2 in the system. The systems become more and more complex with decreasing ionic radi and the number of stable carbonate phases increases. Ln2(CO3)3 · 3H2O orthorhombic (tengerate-like phase) is stable from Sm to Gd in addition to the other phases. The Gd(OH)CO3-A (ancylite-like phase) is hydrothermally stable at XCO2 greater-or-equal, slanted 0.5 while its hexagonal polymorph, Gd(OH)CO3-B is stable at low partial pressures of CO2 in the system.

Reversible Insertion of a Trivalent Cation onto MnO2 Leading to Enhanced Capacitance

Supercapacitor properties of MnO2 are studied generally in aqueous alkali metal salt solutions, often in a Na salt solution. During electrochemical discharge-charge processes, Na+ ions from the electrolyte get reversibly inserted/deinserted on the surface of MnO2 particles, which leads to redox reaction between MnOONa and MnO2. In the present study, it has been shown that MnO2 exhibits enhanced capacitance behaviour in a rare earth metal salt solution, namely, La(NO3)(3) solution in comparison with NaNO3 and Mg(NO3)(2) aqueous solutions. The specific capacitance increases with an increase in charge on the solution cation (Na+, Mg2+ and La3+). It is proposed that the number of surface sites for adsorption of cations remains unaltered in all solutions. The surface insertion of cation facilitates the reduction of Mn4+ in MnO2 to Mn3+ equivalent to the charge present on the cation. As the specific capacitance is related to the quantity of charge that is exchanged between the solid MnO2 and the aqueous solution, the trivalent cation (La3+) provides greater specific capacitance than in Mg(NO3)(2) and NaNO3 electrolytes. Accordingly, the number of Mn(IV)/Mn(III) redox pairs involved in the neighbourhood of the adsorption site is one, two and three when Na+, Mg2+ and La3+ ions, respectively, are adsorbed. (C) 2011 The Electrochemical Society. DOI: 10.1149/1.3565177] All rights reserved.

On the existence of hydrotalcite-like phases in the absence of trivalent cations

alpha-Hydroxides of nickel(II) and cobalt(II) are hydrotalcite-like phases, possessing a layered double hydroxide (LDH) structure even though there are no trivalent cations in the lattice. While the LDHs acquire a positive charge on the hydroxide layers by the incorporation of trivalent cations, we suggest that the alpha-hydroxides acquire a positive charge by partial protonation of the hydroxyl ions according to the equation M(OH)(2)+xH(+) --> [M(OH)(2-x)(H2O)(x)](x+). As in the LDHs, charge balance is restored by the incorporation of anions in the interlayer region. (C) 1997 Academic Press.

Comparative Studies on the Bioremediation of Hexavalent and Trivalent Chromium using Citrobacter freundii: Part I-Effect of parameters controlling Biosorption

The potential of Citrobacter freundii, a Gram negative bacteria for the remediation of hexavalent chromium (Cr(VI)) and trivalent chromium (Cr(III))) from aqueous solutions was investigated. Bioremediation of Cr(VI) involved both biosorption and bioreduction processes, as compared to only biosorption process observed with respect to Cr(III) bioremediation. In the case of Cr(VI) bioremediation studies, about 59 % biosorption was achieved at an equilibrium time of 2 h, initial Cr(VI) concentration of 4 mg/L, pH 1 and a biomass loading of 5x10(11) cells/mL. The remainder, 41 %, was found to be in the form of Cr(111) ions owing to bioreduction of Cr(VI) by the bacteria resulting in the absence of Cr(VI) ions in the residue, there by meeting the USEPA specifications. Similar studies were carried out using Cr(III) solution for an equilibrium time of 2 h, Cr(III) concentration of 4 mg/L, pH 3 and a biomass loading of 6.3x10(11) cells/mL., wherein a maximum biosorption of about 30 % was achieved.

Three-dimensional 3d-4f heterometallic polymers containing both azide and carboxylate as co-ligands

The hydrothermal reaction of Ln(NO3)(3), Ni(NO3)(2), NaN3, and isonicotinic acid (L) yielded two novel 3-D coordination frameworks (1 and 2) of general formula [Ni(2)Ln(L)(5)(N-3)(2)(H2O)(3)] center dot 2H(2)O (Ln = Pr(III) for 1 and Nd(III) for 2), containing Ni-Pr or Ni-Nd hybrid extended three-dimensional networks containing both azido and carboxylate as co-ligands. Both the compounds are found to be isostructural and crystallize in monoclinic system having P2(1)/n space group. Here the lanthanide ions are found to be nonacoordinated. Both bidentate and monodentate modes of binding of the carboxylate with the lanthanides have been observed in the above complexes. Variable temperature magnetic studies of the above two complexes have been investigated in the temperature range 2-300 K which showed dominant antiferromagnetic interaction in both the cases and these experimental results are analyzed with the theoretical models. (c) 2008 Elsevier B.V. All rights reserved.

Aducts of Lanthanide Perchlorates with N,N,N',N'-Tetramethyl Oxydiacetamide

Lanthanide coordination complexes with unidentate and bidentate amide ligands have been widely reported in the literature[l].In contrast, however, coordination compounds with tridentate ligands and with ligands containing ether oxygen as donor atoms to lanthanides have received little attention. In this paper we report the preparation and characterization of complexes formed by the interaction of the lanthanide perchlorates with N, N, N', N'- tetramethyloxydiacetamide (TMODA). The new complexes have been characterized by analysis, conductance, IR and electronic spectra. In addition, ~H and '3C NMR spectra of the ligand and its diamagnetic La ~+ and y3+ complexes are also discussed.

Phase transition in ammonium aluminium and ammonium chromium alums-A high pressure EPR study

An investigation of the phase transitions at high pressures in the alums mentioned in the title has been carried out using EPR of the Cr3+ ion (at the trivalent metal ion site). It is observed that at ambient as well as at high pressures there is a change of slope in the linear variations of the zero field splitting with temperature and that the low temperature phase is characterised by a large number of lines in the EPR spectra. The transition temperature shows a large positive shift with pressure, for both the alums. All these facts are explained in terms of our model of the origin of the trigonal field at the trivalent metal ion site as well as the details of the motion of NH4+ ion.

Hydrothermal phase equilibria studies in Ln2O3---H2O systems and synthesis of cubic lanthanide oxides

Phase diagrams for the systems Ln2O3---H2O (Ln = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Lu and Y) studied at 5000 to 10,000 psi and temperature range of 200–900°C, show that Ln(OH)3 hexagonal and LnOOH monoclinic are the only stable phases from Nd to Ho. The cubic oxide phase (C---Ln2O3) is stable for systems of Er, Tm, Yb and Lu, with no evidence of its equilibrium in the systems of lighter lanthanides. Using strong acids, HNO3 and HCOOH, as mineralisers the cubic oxides could be stabilised from Eu down to Lu. Solid solution phases of CeO2---Y2O3 and Eu2O3---Y2O3 have also been synthesised with HNO3 as mineraliser, since these compounds have promising use as solid electrolyte and phosphor materials respectively.

Complexes of lanthanide perchlorates with two new O,N,O ligands derived from antipyraldehyde and acetic and benzoic acid hydrazides

Antipyrine is a well known ligand for lanthanides (I). A forage through the organic literature of pyrazolones reveals that the 4-position of antipyrine is amenable to a wide variety of organic reactions. It should thus be possible to introduce suitable functional groups at this position and design new multidentate ligands for metal ions. It is also found that the coordination chemistry of lanthanides is much less well developed and far fewer ligands have been used for complexation with lanthanide ions compared to that of the d-transition metal ions. Keeping these points in view we have reported earlier, complexes of lanthanides with a bidentate ligand N,N-diethyl-antipyrine-4-carboxamide (2). In this communication we report the synthesis of two new ligands from Schiff base condensation of antipyraldehyde and the hydrazides of acetic and benzoic acids and the complexes formed by these hydrazones with lanthanide perchlorates.

Correlation Between The Stability Of Carbonates In Ternary Ln2o3-H2o-Co2 Hydrothermal Systems And Lanthanide Systematics

Phase diagrams for ternary Ln2O3-H2O-CO2 systems for the entire lanthanide series (except promethium) were studied at temperatures in the range 100–950 °C and pressures up to 3000 bar. The phase diagrams obtained for the heavier lanthanides are far more complex, with the appearance of a number of stable carbonate phases. New carbonates isolated from lanthanide systems (Ln ≡ Tm, Yb, Lu) include Ln6(OH)4(CO3)7, Ln4(OH)6-(CO3)3, Ln2O(OH)2CO3, Ln6O2(OH)8(CO3)3 and Ln12O7(OH)10(CO3)6. Stable carbonate phases common to all the lighter lanthanides are hexagonal LnOHCO3 and hexagonal Ln2O2CO3. Ln2(CO3)3• 3H2O is stable from samarium onwards and orthorhombic LnOHCO3 is stable from gadolinium onwards. On the basis of the appearance of stable carbonates, four different groups of lanthanides were established: lanthanum to neodymium, promethium to europium, terbium to erbium and thulium to lutetium. Gadolinium is the connecting element between groups II and III. This is in accordance with the tetrad classification for f transition elements.

Synthesis and structure of some interesting oxides of bismuth

Synthesis and structures of several new oxides containing bismuth are described. Three types of structures are common among the multinary oxides containing trivalent bismuth. They are the sillenite structure of γ-Bi2O3, the layered perovskite structure of Aurivillius phases and the pyrochlore structure. The influence of Bi3+∶6s 2 lone pair electrons is seen in all the three structures. In transition metal oxides containing trivalent bismuth,d o cations (Ti4+, Nb5+, W6+) stabilize the layered perovskite structure, while cations containing partially-filledd orbitals (V4+, Cr3+, Fe3+) favour pyrochlore-related structures. Ferroelectric distortion ofMO6 octahedra of thed o cations seems to play an important role in stabilizing layered perovskite structures.

Complexes of lanthanide perchlorates with two new " O,N,O " ligands derived from antipyraldehyde and acetic and benzoic acid hydrazides

Antipyrlne is a well known llgand for lanthanldes (i). A forage through the organic literature of pyrazolones reveals that the 4-position of antipyrlne is amenable to a wide variety of organic reactions. It should thus be possible to introduce suitable functional groups at this position and design new multidentate ligands for metal ions. It is also found that the coordination chemistry of lanthanides is much less well developed and far fewer ligands have been used for complexation with lanthanide ions compared to that of the d-transition metal ions.

Hydrothermal phase equilibria in Ln2O3-H2O-CO2 systems for Tm, Yb and Lu

Phase diagrams for Tm2O3-H2O-CO2. Yb2O3-H2O-CO2 and Lu2O3-H2O-CO2 systems at 650 and 1300 bars have been investigated in the temperature range of 100–800°C. The phase diagrams are far more complex than those for the lighter lanthanides. The stable phases are Ln(OH)3, Ln2(CO3)3.3H2O (tengerite phase), orthorhombic-LnOHCO3, hexagonal-Ln2O2CO3. LnOOH and cubic-Ln2O3. Ln(OH)3 is stable only at very low partial pressures of CO2. Additional phases stabilised are Ln2O(OH)2CO3and Ln6(OH)4(CO3)7 which are absent in lighter lanthanide systems. Other phases, isolated in the presence of minor alkali impurities, are Ln6O2(OH)8(CO3)3. Ln4(OH)6(CO3)3 and Ln12O7(OH)10,(CO3)6. The chemical equilibria prevailing in these hydrothermal systems may be best explained on the basis of the four-fold classification of lanthanides.

Rare earth transition metal sulfides, LnMS3

Ternary rare earth transition metal sulfides LnMS3 with Ln = La, Nd, and Gd, and M = V and Cr; as well as Ln = La and M = Mn, Fe, Co, and Ni have been prepared and characterized. The vanadium and chromium sulfides crystallize in a monoclinic layer structure isotypic with LaCrS3, while the other LnMS3 sulfides crystallize in a hexagonal structure. Chemical shifts of the metal K-absorption edge and XPS binding energies of core levels indicate that the transition metal is trivalent in the V and Cr sulfides, while it is divalent in the Mn, Fe, Co, and Ni sulfides. Electrical and magnetic properties of the sulfides are discussed in terms of their structures and the electronic configurations of the transition metal ions.