0000000000004241
AUTHOR
Judith Oró-solé
Synthesis and crystal structure of novel Ruddlesden–Popper strontium niobium oxynitrides
Abstract The family (SrO)(SrNbO 2-x N) n is the first example of Ruddlesden-Popper strontium niobium oxynitrides and provides layered structures to obtain mixed valence niobium compounds with a variety of oxidation states and transport properties. We have prepared members with n =1 (Sr 2 NbO 3 N) and n =2 (Sr 3 Nb 2 O 5 N 2 ) by solid state reaction of Nb 2 O 5 and SrCO 3 at 900–1050 °C under ammonia flow. These compounds crystallize in the I4/mmm space group and show a range of anionic stoichiometry that together with the N/O ratio determines the formal oxidation state for niobium and therefore the resultant physical properties. Samples of the n =1 member show mixed valence Nb 5+ /Nb 4+ an…
Intercalation chemistry of superconducting zirconium and hafnium nitride halides
Abstract Lithium intercalation in MNX (M=Zr, Hf; X=Cl, Br) may lead to superconducting compounds with critical temperatures up to 24 K. Electrochemical lithiation experiments agree with the results obtained with chemical methods, as samples with larger capacity on discharge are also those having larger lithium contents after chemical lithiation. Variations exist in the electrochemical profiles of different batches for these compounds indicating differences in the intercalation reaction pathway. High-resolution electron microscopy images confirm the structural model isotypic to SmSI for β-MNX phases. The major part of crystals from ZrNX as well as from the HfNCl samples showing a high lithiu…
Crystal structures of superconducting sodium intercalates of hafnium nitride chloride
Sodium intercalation compounds of HfNCl have been prepared at room temperature in naphtyl sodium solutions in tetrahydrofuran and their crystal structure has been investigated by Rietveld refinement using X-ray powder diffraction data and high-resolution electron microscopy. The structure of two intercalates with space group Rm and lattice parameters a = 3.58131(6) A u , c = 57.752(6) A u , and a = 3.58791(8) A u , c = 29.6785(17) A u is reported, corresponding to the stages 2 and 1, respectively, of NaxHfNCl. For the stage 2 phase an ordered model is presented, showing two crystallographically independent (HfNCl) units with an alternation of the Hf-Hf interlayer distance along the c-axis, …
Lithium intercalation chemistry, microstructure and superconductivity in zirconium and hafnium nitride halides
Abstract Lithium intercalation in β-MNX (M=Zr, Hf; X=Cl, Br) leads to superconducting compounds with critical temperatures between 12 and 24 K. The lithium uptakes after treatment of the host materials with n-butyllithium/hexane solutions are ca. 0.2 atoms per formula for β-ZrNCl and β-ZrNBr, and between 0.07 and 0.67 for β-HfNCl. Electrochemical lithiation experiments agree with the results obtained with chemical methods, as samples with larger capacity on discharge are also those having larger lithium contents after chemical lithiation. Variations exist in the electrochemical profiles of different batches for the three compounds indicating differences in the intercalation reaction pathway…
New Family of Ruddlesden−Popper Strontium Niobium Oxynitrides: (SrO)(SrNbO2-xN)n (n = 1, 2)
The new family (SrO)(SrNbO2-xN)n (n = 1, n = 2) constitutes the first example of strontium niobium Ruddlesden−Popper oxynitrides and provides layered structures to obtain mixed valence niobium comp...
A new intermediate intercalate in superconducting sodium-doped hafnium nitride chloride
Anew phase has been observed during the sodiumintercalation of hafnium nitride chloride as intermediate between the host β-HfNCl and the already reported Na 0.29 HfNCl with Tc of 24 K; the new intermediate shows interlayer spacings ranging from 9.48 to 9.67 A°, corresponds to a second stage intercalate of HfNCl and is superconducting with a critical temperature of 20 K. Beltran Porter, Daniel, Daniel.Beltran@uv.es
Synthesis and crystal structure of the α polytype of HfNBr
Abstract α-HfNBr has been prepared at 760 °C in a sealed evacuated fused silica tube by reaction between NH4Br and Hf followed by purification through chemical vapour transport under a temperature gradient. The crystal structure of this compound at room temperature has been determined for the first time by Rietveld refinement of X-ray powder diffraction data, electron diffraction and high resolution electron microscopy. It crystallises in the orthorhombic space group Pmmn with the unit cell parameters a=4.1165(2), b=3.5609(2), c=8.6440(3) A. α-HfNBr is isotypic to FeOCl and is built from layers of composition BrHfNNHfBr stacked along c that are separated by a Van der Waals gap. The haf…
Lattice dynamics of superconducting zirconium and hafnium nitride halides
We have performed a study of the Raman active modes of β-HfNCl, β-ZrNCl, and β-ZrNBr and Na-doped β-HfNCl in various scattering configurations. The experimental values are compared with a lattice dynamical calculation andassigned to definite atomic motions. The variation of the atomic force constants are analyzed as a function of the bond length, relating their relative strength with the atomic characteristics of the compound.