Synthesis and characterization of oxide interstitial derivatives of zirconium monochloride and monobromide

Seaverson, L. M.; Corbett, John D.

doi:10.1021/ic00164a008

Cited by 25 publications

(8 citation statements)

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“…They span metallic behavior from the physical and chemical points of view. The basic structure of the monohalide is preserved after oxidative chemical reactions, leading to M 2 X 2 Z 2 or M 2 X 2 Z (M = Sc, Y, Ln; Z = H, C) and MXZ or MXZ 0.5 (M = Zr, Hf; Z = H, C, O, N), where the nonmetal atoms (Z) occupy interstitial sites in the double metal layers. − In the zirconium halide derivatives, the anions O 2- (in ZrClO 0.5 ), C 4- (in ZrClC 0.5 ), H - (in Zr 2 X 2 H), and N 3- (in β-ZrNX) 3 occupy the tetrahedral sites, whereas in the lanthanide derivatives the Z anions occupy either the tetrahedral or the octahedral sites. The insertion of anions modifies the band population and affects the electronic properties, the result being normal valence or semiconducting compounds.…”

Section: Introductionmentioning

confidence: 99%

Chemical Transport Synthesis, Electrochemical Behavior, and Electronic Structure of Superconducting Zirconium and Hafnium Nitride Halides

Vlassov

Beltrán-Porter

et al. 1999

Inorg. Chem.

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The layered nitrides beta-MNX (M = Zr, Hf; X = Cl, Br) crystallize in the space group R&thremacr;m with a hexagonal cell of dimensions a = 3.6031(6) Å, c = 27.672(2) Å for beta-ZrNCl, a = 3.5744(3) Å, c = 27.7075(9) Å for beta-HfNCl, and a = 3.6379(5) Å, c = 29.263(2) Å for beta-ZrNBr. Lithium intercalation using n-buthyllithium in hexane solutions leads to solvent free superconductors of formula Li(0.20)ZrNCl, Li(0.42)HfNCl, Li(0.67)HfNCl, and Li(0.17)ZrNBr showing critical temperatures of 12, 18, 24, and 13.5 K, respectively. Whereas several samples of beta-ZrNBr and beta-ZrNCl showed reproducibility in the lithium uptake and in the corresponding critical temperatures, different samples of beta-HfNCl subjected to the same treatment in n-buthyllithium showed lithium uptakes ranging from 0.07 to 0.67, and corresponding critical temperatures between 0 and 24 K. A linear dependence of T(c) versus the lithium content is observed when all the superconducting samples are considered. The results obtained from electrochemical lithiation are consistent with those obtained with chemical methods, as samples with larger capacity on discharge are also those found to have larger lithium contents after chemical lithiation. Most samples present a reduction step around 1.8 V vs Li(0)-Li(+) whose origin is still unclear. The electrochemical capacity on discharge for beta-HfNCl and beta-ZrNBr depends on the milling time spent in the preparation of the electrodes, with long milling times resulting in lower intercalation degree. Possible causes for this effect are either the creation of structural defects (e.g., stacking faults) or some sample decomposition induced by local heating. The same phenomena are proposed to account for the different behavior of beta-HfNCl samples, although additional aspects such as the presence of hydrogen, oxygen, or extra hafnium atoms in the structure have to be considered. Tight-binding band structure calculations for beta-MNX (M = Zr, X = Cl, Br; M = Hf, X = Cl), ZrCl, and Y(2)C(2)Br(2) are reported. The density of states and Fermi surfaces of the beta-MNX phases as well as the relationship between the electronic structure of the beta-ZrNCl and ZrCl are discussed. Despite the structural relationships, the electronic structures near the Fermi level of the beta-MNX and Y(2)Br(2)C(2) phases are found to be very different.

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Section: Introductionmentioning

confidence: 99%

Chemical Transport Synthesis, Electrochemical Behavior, and Electronic Structure of Superconducting Zirconium and Hafnium Nitride Halides

Vlassov

Beltrán-Porter

et al. 1999

Inorg. Chem.

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“…They span metallic behavior from the physical and chemical points of view. The basic structure of the monohalide is preserved after oxidative chemical reactions providing M 2 X 2 Z 2 or M 2 X 2 Z (M = Sc, Y, Ln; Z = H, C) and MXZ or MXZ 0.5 (M = Zr, Hf; Z = H, C, O, N), where the nonmetal atoms (Z) occupy interstitial positions between the double metal layers. − In the zirconium halide derivatives, the anions O 2- (in ZrClO 0.5 ), C 4- (in ZrClC 0.5 ), H - (in Zr 2 X 2 H), and N 3- (in β-ZrNX) (this work) occupy the tetrahedral sites. The insertion of the nonmetal atoms modifies the conduction band population.…”

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confidence: 99%

Crystal Structure of the Host Lattices of the Superconductors Li_xMNX (M = Zr, Hf; X = Cl, Br)

et al. 1999

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The crystal structure of the host lattice for the new family of layered superconductors Li x HfNCl, Li x ZrNCl, and Li x ZrNBr is derived from the ZrCl polytype structure. As in the superconducting halide carbides Ln2C2X2 (Ln = La, Y, Lu; X = Br, I), the new structures can be considered as a result of the intercalation of nonmetal atoms (N3- in the nitrides, C2 4- in the carbides) in the interstices between the metal layers of the ZrCl structure. This suggests the existence of a new class of layered covalent superconductors with critical temperatures higher than for Nb3Ge that opens novel perspectives in the search for new non-oxide superconducting materials.

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“…A well known example is the mineral baddeleyite with Zr–O bond lengths between 2.04 and 2.26 Å, which fits well to the Zr–O bonds found for 1 . In the layered structure of ZrO 0.43 Cl, Zr exhibits a trigonal prismatic coordination by chlorine and oxygen atoms completed by a seventh oyxgen atom capping the trigonal prism over a square face, but with the restriction that only about one half of these oxygen positions are occupied.…”

Section: Resultsmentioning

confidence: 99%

Double Salts and Mixed Crystals of Tellurium Clusters Te₄²⁺/Te₈²⁺ and TeCl₃⁺ Ions with Anions based on Molybdenum and Zirconium (Oxy)chlorides

Forge

Beck

2018

Zeitschrift anorg allge chemie

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The reaction of elemental tellurium, tellurium tetrachloride, zirconium tetrachloride, and molybdenum oxytetrachloride yields black plate‐like crystals of Te4[MoZr2O2Cl11] (1) and yellow crystals of (TeCl3)2[Mo2O2Cl8]x[Zr2Cl10]1–x (2). Using molybdenum oxytrichloride instead of the oxytetrachloride, black crystals of (Te4)2[Mo2O2Cl8][ZrCl6] (3), Te8[ZrCl6] (4), and bronze‐colored crystals of Te4[ZrCl6] (5) are obtained. All obtained crystals are air‐sensitive and were characterized by single‐crystal X‐ray diffraction and energy‐dispersive X‐ray fluorescence spectroscopy. 1 contains a layered polymeric anion of unprecedented structural features with zirconium atoms coordinated in a pentagonal bipyramidal ZrO3Cl4 and ZrOCl6 environment. Magnetic susceptibility data of 1 and 2 show nearly ideal paramagnetic behavior according to the Curie law with magnetic moments of 1.55(7) μB for 1 and 1.66(6) μB for 2 indicating the presence of magnetically isolated d1 configured MoV. The double salt 3 adopts the structure type of the selenium containing congener (Se4)2[Mo2O2Cl8][ZrCl6], 4 and 5 are isotypic to the respective hafnium containing representatives Te4[HfCl6] and Te8[HfCl6].

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Synthesis and characterization of oxide interstitial derivatives of zirconium monochloride and monobromide

Cited by 25 publications

References 4 publications

Chemical Transport Synthesis, Electrochemical Behavior, and Electronic Structure of Superconducting Zirconium and Hafnium Nitride Halides

Chemical Transport Synthesis, Electrochemical Behavior, and Electronic Structure of Superconducting Zirconium and Hafnium Nitride Halides

Crystal Structure of the Host Lattices of the Superconductors Li_xMNX (M = Zr, Hf; X = Cl, Br)

Double Salts and Mixed Crystals of Tellurium Clusters Te₄²⁺/Te₈²⁺ and TeCl₃⁺ Ions with Anions based on Molybdenum and Zirconium (Oxy)chlorides

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Synthesis and characterization of oxide interstitial derivatives of zirconium monochloride and monobromide

Cited by 25 publications

References 4 publications

Chemical Transport Synthesis, Electrochemical Behavior, and Electronic Structure of Superconducting Zirconium and Hafnium Nitride Halides

Chemical Transport Synthesis, Electrochemical Behavior, and Electronic Structure of Superconducting Zirconium and Hafnium Nitride Halides

Crystal Structure of the Host Lattices of the Superconductors LixMNX (M = Zr, Hf; X = Cl, Br)

Double Salts and Mixed Crystals of Tellurium Clusters Te42+/Te82+ and TeCl3+ Ions with Anions based on Molybdenum and Zirconium (Oxy)chlorides

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Crystal Structure of the Host Lattices of the Superconductors Li_xMNX (M = Zr, Hf; X = Cl, Br)

Double Salts and Mixed Crystals of Tellurium Clusters Te₄²⁺/Te₈²⁺ and TeCl₃⁺ Ions with Anions based on Molybdenum and Zirconium (Oxy)chlorides