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Synthesis and Characterization of Th2N2(NH) Isomorphous to Th2N3

Journal Article · · Inorganic Chemistry
DOI:https://doi.org/10.1021/ic300025b· OSTI ID:1036547
 [1];  [2];  [3];  [4];  [4]
  1. University of California, Berkeley
  2. ORNL
  3. Argonne National Laboratory (ANL)
  4. University of Nevada, Las Vegas
Using a new, low-temperature, fluoride-based process, thorium nitride imide of the chemical formula Th{sub 2}N{sub 2}(NH) was synthesized from thorium dioxide via an ammonium thorium fluoride intermediate. The resulting product phase was characterized by powder X-ray diffraction (XRD) analysis and was found to be crystallographically similar to Th{sub 2}N{sub 3}. Its unit cell was hexagonal with a space group of P3m{bar 1} and lattice parameters of a = b = 3.886(1) and c = 6.185(2) {angstrom}. The presence of -NH in the nitride phase was verified by Fourier transform infrared spectroscopy (FTIR). Total energy calculations performed using all-electron scalar relativistic density functional theory (DFT) showed that the hydrogen atom in the Th{sub 2}N{sub 2}(NH) prefers to bond with nitrogen atoms occupying 1a Wyckoff positions of the unit cell. Lattice fringe disruptions observed in nanoparticle areas of the nitride species by high-resolution transmission electron microscopic (HRTEM) images also displayed some evidence for the presence of -NH group. As ThO{sub 2} was identified as an impurity, possible reaction mechanisms involving its formation are discussed.
Research Organization:
Oak Ridge National Laboratory (ORNL)
Sponsoring Organization:
NE USDOE - Office of Nuclear Energy
DOE Contract Number:
AC05-00OR22725
OSTI ID:
1036547
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 51; ISSN 0020-1669; ISSN INOCAJ
Country of Publication:
United States
Language:
English

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