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Title: Nanoparticles of superconducting {gamma}-Mo{sub 2}N and {delta}-MoN

Abstract

We have been able to prepare nanoparticles ({approx}4 nm diameter) of cubic {gamma}-Mo{sub 2}N by a simple procedure involving the reaction of MoCl{sub 5} with urea at 873 K. The nanoparticles show a superconducting transition around 6.5 K. The {gamma}-Mo{sub 2}N nanoparticles are readily transformed to nanoparticles of {delta}-MoN with a slightly larger diameter on heating in a NH{sub 3} atmosphere at 573 K. Phase-pure {delta}-MoN obtained by this means shows a superconducting transition around 5 K. - Graphical abstract: TEM image of the {gamma}-Mo{sub 2}N particles with the inset showing the resistivity of the sample as a function of temperature.

Authors:
 [1];  [1];  [2]
  1. Chemistry and Physics of Materials Unit, DST Unit on Nanoscience and CSIR Centre of Excellence in Chemistry, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India)
  2. Chemistry and Physics of Materials Unit, DST Unit on Nanoscience and CSIR Centre of Excellence in Chemistry, Jawaharlal Nehru Centre for Advanced Scientific Research, Jakkur P.O., Bangalore 560064 (India), E-mail: cnrrao@jncasr.ac.in
Publication Date:
OSTI Identifier:
21015649
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2006.10.020; PII: S0022-4596(06)00557-3; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMMONIA; MOLYBDENUM CHLORIDES; MOLYBDENUM NITRIDES; NANOSTRUCTURES; PARTICLES; TEMPERATURE DEPENDENCE; TEMPERATURE RANGE 0400-1000 K; TRANSMISSION ELECTRON MICROSCOPY; UREA

Citation Formats

Gomathi, A., Sundaresan, A., and Rao, C.N.R.. Nanoparticles of superconducting {gamma}-Mo{sub 2}N and {delta}-MoN. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.10.020.
Gomathi, A., Sundaresan, A., & Rao, C.N.R.. Nanoparticles of superconducting {gamma}-Mo{sub 2}N and {delta}-MoN. United States. doi:10.1016/j.jssc.2006.10.020.
Gomathi, A., Sundaresan, A., and Rao, C.N.R.. Mon . "Nanoparticles of superconducting {gamma}-Mo{sub 2}N and {delta}-MoN". United States. doi:10.1016/j.jssc.2006.10.020.
@article{osti_21015649,
title = {Nanoparticles of superconducting {gamma}-Mo{sub 2}N and {delta}-MoN},
author = {Gomathi, A. and Sundaresan, A. and Rao, C.N.R.},
abstractNote = {We have been able to prepare nanoparticles ({approx}4 nm diameter) of cubic {gamma}-Mo{sub 2}N by a simple procedure involving the reaction of MoCl{sub 5} with urea at 873 K. The nanoparticles show a superconducting transition around 6.5 K. The {gamma}-Mo{sub 2}N nanoparticles are readily transformed to nanoparticles of {delta}-MoN with a slightly larger diameter on heating in a NH{sub 3} atmosphere at 573 K. Phase-pure {delta}-MoN obtained by this means shows a superconducting transition around 5 K. - Graphical abstract: TEM image of the {gamma}-Mo{sub 2}N particles with the inset showing the resistivity of the sample as a function of temperature.},
doi = {10.1016/j.jssc.2006.10.020},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 180,
place = {United States},
year = {Mon Jan 15 00:00:00 EST 2007},
month = {Mon Jan 15 00:00:00 EST 2007}
}
  • The electronic structures of B1 MoN, fcc Mo/sub 2/N, and hexagonal MoN were observed by photoelectron spectroscopic measurement. The B1-MoN phase has been predicted to be a high-T/sub c/ superconductor because of a large density of states at Fermi level. The observed electronic structure of the stoichiometric B1-MoN phase is different from that of the real B1-MoN type. The nitrogen excess B1-MoN/sub x/ (x> or =1.3) phase, however, shows the B1-type electronic structure. This is explained by the occurrence of a nitrogen vacancy in the apparent stoichiometric B1 phase and the occupation of the nitrogen vacancy in the nitrogen-excess B1more » phase. This property is related to the previously reported low T/sub c/ of the B1-MoN crystals.« less
  • We report compressibility measurements for three transition metal nitrides ({epsilon}-TaN, {delta}-MoN, Cr{sub 2}N) that have structures based on hexagonal arrangements of the metal atoms. The studies were performed using monochromatic synchrotron x-ray diffraction at high pressure in a diamond anvil cell. The three nitride compounds are well-known high hardness materials, and they are found to be highly incompressible. The bulk modulus values measured for {epsilon}-TaN, Cr{sub 2}N, and {delta}-MoN are K{sub 0}=288(6) GPa, 275(23) GPa, and 345(9) GPa, respectively. The data were analyzed using a linearized plot of reduced pressure (F) vs the Eulerian finite strain variable f within amore » third-order Birch-Murnaghan equation of state formulation. The K{sub 0}{sup '} values for {epsilon}-TaN and {delta}-MoN were 4.7(0.5) and 3.5(0.3), respectively, close to the value of K{sub 0}{sup '}=4 that is typically assumed in fitting compressibility data in equation of state studies using a Birch-Murnaghan equation. However, Cr{sub 2}N was determined to have a much smaller value, K{sub 0}{sup '}=2.0(2.0), indicating a significantly smaller degree of structural stiffening with increased pressure. We also present Raman data for {epsilon}-TaN and {delta}-MoN at high pressure in order to characterize the phonon behavior in these materials. All of the Raman active modes for {epsilon}-TaN were identified using polarized spectroscopy. Peaks at low frequency are due to Ta motions, whereas modes at higher wave number contain a large component of N motion. The high frequency modes associated with Ta-N stretching vibrations are more sensitive to compression than the metal displacements occurring at lower wave number. The mode assignments can be generally extended to {delta}-MoN, that has a much more complex Raman spectrum. The x-ray and Raman data for {epsilon}-TaN show evidence for structural disordering occurring above 20 GPa, whereas no such change is observed for {delta}-MoN.« less
  • The reactions of ammonia with MoO{sub 3}, (NH{sub 4}){sub 6}Mo{sub 7}O{sub 24} {times} 4H{sub 2}O, (NH{sub 4}){sub 2}MoO{sub 4}, and H{sub x}MoO{sub 3} to produce MoN and Mo{sub 2}N with high surface areas have been studied. Thermogravimetric analysis (TGA) and in situ x-ray diffraction (XRD) were used to follow the reaction pathway and determine the structure of the reaction intermediates and products. The surface areas of the starting materials, intermediates, and products were determined by using the BET method. The results show that all four reactants form the same oxynitride intermediate; this oxynitride converts directly to a nitride.
  • Hydrothermal reactions of molybdenum-oxide precursors with polyalcohols in the presence of base yielded two series of mixed-valence oxomolybdenum clusters, the hexadecanuclear species [XH{sub 12}(Mo{sup VI}O{sub 3}){sub 4}Mo{sup V}{sub 12}O{sub 40}]{sup m{minus}}(X=Na{sup +}, m=7; X=2H{sup +}, m=6) and the superclusters [XH{sub n}Mo{sup VI}{sub 6}Mo{sup V}{sub 36}O{sub 109}(OCH{sub 2}){sub 3}CR{sub 7}]{sup m{minus}} (X=Na-(H{sub 2}O){sub 3}{sup +}, m=9, n=13; X=Na(H{sub 2}O){sub 3}{sup +}, m=7, n=15; X=MoO{sub 3}, m=9, n=14; X=MoO{sub 3}, m=10, n=13). In a representative synthesis for the hexadencanuclear class of materials, the hydrothermal reaction of a mixture of Na{sub 2}MoO{sub 4}{center_dot}2H{sub 2}O, MoO{sub 3}, Mo metal, and NH{sub 4}Cl produced (NH{submore » 4}){sub 7}[NaMo{sub 16}(OH){sub 12}O{sub 40}]{center_dot}4h{sub 2}O (1{center_dot}4H{sub 2}O) as red-orange crystals. The compound (Me{sub 3}NH){sub 4}K{sub 2}[H{sub 2}Mo{sub 16}(OH){sub 40}]{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O(2{center_dot}8H{sub 2}O) was prepared in a similar fashion. The structure of the anion of 1 consists of an {epsilon}-Keggin core H{sub 12}Mo{sub 12}O{sub 40}, capped on four hexagonal faces by MoO{sub 3} units and encapsulating a Na{sup +} cation. The structure of the oxomolybdenum framework of 2 is essentially identical to that of 1; however, the central cavity is now occupied by 2H{sup +}.« less