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Title: Synthesis and spectroscopic characterization of P-doped Na{sub 4}Si{sub 4}

Abstract

Na{sub 4}Si{sub 4} is a Zintl salt composed of Na{sup +} cations and Si{sub 4}{sup 4-} tetrahedral anions and is a unique solid-state precursor to clathrate structures and nanomaterials. In order to provide opportunities for the synthesis of complex materials, phosphorus was explored as a possible substituent for silicon. Phosphorus doped sodium silicides Na{sub 4}Si{sub 4-x}P{sub x} (x{<=}0.04) were prepared by reaction of Na with the mechanically alloyed Si{sub 4-x}:P{sub x} (x=0.04, 0.08, 0.12) mixture in a sealed Nb tube at 650 {sup o}C for 3 days. Energy dispersive X-ray spectroscopy confirms the presence of P in all products. Powder X-ray diffraction patterns are consistent with the retention of the Na{sub 4}Si{sub 4} crystal structure. As the amount of P increases, a new peak in the diffraction pattern that can be assigned to black phosphorus is apparent above the background. Raman and solid-state NMR provide information on phosphorus substitution in the Na{sub 4}Si{sub 4} structure. Raman spectroscopy shows a shift of the most intense band assigned to the Si{sub 4}{sup 4-} {nu}{sub 1} (A{sub 1}) mode from 486.4 to 484.0 cm{sup -1} with increasing P, consistent with P replacement of Si. Differential nuclear spin-lattice relaxation for the Si sites determinedmore » via {sup 29}Si solid-state NMR provides direct evidence for Si-P bonding in the (Si{sub 1-x}P{sub x}){sup 4-} tetrahedron. The {sup 23}Na NMR shows additional Na...P interactions and the {sup 31}P NMR shows two P sites, consistent with P presence in both of the crystallographic sites in the (Si{sub 4}){sup 4-} tetrahedron. - Graphical abstract: P-doped Na{sub 4}Si{sub 4} has been prepared and Raman spectroscopy and {sup 29}Si, {sup 23}Na, and {sup 31}P multinuclear NMR show that P dopes into both crystallographic sites for Si. Display Omitted« less

Authors:
 [1];  [2];  [3];  [2]
  1. Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616 (United States)
  2. Department of Chemical Engineering and Materials Science, University of California, One Shields Avenue, Davis, CA 95616 (United States)
  3. NMR Facility, University of California, One Shields Avenue, Davis, CA 95616 (United States)
Publication Date:
OSTI Identifier:
21494106
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 183; Journal Issue: 11; Other Information: DOI: 10.1016/j.jssc.2010.07.051; PII: S0022-4596(10)00335-X; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; CATIONS; CLATHRATES; CRYSTAL STRUCTURE; CRYSTALLOGRAPHY; DOPED MATERIALS; NANOSTRUCTURES; NUCLEAR MAGNETIC RESONANCE; PHOSPHORUS; RAMAN SPECTROSCOPY; SILICON; SODIUM IONS; SODIUM SILICIDES; SPIN-LATTICE RELAXATION; SYNTHESIS; X-RAY DIFFRACTION; X-RAY SPECTROSCOPY; ALKALI METAL COMPOUNDS; CHARGED PARTICLES; COHERENT SCATTERING; DIFFRACTION; ELEMENTS; IONS; LASER SPECTROSCOPY; MAGNETIC RESONANCE; MATERIALS; NONMETALS; RELAXATION; RESONANCE; SCATTERING; SEMIMETALS; SILICIDES; SILICON COMPOUNDS; SODIUM COMPOUNDS; SPECTROSCOPY

Citation Formats

Jialing, Wang, Sen, Sabyasachi, Ping, Yu, Browning, Nigel D, and Kauzlarich, Susan M., E-mail: smkauzlarich@ucdavis.ed. Synthesis and spectroscopic characterization of P-doped Na{sub 4}Si{sub 4}. United States: N. p., 2010. Web. doi:10.1016/j.jssc.2010.07.051.
Jialing, Wang, Sen, Sabyasachi, Ping, Yu, Browning, Nigel D, & Kauzlarich, Susan M., E-mail: smkauzlarich@ucdavis.ed. Synthesis and spectroscopic characterization of P-doped Na{sub 4}Si{sub 4}. United States. https://doi.org/10.1016/j.jssc.2010.07.051
Jialing, Wang, Sen, Sabyasachi, Ping, Yu, Browning, Nigel D, and Kauzlarich, Susan M., E-mail: smkauzlarich@ucdavis.ed. 2010. "Synthesis and spectroscopic characterization of P-doped Na{sub 4}Si{sub 4}". United States. https://doi.org/10.1016/j.jssc.2010.07.051.
@article{osti_21494106,
title = {Synthesis and spectroscopic characterization of P-doped Na{sub 4}Si{sub 4}},
author = {Jialing, Wang and Sen, Sabyasachi and Ping, Yu and Browning, Nigel D and Kauzlarich, Susan M., E-mail: smkauzlarich@ucdavis.ed},
abstractNote = {Na{sub 4}Si{sub 4} is a Zintl salt composed of Na{sup +} cations and Si{sub 4}{sup 4-} tetrahedral anions and is a unique solid-state precursor to clathrate structures and nanomaterials. In order to provide opportunities for the synthesis of complex materials, phosphorus was explored as a possible substituent for silicon. Phosphorus doped sodium silicides Na{sub 4}Si{sub 4-x}P{sub x} (x{<=}0.04) were prepared by reaction of Na with the mechanically alloyed Si{sub 4-x}:P{sub x} (x=0.04, 0.08, 0.12) mixture in a sealed Nb tube at 650 {sup o}C for 3 days. Energy dispersive X-ray spectroscopy confirms the presence of P in all products. Powder X-ray diffraction patterns are consistent with the retention of the Na{sub 4}Si{sub 4} crystal structure. As the amount of P increases, a new peak in the diffraction pattern that can be assigned to black phosphorus is apparent above the background. Raman and solid-state NMR provide information on phosphorus substitution in the Na{sub 4}Si{sub 4} structure. Raman spectroscopy shows a shift of the most intense band assigned to the Si{sub 4}{sup 4-} {nu}{sub 1} (A{sub 1}) mode from 486.4 to 484.0 cm{sup -1} with increasing P, consistent with P replacement of Si. Differential nuclear spin-lattice relaxation for the Si sites determined via {sup 29}Si solid-state NMR provides direct evidence for Si-P bonding in the (Si{sub 1-x}P{sub x}){sup 4-} tetrahedron. The {sup 23}Na NMR shows additional Na...P interactions and the {sup 31}P NMR shows two P sites, consistent with P presence in both of the crystallographic sites in the (Si{sub 4}){sup 4-} tetrahedron. - Graphical abstract: P-doped Na{sub 4}Si{sub 4} has been prepared and Raman spectroscopy and {sup 29}Si, {sup 23}Na, and {sup 31}P multinuclear NMR show that P dopes into both crystallographic sites for Si. Display Omitted},
doi = {10.1016/j.jssc.2010.07.051},
url = {https://www.osti.gov/biblio/21494106}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 11,
volume = 183,
place = {United States},
year = {Mon Nov 15 00:00:00 EST 2010},
month = {Mon Nov 15 00:00:00 EST 2010}
}