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 »
- Authors:
-
- Department of Chemistry, University of California, One Shields Avenue, Davis, CA 95616 (United States)
- Department of Chemical Engineering and Materials Science, University of California, One Shields Avenue, Davis, CA 95616 (United States)
- 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}
}