Journal article
Synthesis and Structural Characterization of a Family of Modified Hafnium tert-Butoxide for Use as Precursors to Hafnia Nanoparticles
Inorganic chemistry, v 51(22), pp 12075-12092
19 Nov 2012
PMID: 23131086
Abstract
A series of modified, hafnium tert-butoxide ([Hf(OBut)(4)]) compounds (1-26) were crystallographically characterized, and representative species were then used to produce HfO2 nanopartides. This systematically varied family of [Hf(OR)(4)] compounds was developed from the reaction of [Hf(OBut)(4)] with a series of (i) Lewis basic solvents, tetrahydrofuran, pyridine, or 1-methylimidazole; (ii) simple phenols, HOC6H4(R)-2 or HOC6H3(R)(2)-2,6 where R = CH3, CH(CH3)(2), or C(CH3)(3); and (iii) complex polydentate alcohols, tetrahydrofuran methanol (H-OTHF), pyridinecarbinol (H-OPy), and tris(hydroxymethylethane) (TIME-H-3). The solvent-modified products were crystallographically characterized as [Hf(OBut)(4)](solv)(n)] (1-3). The phenoxide (OAr)-exchanged [Hf(OBut)(4)] products isolated from toluene were characterized as dimeric [Hf(OAr)(n)(OBut)(4-n)](2) (4 and 5) or [Hf(mu-OH)(OAr)(3)(HOBut](2) (6 and 7) for the less sterically demanding OAr ligands and [Hf(OAr)(n)(OBut)(4-n)(HOBut)] (8 and 9) monomers for the larger OAr ligands. When Lewis basic solvents were employed, solvated monomers of varied OAr substitutions were observed as [Hf(OAr)(n)(OBut)(4-n)(solv)(x)], where solv = THF (10, 11, and 13-15) and py (16 and 19-21). The nuclearities of the remaining complex polydentate alcohol derivatives ranged from monomers (24, OPy) to dimers (22, OTHF; 23, OPy) to tetramers (25 and 26, THME). On the basis of their nuclearities, select members of this family of [Hf(OR)(4)] compounds (monomer,[Hf(OBut)(4)], 8; dimer, 19a, 22; tetramer, 25) were used to determine the validity of using [Hf(OR)(4)] precursors for the production of hafnia (HfO2) nanoparticles under solvothermal (oleylamine/oleic acid) conditions. After a 650 degrees C thermal treatment, the resulting powder X-ray diffraction pattern for each powder was found to be consistent with HfO2 (PDF 00-040-1173), and after a 1000 degrees C treatment, larger particles of HfO2 (PDF 00-043-1017) were reported. Transmission electron microscopy images confirmed that nanomaterials had formed. Because identical processing conditions had been employed for each HfO2 nanomaterial, the morphological variations observed in this study may be attributed to the individual precursors ("precursor structure affect").
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Details
- Title
- Synthesis and Structural Characterization of a Family of Modified Hafnium tert-Butoxide for Use as Precursors to Hafnia Nanoparticles
- Creators
- Timothy J. Boyle - Sandia National LaboratoriesLeigh Anna M. Steele - Sandia National LaboratoriesPatrick D. Burton - University of New MexicoSarah M. Hoppe - Sandia National LaboratoriesChelsea Lockhart - Sandia National LaboratoriesMark A. Rodriguez - Sandia National LaboratoriesLindsay A Steele - School of Biomedical Engineering, Science, and Health Systems (1997-)
- Publication Details
- Inorganic chemistry, v 51(22), pp 12075-12092
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 18
- Grant note
- CHE04-43580 / National Science Foundation CRIF:MU award DE-AC04-94AL85000 / U.S. Department of Energy's National Nuclear Security Administration; National Nuclear Security Administration National Institute for Nanoengineering and Laboratory Directed Research and Development programs at Sandia National Laboratories
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- School of Biomedical Engineering, Science, and Health Systems; Drexel University
- Web of Science ID
- WOS:000311173700005
- Scopus ID
- 2-s2.0-84869410432
- Other Identifier
- 991019356342204721
InCites Highlights
Data related to this publication, from InCites Benchmarking & Analytics tool:
- Collaboration types
- Domestic collaboration
- Web of Science research areas
- Chemistry, Inorganic & Nuclear