skip to main content

DOE PAGESDOE PAGES

  • DOE PAGES
  • Accepted Manuscript: Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production

Title: Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production

We synthesized a series of nickel(II) aryloxide ([Ni(OAr) 2(py) x]) precursors from an amide-alcohol exchange using [Ni(NR 2) 2] in the presence of pyridine (py). The H-OAr selected were the mono- and di-ortho-substituted 2-alkyl phenols: alkyl = methyl (H-oMP), iso-propyl (H-oPP), tert-butyl (H-oBP) and 2,6-di-alkyl phenols (alkyl = di-iso-propyl (H-DIP), di-tert-butyl (H-DBP), di-phenyl (H-DPhP)). Furthermore, the crystalline products were solved as solvated monomers and structurally characterized as [Ni(OAr) 2(py) x], where x = 4: OAr = oMP (1), oPP (2); x = 3: OAr = oBP (3), DIP (4); x = 2: OAr = DBP (5), DPhP (6). The excited states (singlet or triplet) and various geometries of 1–6 were identified by experimental UV-vis and verified by computational modeling. Magnetic susceptibility of the representative compound 4 was fit to a Curie Weiss model that yielded a magnetic moment of 4.38(3)μ B consistent with a Ni 2+ center. Compounds 1 and 6 were selected for decomposition studied under solution precipitation routes since they represent the two extremes of coordination. The particle size and crystalline structure were characterized using transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD). Finally, the materials isolated from 1 and 6 were found by TEM to formmore » irregular shape nanomaterials (8–15 nm), which by PXRD were found to be Ni 0 hcp (PDF: 01-089-7129) and fcc (PDF: 01-070-0989), respectively.« less
Authors:
 [1] ; ORCiD logo [1] ;  [2] ;  [1] ;  [2]
+ Show Author Affiliations
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Advanced Materials Lab.
  2. Louisiana State Univ., Baton Rouge, LA (United States). Dept. of Physics and Astronomy
Publication Date:
Report Number(s):
SAND2017-5498J
Journal ID: ISSN 1477-9226; ICHBD9; 653577
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 46; Journal Issue: 18; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE
OSTI Identifier:
1360928
Citation Formats
Treadwell, LaRico J., Boyle, Timothy J., Phelan, W. Adam, Parkes, Marie V., and Young, David P.. Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production. United States: N. p., Web. doi:10.1039/c6dt04083g.
Copy to clipboard
Treadwell, LaRico J., Boyle, Timothy J., Phelan, W. Adam, Parkes, Marie V., & Young, David P.. Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production. United States. doi:10.1039/c6dt04083g.
Copy to clipboard
Treadwell, LaRico J., Boyle, Timothy J., Phelan, W. Adam, Parkes, Marie V., and Young, David P.. 2017. "Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production". United States. doi:10.1039/c6dt04083g. https://www.osti.gov/servlets/purl/1360928.
Copy to clipboard
@article{osti_1360928,
title = {Synthesis and characterization of a series of nickel( ii ) alkoxide precursors and their utility for Ni(0) nanoparticle production},
author = {Treadwell, LaRico J. and Boyle, Timothy J. and Phelan, W. Adam and Parkes, Marie V. and Young, David P.},
abstractNote = {We synthesized a series of nickel(II) aryloxide ([Ni(OAr)2(py)x]) precursors from an amide-alcohol exchange using [Ni(NR2)2] in the presence of pyridine (py). The H-OAr selected were the mono- and di-ortho-substituted 2-alkyl phenols: alkyl = methyl (H-oMP), iso-propyl (H-oPP), tert-butyl (H-oBP) and 2,6-di-alkyl phenols (alkyl = di-iso-propyl (H-DIP), di-tert-butyl (H-DBP), di-phenyl (H-DPhP)). Furthermore, the crystalline products were solved as solvated monomers and structurally characterized as [Ni(OAr)2(py)x], where x = 4: OAr = oMP (1), oPP (2); x = 3: OAr = oBP (3), DIP (4); x = 2: OAr = DBP (5), DPhP (6). The excited states (singlet or triplet) and various geometries of 1–6 were identified by experimental UV-vis and verified by computational modeling. Magnetic susceptibility of the representative compound 4 was fit to a Curie Weiss model that yielded a magnetic moment of 4.38(3)μB consistent with a Ni2+ center. Compounds 1 and 6 were selected for decomposition studied under solution precipitation routes since they represent the two extremes of coordination. The particle size and crystalline structure were characterized using transmission electron microscopy (TEM) and powder X-ray diffraction (PXRD). Finally, the materials isolated from 1 and 6 were found by TEM to form irregular shape nanomaterials (8–15 nm), which by PXRD were found to be Ni0 hcp (PDF: 01-089-7129) and fcc (PDF: 01-070-0989), respectively.},
doi = {10.1039/c6dt04083g},
journal = {Dalton Transactions},
number = 18,
volume = 46,
place = {United States},
year = {2017},
month = {2}
}
Copy to clipboard
[ × clear filter / sort ]

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996
  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865
The Cambridge Structural Database
journal, April 2016
  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179
  • DOI: 10.1107/S2052520616003954
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals
journal, January 1985
  • Hay, P. Jeffrey; Wadt, Willard R.
  • The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310
  • DOI: 10.1063/1.448975
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements
journal, October 1982
  • Francl, Michelle M.; Pietro, William J.; Hehre, Warren J.
  • The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665
  • DOI: 10.1063/1.444267
Controlled Design of Size-Tunable Monodisperse Nickel Nanoparticles
journal, February 2010
  • Carenco, Sophie; Boissière, Cédric; Nicole, Lionel
  • Chemistry of Materials, Vol. 22, Issue 4, p. 1340-1349
  • DOI: 10.1021/cm902007g
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972
  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527

    Similar records in DOE PAGES and OSTI.GOV collections: