Determination of Bulk and Surface Atomic Arrangement in Ni-Zn γ-Brass Phase at Different Ni to Zn Ratios

Charles S. Spanjers, Anish Dasgupta, Melanie Kirkham, Blake A. Burger, Gaurav Kumar, Michael J. Janik, Robert M. Rioux

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Previous attempts to characterize the γ-brass crystal structure of Ni-Zn (15.4-24% Ni) have failed to identify the location of the Ni and Zn atoms in the crystal lattice for more than 15.4% Ni content (Ni8Zn44) due to the similar X-ray diffraction cross sections of Ni and Zn. Ni8Zn44 is known to have a typical γ-brass crystal structure (space group 217, I43m, 52 atom unit cell with four distinct symmetry positions: inner tetrahedral, outer tetrahedral, octahedral, and cuboctahedral) where Ni atoms reside in outer tetrahedral sites completely isolated from each other and coordinated by 12 Zn atoms. We utilize neutron diffraction to identify the substitution positions of Zn by Ni when the Ni content is increased above 15.4% and up to 19.2% (Ni10Zn42). Upon increasing the Ni content above 15.4% (Ni9Zn43 and Ni10Zn42), Zn in the γ-brass octahedral positions are replaced by Ni leading to the formation of Ni-Ni-Ni trimers, which are absent in Ni8Zn44. Density functional theory (DFT) calculations confirm our neutron diffraction results regarding the optimal position of excess Ni in the γ-brass unit cell. The well-defined atomic site distribution in γ-brass Ni-Zn provides an excellent opportunity for producing site-isolated base metal catalysts that may find application in selective semihydrogenation. We investigated the presence of Ni-Ni-Ni trimers on the surface using H-D exchange and ethylene hydrogenation as probe reactions, observing the influence of Ni concentration on catalysis. We conclude the catalytic performance is insensitive to Ni content. We provide a possible explanation for this observation using DFT calculations, which demonstrate that surface containing trimer sites are energetically unfavorable and therefore not exposed on Wulff reconstructions of γ-brass phase Ni-Zn particles.

Original languageEnglish (US)
Pages (from-to)504-512
Number of pages9
JournalChemistry of Materials
Volume29
Issue number2
DOIs
StatePublished - Jan 24 2017

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Brass
Atoms
Neutron diffraction
Density functional theory
Crystal structure
Crystal lattices
Catalysis
Hydrogenation
brass
Ion exchange
Ethylene
Substitution reactions
Metals
X ray diffraction
Catalysts

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Materials Chemistry

Cite this

Spanjers, Charles S. ; Dasgupta, Anish ; Kirkham, Melanie ; Burger, Blake A. ; Kumar, Gaurav ; Janik, Michael J. ; Rioux, Robert M. / Determination of Bulk and Surface Atomic Arrangement in Ni-Zn γ-Brass Phase at Different Ni to Zn Ratios. In: Chemistry of Materials. 2017 ; Vol. 29, No. 2. pp. 504-512.
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title = "Determination of Bulk and Surface Atomic Arrangement in Ni-Zn γ-Brass Phase at Different Ni to Zn Ratios",
abstract = "Previous attempts to characterize the γ-brass crystal structure of Ni-Zn (15.4-24{\%} Ni) have failed to identify the location of the Ni and Zn atoms in the crystal lattice for more than 15.4{\%} Ni content (Ni8Zn44) due to the similar X-ray diffraction cross sections of Ni and Zn. Ni8Zn44 is known to have a typical γ-brass crystal structure (space group 217, I43m, 52 atom unit cell with four distinct symmetry positions: inner tetrahedral, outer tetrahedral, octahedral, and cuboctahedral) where Ni atoms reside in outer tetrahedral sites completely isolated from each other and coordinated by 12 Zn atoms. We utilize neutron diffraction to identify the substitution positions of Zn by Ni when the Ni content is increased above 15.4{\%} and up to 19.2{\%} (Ni10Zn42). Upon increasing the Ni content above 15.4{\%} (Ni9Zn43 and Ni10Zn42), Zn in the γ-brass octahedral positions are replaced by Ni leading to the formation of Ni-Ni-Ni trimers, which are absent in Ni8Zn44. Density functional theory (DFT) calculations confirm our neutron diffraction results regarding the optimal position of excess Ni in the γ-brass unit cell. The well-defined atomic site distribution in γ-brass Ni-Zn provides an excellent opportunity for producing site-isolated base metal catalysts that may find application in selective semihydrogenation. We investigated the presence of Ni-Ni-Ni trimers on the surface using H-D exchange and ethylene hydrogenation as probe reactions, observing the influence of Ni concentration on catalysis. We conclude the catalytic performance is insensitive to Ni content. We provide a possible explanation for this observation using DFT calculations, which demonstrate that surface containing trimer sites are energetically unfavorable and therefore not exposed on Wulff reconstructions of γ-brass phase Ni-Zn particles.",
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Determination of Bulk and Surface Atomic Arrangement in Ni-Zn γ-Brass Phase at Different Ni to Zn Ratios. / Spanjers, Charles S.; Dasgupta, Anish; Kirkham, Melanie; Burger, Blake A.; Kumar, Gaurav; Janik, Michael J.; Rioux, Robert M.

In: Chemistry of Materials, Vol. 29, No. 2, 24.01.2017, p. 504-512.

Research output: Contribution to journalArticle

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AU - Spanjers, Charles S.

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AB - Previous attempts to characterize the γ-brass crystal structure of Ni-Zn (15.4-24% Ni) have failed to identify the location of the Ni and Zn atoms in the crystal lattice for more than 15.4% Ni content (Ni8Zn44) due to the similar X-ray diffraction cross sections of Ni and Zn. Ni8Zn44 is known to have a typical γ-brass crystal structure (space group 217, I43m, 52 atom unit cell with four distinct symmetry positions: inner tetrahedral, outer tetrahedral, octahedral, and cuboctahedral) where Ni atoms reside in outer tetrahedral sites completely isolated from each other and coordinated by 12 Zn atoms. We utilize neutron diffraction to identify the substitution positions of Zn by Ni when the Ni content is increased above 15.4% and up to 19.2% (Ni10Zn42). Upon increasing the Ni content above 15.4% (Ni9Zn43 and Ni10Zn42), Zn in the γ-brass octahedral positions are replaced by Ni leading to the formation of Ni-Ni-Ni trimers, which are absent in Ni8Zn44. Density functional theory (DFT) calculations confirm our neutron diffraction results regarding the optimal position of excess Ni in the γ-brass unit cell. The well-defined atomic site distribution in γ-brass Ni-Zn provides an excellent opportunity for producing site-isolated base metal catalysts that may find application in selective semihydrogenation. We investigated the presence of Ni-Ni-Ni trimers on the surface using H-D exchange and ethylene hydrogenation as probe reactions, observing the influence of Ni concentration on catalysis. We conclude the catalytic performance is insensitive to Ni content. We provide a possible explanation for this observation using DFT calculations, which demonstrate that surface containing trimer sites are energetically unfavorable and therefore not exposed on Wulff reconstructions of γ-brass phase Ni-Zn particles.

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