Addition of ethylene to a π-conjugated two-dimensional nickel-based organometallic framework with implications for olefin separation

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Abstract

We have investigated the mechanism for the reversible addition of ethylene to a periodic 2D network of square-planar nickel centers ([Ni(SC)4]n) using density functional theory. The mechanism is analogous to that for homogeneous olefin binding to metal bis(dithiolene) complexes. We considered periodic boundary calculations (PBC) as well as clusters containing up to 12 nickel atoms using a screened hybrid density functional to obtain accurate reaction barriers. Several different products were analyzed. The lowest-energy route begins with the addition of ethylene across the nickel–sulfur bond, which has previously not been considered for this system. The effect of the addition of several alkene molecules simultaneously on the surface was investigated to determine the potential efficiency of this material. This material is a candidate for alkene purification as it exhibits similar reactivity to its molecular analog in terms of the relative stability of products, energy barriers, and molecular efficiency while also providing the intrinsic technical benefits of heterogeneous catalysis.

Original languageEnglish
JournalJournal of Molecular Modeling
Volume21
Issue number5
DOIs
Publication statusPublished - 1 May 2015

Fingerprint

Alkenes
Organometallics
Nickel
alkenes
Olefins
Ethylene
ethylene
nickel
Energy barriers
products
purification
Catalysis
catalysis
Purification
Density functional theory
reactivity
Metals
routes
analogs
density functional theory

Keywords

  • Density functional theory
  • Nanomaterials
  • Nickel
  • Olefin purification
  • Periodic boundary conditions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications
  • Computational Theory and Mathematics
  • Catalysis
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

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abstract = "We have investigated the mechanism for the reversible addition of ethylene to a periodic 2D network of square-planar nickel centers ([Ni(SC)4]n) using density functional theory. The mechanism is analogous to that for homogeneous olefin binding to metal bis(dithiolene) complexes. We considered periodic boundary calculations (PBC) as well as clusters containing up to 12 nickel atoms using a screened hybrid density functional to obtain accurate reaction barriers. Several different products were analyzed. The lowest-energy route begins with the addition of ethylene across the nickel–sulfur bond, which has previously not been considered for this system. The effect of the addition of several alkene molecules simultaneously on the surface was investigated to determine the potential efficiency of this material. This material is a candidate for alkene purification as it exhibits similar reactivity to its molecular analog in terms of the relative stability of products, energy barriers, and molecular efficiency while also providing the intrinsic technical benefits of heterogeneous catalysis.",
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T1 - Addition of ethylene to a π-conjugated two-dimensional nickel-based organometallic framework with implications for olefin separation

AU - Moncho Escriva, Salvador

AU - Brothers, Edward

AU - Hall, Michael B.

PY - 2015/5/1

Y1 - 2015/5/1

N2 - We have investigated the mechanism for the reversible addition of ethylene to a periodic 2D network of square-planar nickel centers ([Ni(SC)4]n) using density functional theory. The mechanism is analogous to that for homogeneous olefin binding to metal bis(dithiolene) complexes. We considered periodic boundary calculations (PBC) as well as clusters containing up to 12 nickel atoms using a screened hybrid density functional to obtain accurate reaction barriers. Several different products were analyzed. The lowest-energy route begins with the addition of ethylene across the nickel–sulfur bond, which has previously not been considered for this system. The effect of the addition of several alkene molecules simultaneously on the surface was investigated to determine the potential efficiency of this material. This material is a candidate for alkene purification as it exhibits similar reactivity to its molecular analog in terms of the relative stability of products, energy barriers, and molecular efficiency while also providing the intrinsic technical benefits of heterogeneous catalysis.

AB - We have investigated the mechanism for the reversible addition of ethylene to a periodic 2D network of square-planar nickel centers ([Ni(SC)4]n) using density functional theory. The mechanism is analogous to that for homogeneous olefin binding to metal bis(dithiolene) complexes. We considered periodic boundary calculations (PBC) as well as clusters containing up to 12 nickel atoms using a screened hybrid density functional to obtain accurate reaction barriers. Several different products were analyzed. The lowest-energy route begins with the addition of ethylene across the nickel–sulfur bond, which has previously not been considered for this system. The effect of the addition of several alkene molecules simultaneously on the surface was investigated to determine the potential efficiency of this material. This material is a candidate for alkene purification as it exhibits similar reactivity to its molecular analog in terms of the relative stability of products, energy barriers, and molecular efficiency while also providing the intrinsic technical benefits of heterogeneous catalysis.

KW - Density functional theory

KW - Nanomaterials

KW - Nickel

KW - Olefin purification

KW - Periodic boundary conditions

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