Reversible Olefin Addition to Extended Lattices of a Nickel-Selenium Framework

Dušan N. Sredojević, Salvador Moncho Escriva, Rajesh Kumar Raju, Milivoj R. Belić, Edward Brothers

Research output: Contribution to journalArticle

Abstract

We performed density functional theory computations to study the structural and electronic properties as the basis of ethylene addition activity for [Ni(XC)4]n (X = Se, S)-extended lattices. We demonstrated that the mechanism of ethylene cycloaddition to a periodic [Ni(SeC)4]n two-dimensional (2D) network is analogous to that previously described for [Ni(SC)4]n 2D sheets and similar to the metal bis(dithiolene) molecular complexes [M(S2C2R2)2] (M = Ni, Pd, Pt, Co, Cu). These nanosheet materials avoid decomposition upon olefin addition, which is one of the main limitations of the molecular metal bis(dithiolene) complexes, as we find the decomposition processes to be thermodynamically unfavorable. Our calculations also suggest that the preferred conformation of the [Ni(SeC)4]n bilayer lattice is parallel displaced, with the Se atoms positioned above the Ni atoms, which is different from the eclipsed conformation found for [Ni(SC)4]n. We also managed to optimize an adduct of [Ni(SC)4]n in the bilayer form, which exceed the ethylene coverage of molecular complexes. We calculate that the preferred three-dimensional geometry of the stacked sheets is eclipsed because of strong van der Waals interactions. Such an arrangement of the sheets indicates that these materials should be highly porous, pointing to the high capacity for olefin bindings. Indeed, a few moderately stable ethylene adducts have been located. Owing to their unique structures and chemical reactivity, these newly predicted materials can be potentially developed as electrocatalysts for olefin purification.

Original languageEnglish
Pages (from-to)22424-22434
Number of pages11
JournalJournal of Physical Chemistry C
Volume122
Issue number39
DOIs
Publication statusPublished - 4 Oct 2018

Fingerprint

Selenium
Alkenes
selenium
Nickel
alkenes
Olefins
Ethylene
ethylene
nickel
adducts
Conformations
Metals
Decomposition
decomposition
Atoms
Chemical reactivity
Cycloaddition
electrocatalysts
Nanosheets
Electrocatalysts

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

Cite this

Reversible Olefin Addition to Extended Lattices of a Nickel-Selenium Framework. / Sredojević, Dušan N.; Moncho Escriva, Salvador; Raju, Rajesh Kumar; Belić, Milivoj R.; Brothers, Edward.

In: Journal of Physical Chemistry C, Vol. 122, No. 39, 04.10.2018, p. 22424-22434.

Research output: Contribution to journalArticle

Sredojević, Dušan N. ; Moncho Escriva, Salvador ; Raju, Rajesh Kumar ; Belić, Milivoj R. ; Brothers, Edward. / Reversible Olefin Addition to Extended Lattices of a Nickel-Selenium Framework. In: Journal of Physical Chemistry C. 2018 ; Vol. 122, No. 39. pp. 22424-22434.
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