Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene

Steven Pellizzeri, Melissa Barona, Varinia Bernales, Pere Miró, Peilin Liao, Laura Gagliardi, Randall Q. Snurr, Rachel B. Getman

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Six first-row transition metal cations (Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+) were evaluated as catalysts for ethene dimerization to 1-butene. This is an important reaction in the chemistry of C–C bond formation and in the conversion of natural gas to higher hydrocarbons. Two related classes of transition metal cation catalysts were investigated: 1) single transition metal cations supported on zirconium oxide nodes of the metal–organic framework NU-1000 and 2) small metal hydroxide clusters with two metal atoms (M2) that could be grown by atomic layer deposition on a support exhibiting isolated hydroxyl groups. Using scaling relations, the free energies of co-adsorbed hydrogen and ethene (i.e., (H/C2H4)*) and adsorbed ethyl (i.e., C2H5*) were identified as descriptors for ethene dimerization catalysis. Using degree of rate control analysis, it was determined that the rate controlling steps are either ethene insertion (C–C bond forming) or β-hydride elimination (C–H bond breaking), depending on the metal. Using degree of catalyst control analysis, it was determined that activity on all the catalysts studied could be improved by tuning the free energy of C2H5*.

Original languageEnglish (US)
Pages (from-to)149-157
Number of pages9
JournalCatalysis Today
Volume312
DOIs
StatePublished - Aug 15 2018

Fingerprint

Dimerization
Butenes
Electronic properties
Transition metals
Cations
Catalysts
Positive ions
Metals
Free energy
Hydrogen
Atomic layer deposition
Hydrocarbons
Hydrides
Zirconia
Hydroxyl Radical
Catalysis
Catalyst activity
Natural gas
Tuning
Atoms

Keywords

  • Atomically dispersed catalyst
  • Computational catalysis
  • Hydrocarbon chemistry
  • Metal-organic framework
  • Microkinetic modeling
  • Single atom catalyst

Cite this

Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene. / Pellizzeri, Steven; Barona, Melissa; Bernales, Varinia; Miró, Pere; Liao, Peilin; Gagliardi, Laura; Snurr, Randall Q.; Getman, Rachel B.

In: Catalysis Today, Vol. 312, 15.08.2018, p. 149-157.

Research output: Contribution to journalArticle

Pellizzeri, Steven ; Barona, Melissa ; Bernales, Varinia ; Miró, Pere ; Liao, Peilin ; Gagliardi, Laura ; Snurr, Randall Q. ; Getman, Rachel B. / Catalytic descriptors and electronic properties of single-site catalysts for ethene dimerization to 1-butene. In: Catalysis Today. 2018 ; Vol. 312. pp. 149-157.
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