Beyond the Active Site

Tuning the Activity and Selectivity of a Metal-Organic Framework-Supported Ni Catalyst for Ethylene Dimerization

Jian Liu, Jingyun Ye, Zhanyong Li, Ken Ichi Otake, Yijun Liao, Aaron W. Peters, Hyunho Noh, Donald G. Truhlar, Laura Gagliardi, Christopher J. Cramer, Omar K. Farha, Joseph T Hupp

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

To modify its steric and electronic properties as a support for heterogeneous catalysts, electron-withdrawing and electron-donating ligands, hexafluoroacetylacetonate (Facac-) and acetylacetonate (Acac-), were introduced to the metal-organic framework (MOF), NU-1000, via a process akin to atomic layer deposition (ALD). In the absence of Facac- or Acac-, NU-1000-supported, AIM-installed Ni(II) sites yield a mixture of C4, C6, C8, and polymeric products in ethylene oligomerization. (AIM = ALD-like deposition in MOFs). In contrast, both Ni-Facac-AIM-NU-1000 and Ni-Acac-AIM-NU-1000 exhibit quantitative catalytic selectivity for C4 species. Experimental findings are supported by density functional theory calculations, which show increases in the activation barrier for the C-C coupling step, due mainly to rearrangement of the siting of Facac- or Acac- to partially ligate added nickel. The results illustrate the important role of structure-tuning support modifiers in controlling the activity of MOF-sited heterogeneous catalysts and in engendering catalytic selectivity. The results also illustrate the ease with which crystallographically well-defined modifications of the catalyst support can be introduced when the node-coordinating molecular modifier is delivered via the vapor phase.

Original languageEnglish
Pages (from-to)11174-11178
Number of pages5
JournalJournal of the American Chemical Society
Volume140
Issue number36
DOIs
Publication statusPublished - Sep 12 2018

Fingerprint

Dimerization
Atomic layer deposition
Catalyst selectivity
Catalyst supports
Catalytic Domain
Ethylene
Tuning
Metals
Electrons
Oligomerization
Catalysts
Nickel
Electronic properties
Density functional theory
Chemical activation
Vapors
Ligands
ethylene
hexafluoroacetylacetonate
acetyl acetonate

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Beyond the Active Site : Tuning the Activity and Selectivity of a Metal-Organic Framework-Supported Ni Catalyst for Ethylene Dimerization. / Liu, Jian; Ye, Jingyun; Li, Zhanyong; Otake, Ken Ichi; Liao, Yijun; Peters, Aaron W.; Noh, Hyunho; Truhlar, Donald G.; Gagliardi, Laura; Cramer, Christopher J.; Farha, Omar K.; Hupp, Joseph T.

In: Journal of the American Chemical Society, Vol. 140, No. 36, 12.09.2018, p. 11174-11178.

Research output: Contribution to journalArticle

Liu, J, Ye, J, Li, Z, Otake, KI, Liao, Y, Peters, AW, Noh, H, Truhlar, DG, Gagliardi, L, Cramer, CJ, Farha, OK & Hupp, JT 2018, 'Beyond the Active Site: Tuning the Activity and Selectivity of a Metal-Organic Framework-Supported Ni Catalyst for Ethylene Dimerization', Journal of the American Chemical Society, vol. 140, no. 36, pp. 11174-11178. https://doi.org/10.1021/jacs.8b06006
Liu, Jian ; Ye, Jingyun ; Li, Zhanyong ; Otake, Ken Ichi ; Liao, Yijun ; Peters, Aaron W. ; Noh, Hyunho ; Truhlar, Donald G. ; Gagliardi, Laura ; Cramer, Christopher J. ; Farha, Omar K. ; Hupp, Joseph T. / Beyond the Active Site : Tuning the Activity and Selectivity of a Metal-Organic Framework-Supported Ni Catalyst for Ethylene Dimerization. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 36. pp. 11174-11178.
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