Introducing Nonstructural Ligands to Zirconia-like Metal-Organic Framework Nodes to Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation

Jian Liu, Zhanyong Li, Xuan Zhang, Ken Ichi Otake, Lin Zhang, Aaron W. Peters, Matthias J. Young, Nicholas M. Bedford, Steven P. Letourneau, David J. Mandia, Jeffrey W. Elam, Omar K. Farha, Joseph T Hupp

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Previous work has shown that introduction of hexafluoroacetylacetone (Facac) units as nonstructural ligands for the zirconia-like nodes of the eight-connected metal-organic framework (MOF), NU-1000, greatly alters the selectivity of node-supported oxy-nickel clusters for ethylene dimerization vs oligomerization. Here we explore a related concept: tuning of support/catalyst interactions, and therefore, catalyst activity, via parallel installation of organic modifiers on the support itself. As modifiers we focused on para-substituted benzoates (R-BA - R = -NH 2 , -OCH 3 , -CH 3 , -H, -F, and -NO 2 ) where the substituents were chosen to present similar steric demand, but varying electron-donating or electron-withdrawing properties. R-benzoate-engendered shifts in the node-based aqua O-H stretching frequency for NU-1000, as measured by DRIFTS (diffuse-reflectance infrared Fourier-transform spectroscopy), together with systematic shifts in Ni 2p peak energies, as measured by X-ray photoelectron spectroscopy, show that the electronic properties of the support can be modulated. The vibrational and electronic peak shifts correlate with the putative electron-withdrawing vs electron-donating strength of the para-substituted benzoate modifiers. Subsequent installation of node-supported, oxy-Ni(II) clusters for ethylene hydrogenation yield a compelling correlation between log (catalyst turnover frequency) and the electron donating or withdrawing character of the substituent of the benzoate units. Single crystal X-ray diffraction measurements reveal that each organic modifier makes use of only one of two available carboxylate oxygens to accomplish grafting. The remaining oxygen atom is, in principle, well positioned to coordinate directly to an installed Ni(II) ion. We postulate that the unanticipated direct coordination of the catalyst by the node-modifier (rather than indirect modifier-based tuning of support(node)/catalyst electronic interactions) is the primary source of the observed systematic tuning of hydrogenation activity. We suggest, however, that regardless of mechanism for communication with active-sites of MOF-supported catalysts, intentional elaboration of nodes via grafted, nonstructural organic species could prove to be a valuable general strategy for fine-tuning supported-catalyst activity and/or selectivity.

Original languageEnglish
Pages (from-to)3198-3207
Number of pages10
JournalACS Catalysis
Volume9
Issue number4
DOIs
Publication statusPublished - Apr 5 2019

Fingerprint

Nickel
Zirconia
Hydrogenation
Benzoates
Ethylene
Metals
Ligands
Tuning
Catalysts
Catalyst supports
Electrons
Catalyst activity
Oxygen
Oligomerization
Dimerization
Catalyst selectivity
Electronic properties
Stretching
Fourier transform infrared spectroscopy
X ray photoelectron spectroscopy

Keywords

  • ethylene hydrogenation
  • Hammett constant
  • heterogeneous catalysis
  • ligand modification
  • metal-organic framework
  • zirconia-like node

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Introducing Nonstructural Ligands to Zirconia-like Metal-Organic Framework Nodes to Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation. / Liu, Jian; Li, Zhanyong; Zhang, Xuan; Otake, Ken Ichi; Zhang, Lin; Peters, Aaron W.; Young, Matthias J.; Bedford, Nicholas M.; Letourneau, Steven P.; Mandia, David J.; Elam, Jeffrey W.; Farha, Omar K.; Hupp, Joseph T.

In: ACS Catalysis, Vol. 9, No. 4, 05.04.2019, p. 3198-3207.

Research output: Contribution to journalArticle

Liu, J, Li, Z, Zhang, X, Otake, KI, Zhang, L, Peters, AW, Young, MJ, Bedford, NM, Letourneau, SP, Mandia, DJ, Elam, JW, Farha, OK & Hupp, JT 2019, 'Introducing Nonstructural Ligands to Zirconia-like Metal-Organic Framework Nodes to Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation', ACS Catalysis, vol. 9, no. 4, pp. 3198-3207. https://doi.org/10.1021/acscatal.8b04828
Liu, Jian ; Li, Zhanyong ; Zhang, Xuan ; Otake, Ken Ichi ; Zhang, Lin ; Peters, Aaron W. ; Young, Matthias J. ; Bedford, Nicholas M. ; Letourneau, Steven P. ; Mandia, David J. ; Elam, Jeffrey W. ; Farha, Omar K. ; Hupp, Joseph T. / Introducing Nonstructural Ligands to Zirconia-like Metal-Organic Framework Nodes to Tune the Activity of Node-Supported Nickel Catalysts for Ethylene Hydrogenation. In: ACS Catalysis. 2019 ; Vol. 9, No. 4. pp. 3198-3207.
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AU - Liu, Jian

AU - Li, Zhanyong

AU - Zhang, Xuan

AU - Otake, Ken Ichi

AU - Zhang, Lin

AU - Peters, Aaron W.

AU - Young, Matthias J.

AU - Bedford, Nicholas M.

AU - Letourneau, Steven P.

AU - Mandia, David J.

AU - Elam, Jeffrey W.

AU - Farha, Omar K.

AU - Hupp, Joseph T

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N2 - Previous work has shown that introduction of hexafluoroacetylacetone (Facac) units as nonstructural ligands for the zirconia-like nodes of the eight-connected metal-organic framework (MOF), NU-1000, greatly alters the selectivity of node-supported oxy-nickel clusters for ethylene dimerization vs oligomerization. Here we explore a related concept: tuning of support/catalyst interactions, and therefore, catalyst activity, via parallel installation of organic modifiers on the support itself. As modifiers we focused on para-substituted benzoates (R-BA - R = -NH 2 , -OCH 3 , -CH 3 , -H, -F, and -NO 2 ) where the substituents were chosen to present similar steric demand, but varying electron-donating or electron-withdrawing properties. R-benzoate-engendered shifts in the node-based aqua O-H stretching frequency for NU-1000, as measured by DRIFTS (diffuse-reflectance infrared Fourier-transform spectroscopy), together with systematic shifts in Ni 2p peak energies, as measured by X-ray photoelectron spectroscopy, show that the electronic properties of the support can be modulated. The vibrational and electronic peak shifts correlate with the putative electron-withdrawing vs electron-donating strength of the para-substituted benzoate modifiers. Subsequent installation of node-supported, oxy-Ni(II) clusters for ethylene hydrogenation yield a compelling correlation between log (catalyst turnover frequency) and the electron donating or withdrawing character of the substituent of the benzoate units. Single crystal X-ray diffraction measurements reveal that each organic modifier makes use of only one of two available carboxylate oxygens to accomplish grafting. The remaining oxygen atom is, in principle, well positioned to coordinate directly to an installed Ni(II) ion. We postulate that the unanticipated direct coordination of the catalyst by the node-modifier (rather than indirect modifier-based tuning of support(node)/catalyst electronic interactions) is the primary source of the observed systematic tuning of hydrogenation activity. We suggest, however, that regardless of mechanism for communication with active-sites of MOF-supported catalysts, intentional elaboration of nodes via grafted, nonstructural organic species could prove to be a valuable general strategy for fine-tuning supported-catalyst activity and/or selectivity.

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KW - ethylene hydrogenation

KW - Hammett constant

KW - heterogeneous catalysis

KW - ligand modification

KW - metal-organic framework

KW - zirconia-like node

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