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

Journal Article · Fri Mar 01 04:00:00 EST 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.8b04828· OSTI ID:1509897

Liu, Jian ^[1]; Li, Zhanyong ^[1]; Zhang, Xuan ^[1]; Otake, Ken-ichi ^[1]; Zhang, Lin ^[1]; Peters, Aaron W. ^[1]; Young, Matthias J. ^[2]; Bedford, Nicholas M. ^[3]; Letourneau, Steven P. ^[2]; Mandia, David J. ^[2]; Elam, Jeffrey W. ^[2]; Farha, Omar K. ^[1]; Hupp, Joseph T. ^[1]

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1. Northwestern Univ., Evanston, IL (United States)
2. Argonne National Lab. (ANL), Argonne, IL (United States)
3. Univ. of New South Wales, Sydney, NSW (Australia)

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 i 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 = -NH₂, -OCH₃, -CH₃, -H, -F, and -NO₂) 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. Here 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.

• Research Organization: Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
• Grant/Contract Number: AC02-06CH11357
• OSTI ID: 1509897
• Journal Information: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 4 Vol. 9; ISSN 2155-5435
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Hammett constant
ethylene hydrogenation
heterogeneous catalysis
ligand modification
metal-organic framework
zirconia-like node