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]
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-basedmore »