University of Minnesota
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MOF nodes as nearly ideal supports for molecular catalysts

Metal-organic frameworks have potential applications as supports for catalysts of molecular precision. A collaborative work between the University of Minnesota, the University of California, Davis, and Northwestern University has investigated metal−organic frameworks with Zr6 nodes, UiO-66 and NU-1000, as supports for Ir(CO)2 and Ir(C2H4)2 complexes. A single bonding site for the iridium is identified on the nodes of NU-1000, whereas two sites are identified on UiO-66, although at low iridium loadings only one site is occupied. Density functional theory calculations provide structural results that are in good agreement with infrared and X-ray absorption fine-structure spectra. The reactivity of node-supported Ir(CO)2 with C2H4 and the catalytic activity and selectivity of the species initially present as Ir(C2H4)2 for ethylene hydrogenation and dimerization were investigated both experimentally and computationally and shown to be strongly influenced by the node.

The computational characterization of the species involved was performed at the University of Minnesota by Post-doctoral Associate Samuel Odoh, Ph.D., in Professor Laura Gagliardi’s group, in collaboration with Professor Christopher Cramer. The catalytic study was performed at the University of California Davis.

A video describing the reaction occurring at the material was produced by Graduate Student Joshua Borycz in Laura Gagliardi’s group, and Ben Lynch, Ph.D., at the Minnesota Supercomputing Institute.

Full details of the study are available at D. Yang, S. O. Odoh, T. C. Wang, O. K. Farha, J. T. Hupp, C. J. Cramer, L. Gagliardi, and B. C. Gates, "Metal-organic framework nodes as nearly ideal supports for molecular catalysts: NU-1000- and UiO-66-supported iridium complexes," Journal of the Americal Chemical Society, (2015). DOI: 10.1021/jacs.5b02956.

This project is sponsored by the Department of Energy-funded Inorganometallic Catalysis Design Center based at the university of Minnesota.