(157d) Metal Oxide-like Clusters in MOFs As Supports for Well-Defined Rhodium Complex and Rhodium Cluster Catalysts | AIChE

(157d) Metal Oxide-like Clusters in MOFs As Supports for Well-Defined Rhodium Complex and Rhodium Cluster Catalysts


Gates, B. C. - Presenter, University of California at Davis
Yang, D., University of California at Davis
Gagliardi, L., University of Minnesota
Gümüslü, G., University of California
Yu, J., University of California
The nodes of some metal-organic frameworks (MOFs) closely resemble small pieces of metal oxides, exemplified by the Zr6 nodes of Nu-1000. Hydroxyl groups on the structural vacancies in Nu-1000 consisting of pairs of terminal OH and OH2 groups have been evidenced by IR spectroscopy and DFT calculations; they are referred to as site 1. We developed a treatment process to convert site 1 to a new proton topology incorporating hydroxyl sites with pairs of terminal OH groups (site 2). A combination of IR spectroscopy and DFT calculations led to the identification of an intermediate structure with organic ligands coordinated to structural vacancies on the node surface which facilitated the conversion of site 1 to site 2. With Rh(C2H4)2(acac) (acac is acetylacetonate) as a probe of the node surfaces, reaction with the hydroxyl groups of site 1 or site 2 of Nu-1000 gave species identified by IR and EXAFS spectroscopies and DFT as mononuclear Rh(C2H4)2 complexes. Information about the nodes as electron-donor ligands was determined in experiments in which the rhodium diethylene complexes were converted to rhodium gem-dicarbonyls by reaction with Co; the νCO values characterize the electron-donor properties of the support sites. The catalytic activity and selectivity of the species initially present as Rh(C2H4)2 for ethylene hydrogenation and dimerization were investigated both experimentally and computationally and shown to be strongly influenced by the node sites. The Nu-1000-supported mononuclear rhodium complexes were treated in H2 to form small supported rhodium clusters, characterized by changes in the IR and EXAFS spectra; the data suggest the formation of approximately Rh2 clusters on the nodes, and these were found to be stable and 6 times more active for ethylene hydrogenation than the supported single rhodium sites.