Principal Investigator Mircea Dinca
Similar to zeolites, metal-organic frameworks could function as veritable solid-state scaffolds for a variety of small molecule transformations relevant to chemical feedstocks and energy conversion. We aim to synthesize new ligands and materials that will take advantage of the inherently rigid nature of MOFs and introduce redox-active metal centers with particularly unusual and reactive coordination spheres. One particularly promising and efficient method to turn MOFs that show no redox reactivity into exciting redox-active materials is ion exchange. We have shown, for instance, that Zn2+ ions in Zn4O(1,4-benzenedicarboxylate)3 (MOF-5), arguably the most famous material in its class, can be substituted with a variety of other metal ions (above), thereby making MOF-5 redox-active and amenable for small molecule activation. We are now exploring the scope of the post-synthetic ion metathesis (PSIM) approach, aiming to understand the fundamentals of this very broad and incredibly useful technique. Ultimately, we wish to explore the reactivity of the highly unusual metal centers that we can isolate within MOFs either directly or via PSIM. These materials could serve as efficient catalysts for a series of transformations of industrial importance. Currently, we are interested in using natural gas as a chemical feedstock and are studying new oxidation chemistry with redox-active MOFs. Students involved in this project become familiar with ligand synthesis and solvothermal techniques, gas sorption studies, and a variety of in-situ spectroscopy techniques that are crucial for characterizing the materials and their reactivity towards molecules such as O2, NO, and N2O.