Tuning Zr-MOF Lewis acidity for heterogeneous catalysis

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Date
2021-08
Authors
Dolge, Kevin Lee
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Stanley, Levi M
Huang, Wenyu Y
Windus, Theresa
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Chemistry
Abstract
This thesis discusses the use of zirconium-based metal-organic frameworks (MOFs) as a heterogeneous catalyst by tuning the Lewis acidity of the nodes. The Zr6-nodes of MOFs NU-1000 and MOF-808 have undergone counterion exchange with sulfate and triflate to increase their Lewis acidity and, subsequently, their chemical activity. Two Lewis acid-catalyzed reactions studied, esterification and Diels-Alder, helped determine the functionalized materials' reactivity. It was shown that triflated analogs of the MOFs shown the highest reactivity in these reactions, as well as higher instability in protic solvents. On the other hand, the sulfated analogs displayed a good balance between reactivity and stability in different environments. The counterion exchange had previously only been observed in MOF-808. Expanding the method to encompass NU-1000 demonstrated that this method could be generically applied to other MOFs. The functionalized NU-1000 material also has a larger pore size than MOF-808, so it has the ability to expose more active node sites to larger, bulkier substrates.
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