Application and Limitations of Nanocasting in Metal-Organic Frameworks

Camille D. Malonzo, Zhao Wang, Jiaxin Duan, Wenyang Zhao, Thomas E. Webber, Zhanyong Li, In Soo Kim, Anurag Kumar, Aditya Bhan, Ana E. Platero-Prats, Karena W. Chapman, Omar K. Farha, Joseph T. Hupp, Alex B.F. Martinson, Lee Penn, Andreas Stein

Research output: Contribution to journalArticlepeer-review

19 Scopus citations


Nanocasting can be a useful strategy to transfer the catalytic metal clusters in metal-organic frameworks (MOFs) to an all-inorganic support such as silica. The incorporation of silica in the MOF pores as a secondary support has the potential to extend the application of the highly tunable metal-based active sites in MOFs to high temperature catalysis. Here, we demonstrate the applicability of the nanocasting method to a range of MOFs that incorporate catalytically attractive hexazirconium, hexacerium, or pentanickel oxide-based clusters (UiO-66, (Ce)UiO-66, (Ce)UiO-67, (Ce)MOF-808, DUT-9, and In- and Ni-postmetalated NU-1000). We describe, in tutorial form, the challenges associated with nanocasting of MOFs that are related to their small pore size and to considerations of chemical and mechanical stability, and we provide approaches to overcome some of these challenges. Some of these nanocast materials feature the site-isolated clusters in a porous, thermally stable silica matrix, suitable for catalysis at high temperatures; in others, structural rearrangement of clusters or partial cluster aggregation occurs, but extensive aggregation can be mitigated by the silica skeleton introduced during nanocasting.

Original languageEnglish (US)
Pages (from-to)2782-2790
Number of pages9
JournalInorganic chemistry
Issue number5
StatePublished - Mar 5 2018

Bibliographical note

Funding Information:
This work was supported as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DE-SC0012702. Work done at Argonne was performed using the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE-AC02-06CH11357. Parts of this work were performed at the University of Minnesota Characterization Facility, which receives partial support from the NSF through the MRSEC, ERC, MRI, and NNIN programs.

Publisher Copyright:
© 2018 American Chemical Society.

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