TY - JOUR
T1 - Application and Limitations of Nanocasting in Metal-Organic Frameworks
AU - Malonzo, Camille D.
AU - Wang, Zhao
AU - Duan, Jiaxin
AU - Zhao, Wenyang
AU - Webber, Thomas E.
AU - Li, Zhanyong
AU - Kim, In Soo
AU - Kumar, Anurag
AU - Bhan, Aditya
AU - Platero-Prats, Ana E.
AU - Chapman, Karena W.
AU - Farha, Omar K.
AU - Hupp, Joseph T.
AU - Martinson, Alex B.F.
AU - Penn, R. Lee
AU - Stein, Andreas
N1 - 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.
PY - 2018/3/5
Y1 - 2018/3/5
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.inorgchem.7b03181
DO - 10.1021/acs.inorgchem.7b03181
M3 - Article
C2 - 29461822
AN - SCOPUS:85043292812
SN - 0020-1669
VL - 57
SP - 2782
EP - 2790
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 5
ER -