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Title: Application and Limitations of Nanocasting in Metal–Organic Frameworks

Abstract

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-post-metalated 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.

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [3];  [4]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, United States
  2. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
  3. Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States
  4. Department of Chemical Engineering and Materials Science, University of Minnesota, Minneapolis, Minnesota 55455, United States
  5. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States
  6. Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States; Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1434932
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 57; Journal Issue: 5
Country of Publication:
United States
Language:
English

Citation Formats

Malonzo, Camille D., Wang, Zhao, Duan, Jiaxin, Zhao, Wenyang, Webber, Thomas E., Li, Zhanyong, Kim, In Soo, Kumar, Anurag, Bhan, Aditya, Platero-Prats, Ana E., Chapman, Karena W., Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., Penn, R. Lee, and Stein, Andreas. Application and Limitations of Nanocasting in Metal–Organic Frameworks. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b03181.
Malonzo, Camille D., Wang, Zhao, Duan, Jiaxin, Zhao, Wenyang, Webber, Thomas E., Li, Zhanyong, Kim, In Soo, Kumar, Anurag, Bhan, Aditya, Platero-Prats, Ana E., Chapman, Karena W., Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., Penn, R. Lee, & Stein, Andreas. Application and Limitations of Nanocasting in Metal–Organic Frameworks. United States. doi:10.1021/acs.inorgchem.7b03181.
Malonzo, Camille D., Wang, Zhao, Duan, Jiaxin, Zhao, Wenyang, Webber, Thomas E., Li, Zhanyong, Kim, In Soo, Kumar, Anurag, Bhan, Aditya, Platero-Prats, Ana E., Chapman, Karena W., Farha, Omar K., Hupp, Joseph T., Martinson, Alex B. F., Penn, R. Lee, and Stein, Andreas. Mon . "Application and Limitations of Nanocasting in Metal–Organic Frameworks". United States. doi:10.1021/acs.inorgchem.7b03181.
@article{osti_1434932,
title = {Application and Limitations of Nanocasting in Metal–Organic Frameworks},
author = {Malonzo, Camille D. and Wang, Zhao and Duan, Jiaxin and Zhao, Wenyang and Webber, Thomas E. and Li, Zhanyong and Kim, In Soo and Kumar, Anurag and Bhan, Aditya and Platero-Prats, Ana E. and Chapman, Karena W. and Farha, Omar K. and Hupp, Joseph T. and Martinson, Alex B. F. and Penn, R. Lee and Stein, Andreas},
abstractNote = {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-post-metalated 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.},
doi = {10.1021/acs.inorgchem.7b03181},
journal = {Inorganic Chemistry},
number = 5,
volume = 57,
place = {United States},
year = {Mon Feb 12 00:00:00 EST 2018},
month = {Mon Feb 12 00:00:00 EST 2018}
}