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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. Finally, 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. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
  2. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
  4. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science
  5. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-ray Science Division
  6. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1434932
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 5; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; active site stabilization; catalysis; metal-organic frameworks; nanocasting; sol-gel

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. Tue . "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. Finally, 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 = {Tue Feb 20 00:00:00 EST 2018},
month = {Tue Feb 20 00:00:00 EST 2018}
}

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