Application and Limitations of Nanocasting in Metal–Organic Frameworks

doi:10.1021/acs.inorgchem.7b03181

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

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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:

Malonzo, Camille D. ^[1]; Wang, Zhao ^[1]; Duan, Jiaxin ^[1];

^[1];

^[2]; Kim, In Soo ^[3]; Kumar, Anurag ^[4];

^[4];

^[5];

^[6];

^[2];

^[3];

^[1];

^[1]

Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry
Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemical Engineering and Materials Science
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS), X-ray Science Division
Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; King Abdulaziz Univ., Jeddah (Saudi Arabia). Dept. of Chemistry

Publication Date:: 2018-02-20

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)

OSTI Identifier:: 1434932

Grant/Contract Number:: AC02-06CH11357

Resource Type:: 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.

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                    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.

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                    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.  https://www.osti.gov/servlets/purl/1434932.

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@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         = {2018},

  month        = {2}

}

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DOI: 10.1021/acs.inorgchem.7b03181

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