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

Journal Article · · Inorganic Chemistry
 [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

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.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1434932
Journal Information:
Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 5 Vol. 57; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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