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Title: Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework

Abstract

Here, direct control over structure and location of catalytic species deposited on amorphous supports represents a formidable challenge in heterogeneous catalysis. In contrast, a structurally well-defined, crystalline metal–organic framework (MOF) can be rationally designed using post-synthetic techniques to allow for desired structural or locational changes of deposited metal ions. Herein, naphthalene dicarboxylate linkers are incorporated in the MOF, NU-1000, to block the small cavities where few-atom clusters of cobalt oxide preferentially grow, inducing catalyst deposition towards hither-to ill-favored grafting sites orientated toward NU-1000’s mesoporous channels. Despite the different cobalt oxide location, the resulting material is still an active propane oxidative dehydrogenation catalyst at low temperature, reaching a turnover frequency of 0.68 ± 0.05 h –1 at 230 °C and confirming the utility of MOFs as crystalline supports to guide rational design of catalysts.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. Autonoma de Madrid, Madrid (Spain)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Northwestern Univ., Evanston, IL (United States); King Abdulaziz, Univ., Jeddah (Saudi Arabia)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1435951
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Materials and Interfaces
Additional Journal Information:
Journal Volume: 10; Journal Issue: 17; Journal ID: ISSN 1944-8244
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Catalyst Location; Cobalt Oxide; Metal–Organic Frameworks; Oxidative Dehydrogenation of Propane; Post-Synthetic Modification

Citation Formats

Peters, Aaron W., Otake, Kenichi, Platero-Prats, Ana E., Li, Zhanyong, DeStefano, Matthew R., Chapman, Karena W., Farha, Omar K., and Hupp, Joseph T. Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework. United States: N. p., 2018. Web. doi:10.1021/acsami.8b02825.
Peters, Aaron W., Otake, Kenichi, Platero-Prats, Ana E., Li, Zhanyong, DeStefano, Matthew R., Chapman, Karena W., Farha, Omar K., & Hupp, Joseph T. Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework. United States. doi:10.1021/acsami.8b02825.
Peters, Aaron W., Otake, Kenichi, Platero-Prats, Ana E., Li, Zhanyong, DeStefano, Matthew R., Chapman, Karena W., Farha, Omar K., and Hupp, Joseph T. Thu . "Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework". United States. doi:10.1021/acsami.8b02825. https://www.osti.gov/servlets/purl/1435951.
@article{osti_1435951,
title = {Site-Directed Synthesis of Cobalt Oxide Clusters in a Metal–Organic Framework},
author = {Peters, Aaron W. and Otake, Kenichi and Platero-Prats, Ana E. and Li, Zhanyong and DeStefano, Matthew R. and Chapman, Karena W. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {Here, direct control over structure and location of catalytic species deposited on amorphous supports represents a formidable challenge in heterogeneous catalysis. In contrast, a structurally well-defined, crystalline metal–organic framework (MOF) can be rationally designed using post-synthetic techniques to allow for desired structural or locational changes of deposited metal ions. Herein, naphthalene dicarboxylate linkers are incorporated in the MOF, NU-1000, to block the small cavities where few-atom clusters of cobalt oxide preferentially grow, inducing catalyst deposition towards hither-to ill-favored grafting sites orientated toward NU-1000’s mesoporous channels. Despite the different cobalt oxide location, the resulting material is still an active propane oxidative dehydrogenation catalyst at low temperature, reaching a turnover frequency of 0.68 ± 0.05 h–1 at 230 °C and confirming the utility of MOFs as crystalline supports to guide rational design of catalysts.},
doi = {10.1021/acsami.8b02825},
journal = {ACS Applied Materials and Interfaces},
number = 17,
volume = 10,
place = {United States},
year = {2018},
month = {4}
}

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Figures / Tables:

Figure 1 Figure 1: Structure of NU-1000 with emphasis on observed electron density of metal ions after post-synthetic anchoring of metal sites (Zr, green spheres; O, red spheres; C, gray). In the absence of NDC (see following text), deposition occurs near exclusively in the 8 Å cavities of NU-1000 (blue mesh) rathermore » than on hydroxides/aqua ligands pointed towards the 30 Å mesopores (purple mesh).« less

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Works referencing / citing this record:

Tuning of the flexibility in metal–organic frameworks based on pendant arm macrocycles
journal, January 2019

  • Jeoung, Sungeun; Lee, Songho; Lee, Jae Hwa
  • Chemical Communications, Vol. 55, Issue 60
  • DOI: 10.1039/c9cc02819f

Tuning of the flexibility in metal–organic frameworks based on pendant arm macrocycles
journal, January 2019

  • Jeoung, Sungeun; Lee, Songho; Lee, Jae Hwa
  • Chemical Communications, Vol. 55, Issue 60
  • DOI: 10.1039/c9cc02819f

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.