Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks

doi:10.1021/acs.cgd.8b00630

Title: Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks

Abstract

A two-dimensional imine-based covalent organic framework (COF) was designed and synthesized such that phenyl and perfluorophenyl structural units can seamlessly alternate between layers of the framework. X-ray diffraction of the COF powders reveals a striking increase in crystallinity for the COF with self-complementary phenyl/perfluorophenyl interactions (FASt-COF). Whereas measured values of the Brunauer-Emmet-Teller (BET) surface areas for the nonfluorinated Base-COF and the COF employing hydrogen bonding were ~37% and 59%, respectively, of their theoretical Connolly surface areas, the BET value for FASt-COF achieves >90% of its theoretical value (~1700 m2/g). Transmission electron microscopy images also revealed unique micron-sized rodlike features in FASt-COF that were not present in the other materials. The results highlight a promising approach for improving surface areas and long-range order in two-dimensional COFs.

Authors:

^[1]; Hurst, Katherine E. ^[1]; Ray, Keith G. ^[2]; Owczarczyk, Zbyslaw R. ^[1]; Martinez, Madison B. ^[3]; Leick, Noemi ^[1]; Keuhlen, Amy ^[4];

^[4];

^[1]

National Renewable Energy Lab. (NREL), Golden, CO (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Colorado School of Mines, Golden, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Colorado School of Mines, Golden, CO (United States)

Publication Date:: 2018-06-05

Research Org.:: National Renewable Energy Lab. (NREL), Golden, CO (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

Sponsoring Org.:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)

OSTI Identifier:: 1457122

Alternate Identifier(s):: OSTI ID: 1502015

Report Number(s):: NREL/JA-5900-70871; LLNL-JRNL-746901
Journal ID: ISSN 1528-7483

Grant/Contract Number:: AC36-08GO28308; AC52-07NA27344

Resource Type:: Accepted Manuscript

Journal Name:: Crystal Growth and Design

Additional Journal Information:: Journal Volume: 18; Journal Issue: 7; Journal ID: ISSN 1528-7483

Publisher:: American Chemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; frameworks; gas storage; crystal; fluorination

Citation Formats


                    Braunecker, Wade A., Hurst, Katherine E., Ray, Keith G., Owczarczyk, Zbyslaw R., Martinez, Madison B., Leick, Noemi, Keuhlen, Amy, Sellinger, Alan, and Johnson, Justin C. Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks.  United States: N. p., 2018. 
        Web.  doi:10.1021/acs.cgd.8b00630.

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                    Braunecker, Wade A., Hurst, Katherine E., Ray, Keith G., Owczarczyk, Zbyslaw R., Martinez, Madison B., Leick, Noemi, Keuhlen, Amy, Sellinger, Alan, & Johnson, Justin C. Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks.  United States.  doi:10.1021/acs.cgd.8b00630.

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                    Braunecker, Wade A., Hurst, Katherine E., Ray, Keith G., Owczarczyk, Zbyslaw R., Martinez, Madison B., Leick, Noemi, Keuhlen, Amy, Sellinger, Alan, and Johnson, Justin C. Tue .  
        "Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks".  United States.  doi:10.1021/acs.cgd.8b00630.  https://www.osti.gov/servlets/purl/1457122.

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@article{osti_1457122,

  title        = {Phenyl/Perfluorophenyl Stacking Interactions Enhance Structural Order in Two-Dimensional Covalent Organic Frameworks},

  author       = {Braunecker, Wade A. and Hurst, Katherine E. and Ray, Keith G. and Owczarczyk, Zbyslaw R. and Martinez, Madison B. and Leick, Noemi and Keuhlen, Amy and Sellinger, Alan and Johnson, Justin C.},

  abstractNote = {A two-dimensional imine-based covalent organic framework (COF) was designed and synthesized such that phenyl and perfluorophenyl structural units can seamlessly alternate between layers of the framework. X-ray diffraction of the COF powders reveals a striking increase in crystallinity for the COF with self-complementary phenyl/perfluorophenyl interactions (FASt-COF). Whereas measured values of the Brunauer-Emmet-Teller (BET) surface areas for the nonfluorinated Base-COF and the COF employing hydrogen bonding were ~37% and 59%, respectively, of their theoretical Connolly surface areas, the BET value for FASt-COF achieves >90% of its theoretical value (~1700 m2/g). Transmission electron microscopy images also revealed unique micron-sized rodlike features in FASt-COF that were not present in the other materials. The results highlight a promising approach for improving surface areas and long-range order in two-dimensional COFs.},

  doi          = {10.1021/acs.cgd.8b00630},

  journal      = {Crystal Growth and Design},

  number       = 7,

  volume       = 18,

  place        = {United States},

  year         = {2018},

  month        = {6}

}

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Journal Article:

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DOI: 10.1021/acs.cgd.8b00630

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Figures / Tables:

Scheme 1: Synthesis of Imine-Based 2-D COFs

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