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

Full Record
Other Related Research

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.

Copy to clipboard


                    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.

Copy to clipboard


                    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.

Copy to clipboard


                    
@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}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1021/acs.cgd.8b00630

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Similar Records in DOE PAGES and OSTI.GOV collections:

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

Journal Article Braunecker, Wade A. ; Hurst, Katherine E. ; Ray, Keith G. ; ... - Crystal Growth and Design
DOI: 10.1021/acs.cgd.8b00630

Full Text Available
Buckling of Two-Dimensional Covalent Organic Frameworks under Thermal Stress

Journal Article Evans, Austin M. ; Ryder, Matthew R. ; Flanders, Nathan C. ; ... - Industrial and Engineering Chemistry Research

Two-dimensional covalent organic frameworks (2D COFs) are periodic, permanently porous, and lightweight solids that are polymerized from topologically designed monomers. The predictable design and structural modularity of these materials make them promising candidates for applications including catalysis, environmental remediation, chemical separations, and organic electronics, many of which will require stability to mechanical and thermal stress. Based on their reinforced structures and high degradation temperatures, as determined by thermal gravimetric analysis (TGA), many reports have claimed that COFs have excellent thermal stability. However, their stability to heat and pressure has not been probed using methods that report on structural changes rathermore »« less
DOI: 10.1021/acs.iecr.9b01288
Stacking order dynamics in the quasi-two-dimensional dichalcogenide 1 T-TaS ₂ probed with MeV ultrafast electron diffraction

Journal Article Le Guyader, L. ; Chase, T. ; Reid, A. H. ; ... - Structural Dynamics

Transitions between different charge density wave (CDW) states in quasi-two-dimensional materials may be accompanied also by changes in the inter-layer stacking of the CDW. Using MeV ultrafast electron diffraction, the out-of-plane stacking order dynamics in the quasi-two-dimensional dichalcogenide 1 T-TaS ₂ is investigated for the first time. From the intensity of the CDW satellites aligned around the commensurate l = 1/6 characteristic stacking order, it is found out that this phase disappears with a 0.3 ps time constant. Simultaneously, in the same experiment, the emergence of the incommensurate phase, with a slightly slower 2.0 ps time constant, is determined frommore »« less
Cited by 2
DOI: 10.1063/1.4982918

Full Text Available
Facile transformation of imine covalent organic frameworks into ultrastable crystalline porous aromatic frameworks

Journal Article Li, Xinle ; Zhang, Changlin ; Cai, Songliang ; ... - Nature Communications

The growing interest in two-dimensional imine-based covalent organic frameworks (COFs) is inspired by their crystalline porous structures and the potential for extensive π-electron delocalization. The intrinsic reversibility and strong polarization of imine linkages, however, leads to insufficient chemical stability and optoelectronic properties. Developing COFs with improved robustness and π-delocalization is highly desirable but remains an unsettled challenge. Here we report a facile strategy that transforms imine-linked COFs into ultrastable porous aromatic frameworks by kinetically fixing the reversible imine linkage via an aza-Diels-Alder cycloaddition reaction. The as-formed, quinoline-linked COFs not only retain crystallinity and porosity, but also display dramatically enhanced chemicalmore »« less
DOI: 10.1038/s41467-018-05462-4

Full Text Available
High temperature ferromagnetism in π-conjugated two-dimensional metal–organic frameworks

Journal Article Li, Wenbin ; Sun, Lei ; Qi, Jingshan ; ... - Chemical Science

Simulations demonstrate the critical roles of π-conjugation and large magnetic anisotropy in realizing high-temperature ferromagnetic 2D metal–organic framework, which is also half-metallic.
Cited by 3
DOI: 10.1039/c6sc05080h

Full Text Available

Similar Records