In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks

Tavakoli, Elham; Kakekhani, Arvin; Kaviani, Shayan; Tan, Peng; Ghaleni, Mahdi Mohammadi; Zaeem, Mohsen Asle; Rappe, Andrew M.; Nejati, Siamak

doi:10.1021/jacs.9b10787

Title: In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks

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Abstract

Synthesis and processing of two- or three- dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electro- chemical deposition of poly(5,10,15,20-tetrakis(4- aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. Here, by adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py- POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.

Authors:

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^[2];

^[1]; Tan, Peng ^[3];

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University of Nebraska−Lincoln, NE (United States)
University of Pennsylvania, Philadelphia, PA (United States)
University of Pennsylvania, Philadelphia, PA (United States); Harbin Institute of Technology (China)
Colorado School of Mines, Golden, CO (United States)

Publication Date:: 2019-12-04

Research Org.:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Org.:: University of Nebraska, Colorado School of Mines, China Scholarship Council, Harbin Institute of Technology

OSTI Identifier:: 1658238

Grant/Contract Number:: SC0019281

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 141; Journal Issue: 50; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 30 DIRECT ENERGY CONVERSION; Covalent organic framework (COF); electrochemical deposition; catalysis; nanoporous; catalyst synthesis; oxygen reduction reaction (ORR); redox reactions; pyridines; electrodes; dendrons

Citation Formats


                    Tavakoli, Elham, Kakekhani, Arvin, Kaviani, Shayan, Tan, Peng, Ghaleni, Mahdi Mohammadi, Zaeem, Mohsen Asle, Rappe, Andrew M., and Nejati, Siamak. In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks.  United States: N. p., 2019. 
Web.  doi:10.1021/jacs.9b10787.

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                    Tavakoli, Elham, Kakekhani, Arvin, Kaviani, Shayan, Tan, Peng, Ghaleni, Mahdi Mohammadi, Zaeem, Mohsen Asle, Rappe, Andrew M., & Nejati, Siamak. In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks.  United States.  https://doi.org/10.1021/jacs.9b10787

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                    Tavakoli, Elham, Kakekhani, Arvin, Kaviani, Shayan, Tan, Peng, Ghaleni, Mahdi Mohammadi, Zaeem, Mohsen Asle, Rappe, Andrew M., and Nejati, Siamak. Wed .  
"In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks".  United States.  https://doi.org/10.1021/jacs.9b10787.  https://www.osti.gov/servlets/purl/1658238.

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@article{osti_1658238,

  title        = {In Situ Bottom-up Synthesis of Porphyrin-Based Covalent Organic Frameworks},

  author       = {Tavakoli, Elham and Kakekhani, Arvin and Kaviani, Shayan and Tan, Peng and Ghaleni, Mahdi Mohammadi and Zaeem, Mohsen Asle and Rappe, Andrew M. and Nejati, Siamak},

  abstractNote = {Synthesis and processing of two- or three- dimensional covalent organic frameworks (COFs) have been limited by solvent intractability and sluggish condensation kinetics. Here, we report on the electro- chemical deposition of poly(5,10,15,20-tetrakis(4- aminophenyl)porphyrin)-covalent organic frameworks (POR-COFs) via formation of phenazine linkages. Here, by adjusting the synthetic parameters, we demonstrate the rapid and bottom-up synthesis of COF dendrites. Both experiment and density functional theory underline the prominent role of pyridine, not only as a polymerization promoter but as a stabilizing sublattice, cocrystallizing with the framework. The crucial role of pyridine in dictating the structural properties of such a cocrystal (Py- POR-COF) is discussed. Also, a structure-to-function relationship for this class of materials, governing their electrocatalytic activity for the oxygen reduction reaction in alkaline media, is reported.},

  doi          = {10.1021/jacs.9b10787},

  journal      = {Journal of the American Chemical Society},

  number       = 50,

  volume       = 141,

  place        = {United States},

  year         = {2019},

  month        = {12}

}

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