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

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:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [2]; ORCiD logo [1]
  1. University of Nebraska−Lincoln, NE (United States)
  2. University of Pennsylvania, Philadelphia, PA (United States)
  3. University of Pennsylvania, Philadelphia, PA (United States); Harbin Institute of Technology (China)
  4. Colorado School of Mines, Golden, CO (United States)
Publication Date:
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. https://doi.org/10.1021/jacs.9b10787.
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
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.
@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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