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:
-
- 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:
- 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.
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}
}
Web of Science