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Title: Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films

Abstract

Two-dimensional covalent organic frameworks (2D COFs) are ideally suited for organizing redox-active subunits into periodic, permanently porous polymer networks of interest for pseudocapacitive energy storage. Currently, we describe a method for synthesizing crystalline, oriented thin films of a redox-active 2D COF on Au working electrodes. The thickness of the COF film was controlled by varying the initial monomer concentration. A large percentage (80–99%) of the anthraquinone groups are electrochemically accessible in films thinner than 200 nm, an order of magnitude improvement over the same COF prepared as a randomly oriented microcrystalline powder. As a result, electrodes functionalized with oriented COF films exhibit a 400% increase in capacitance scaled to electrode area as compared to those functionalized with the randomly oriented COF powder. These findings demonstrate the promise of redox-active COFs for electrical energy storage and highlight the importance of controlling morphology for optimal performance.

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [1]
  1. Cornell Univ., Ithaca, NY (United States). Baker Lab.
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Materials Center at Cornell (EMC2)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1370446
Grant/Contract Number:  
SC0001086; FG02-87ER45298; PHY-936384; DMR-1332208
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
ACS Nano
Additional Journal Information:
Journal Volume: 9; Journal Issue: 3; Related Information: Emc2 partners with Cornell University (lead); Lawrence Berkeley National Laboratory; Journal ID: ISSN 1936-0851
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; covalent organic framework; polymer films; energy storage supercapacitors; nanoporous materials; electrochemistry; surface science

Citation Formats

DeBlase, Catherine R., Hernández-Burgos, Kenneth, Silberstein, Katharine E., Rodríguez-Calero, Gabriel G., Bisbey, Ryan P., Abruña, Héctor D., and Dichtel, William R. Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films. United States: N. p., 2015. Web. doi:10.1021/acsnano.5b00184.
DeBlase, Catherine R., Hernández-Burgos, Kenneth, Silberstein, Katharine E., Rodríguez-Calero, Gabriel G., Bisbey, Ryan P., Abruña, Héctor D., & Dichtel, William R. Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films. United States. https://doi.org/10.1021/acsnano.5b00184
DeBlase, Catherine R., Hernández-Burgos, Kenneth, Silberstein, Katharine E., Rodríguez-Calero, Gabriel G., Bisbey, Ryan P., Abruña, Héctor D., and Dichtel, William R. Wed . "Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films". United States. https://doi.org/10.1021/acsnano.5b00184. https://www.osti.gov/servlets/purl/1370446.
@article{osti_1370446,
title = {Rapid and Efficient Redox Processes within 2D Covalent Organic Framework Thin Films},
author = {DeBlase, Catherine R. and Hernández-Burgos, Kenneth and Silberstein, Katharine E. and Rodríguez-Calero, Gabriel G. and Bisbey, Ryan P. and Abruña, Héctor D. and Dichtel, William R.},
abstractNote = {Two-dimensional covalent organic frameworks (2D COFs) are ideally suited for organizing redox-active subunits into periodic, permanently porous polymer networks of interest for pseudocapacitive energy storage. Currently, we describe a method for synthesizing crystalline, oriented thin films of a redox-active 2D COF on Au working electrodes. The thickness of the COF film was controlled by varying the initial monomer concentration. A large percentage (80–99%) of the anthraquinone groups are electrochemically accessible in films thinner than 200 nm, an order of magnitude improvement over the same COF prepared as a randomly oriented microcrystalline powder. As a result, electrodes functionalized with oriented COF films exhibit a 400% increase in capacitance scaled to electrode area as compared to those functionalized with the randomly oriented COF powder. These findings demonstrate the promise of redox-active COFs for electrical energy storage and highlight the importance of controlling morphology for optimal performance.},
doi = {10.1021/acsnano.5b00184},
url = {https://www.osti.gov/biblio/1370446}, journal = {ACS Nano},
issn = {1936-0851},
number = 3,
volume = 9,
place = {United States},
year = {2015},
month = {2}
}

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Cited by: 170 works
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Works referencing / citing this record:

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