Polymer-Coated Covalent Organic Frameworks as Porous Liquids for Gas Storage
Abstract
Several synthetic methods have recently emerged to develop high-surface-area solid-state organic framework-based materials into free-flowing liquids with permanent porosity. The fluidity of these porous liquid (PL) materials provides them with advantages in certain storage and transport processes. However, most framework-based materials necessitate the use of cryogenic temperatures to store weakly bound gases such as H2, temperatures where PLs lose their fluidity. Covalent organic framework (COF)-based PLs that could reversibly form stable complexes with H2 near ambient temperatures would represent a promising development for gas storage and transport applications. We report here the development, characterization, and evaluation of a material with these remarkable characteristics based on Cu(I)-loaded COF colloids. Our synthetic strategy required tailoring conditions for growing robust coatings of poly(dimethylsiloxane)-methacrylate (PDMS-MA) around COF colloids using atom transfer radical polymerization (ATRP). We demonstrate exquisite control over the coating thickness on the colloidal COF, quantified by transmission electron microscopy and dynamic light scattering. The coated COF material was then suspended in a liquid polymer matrix to make a PL. CO2 isotherms confirmed that the coating preserved the general porosity of the COF in the free-flowing liquid, while CO sorption measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirmed the preservation ofmore »
- Authors:
-
- Materials Science Program, Colorado School of Mines, Golden, Colorado 80401, United States, Chemistry and Nanoscience Center, National Renewable Energy Laboratory, 15013 Denver West Pkwy, Golden, Colorado 80401, United States
- Department of Chemistry, Colorado School of Mines, 1012 14th Street, Golden, Colorado 80401, United States, Chemistry and Nanoscience Center, National Renewable Energy Laboratory, 15013 Denver West Pkwy, Golden, Colorado 80401, United States
- Catalytic Carbon Transformation and Scale-Up Center, National Renewable Energy Laboratory, 15013 Denver West Pkwy, Golden, Colorado 80401, United States
- Materials Science Program, Colorado School of Mines, Golden, Colorado 80401, United States, Department of Chemistry, Colorado School of Mines, 1012 14th Street, Golden, Colorado 80401, United States, Chemistry and Nanoscience Center, National Renewable Energy Laboratory, 15013 Denver West Pkwy, Golden, Colorado 80401, United States
- Publication Date:
- Research Org.:
- National Renewable Energy Laboratory (NREL), Golden, CO (United States)
- Sponsoring Org.:
- USDOE; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Hydrogen Fuel Cell Technologies Office (HFTO)
- OSTI Identifier:
- 2281953
- Alternate Identifier(s):
- OSTI ID: 2316142
- Report Number(s):
- NREL/JA-5900-85257
Journal ID: ISSN 0897-4756
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Published Article
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Name: Chemistry of Materials Journal Volume: 36 Journal Issue: 3; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; controlled radical polymerization; covalent organic framework; hydrogen storage; porous liquid; coating materials; colloids; liquids
Citation Formats
Mow, Rachel E., Russell-Parks, Glory A., Redwine, Grace E. B., Petel, Brittney E., Gennett, Thomas, and Braunecker, Wade A. Polymer-Coated Covalent Organic Frameworks as Porous Liquids for Gas Storage. United States: N. p., 2024.
Web. doi:10.1021/acs.chemmater.3c02828.
Mow, Rachel E., Russell-Parks, Glory A., Redwine, Grace E. B., Petel, Brittney E., Gennett, Thomas, & Braunecker, Wade A. Polymer-Coated Covalent Organic Frameworks as Porous Liquids for Gas Storage. United States. https://doi.org/10.1021/acs.chemmater.3c02828
Mow, Rachel E., Russell-Parks, Glory A., Redwine, Grace E. B., Petel, Brittney E., Gennett, Thomas, and Braunecker, Wade A. Fri .
"Polymer-Coated Covalent Organic Frameworks as Porous Liquids for Gas Storage". United States. https://doi.org/10.1021/acs.chemmater.3c02828.
@article{osti_2281953,
title = {Polymer-Coated Covalent Organic Frameworks as Porous Liquids for Gas Storage},
author = {Mow, Rachel E. and Russell-Parks, Glory A. and Redwine, Grace E. B. and Petel, Brittney E. and Gennett, Thomas and Braunecker, Wade A.},
abstractNote = {Several synthetic methods have recently emerged to develop high-surface-area solid-state organic framework-based materials into free-flowing liquids with permanent porosity. The fluidity of these porous liquid (PL) materials provides them with advantages in certain storage and transport processes. However, most framework-based materials necessitate the use of cryogenic temperatures to store weakly bound gases such as H2, temperatures where PLs lose their fluidity. Covalent organic framework (COF)-based PLs that could reversibly form stable complexes with H2 near ambient temperatures would represent a promising development for gas storage and transport applications. We report here the development, characterization, and evaluation of a material with these remarkable characteristics based on Cu(I)-loaded COF colloids. Our synthetic strategy required tailoring conditions for growing robust coatings of poly(dimethylsiloxane)-methacrylate (PDMS-MA) around COF colloids using atom transfer radical polymerization (ATRP). We demonstrate exquisite control over the coating thickness on the colloidal COF, quantified by transmission electron microscopy and dynamic light scattering. The coated COF material was then suspended in a liquid polymer matrix to make a PL. CO2 isotherms confirmed that the coating preserved the general porosity of the COF in the free-flowing liquid, while CO sorption measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirmed the preservation of Cu(I) coordination sites. We then evaluated the gas sorption phenomenon in the Cu(I)–COF-based PLs using DRIFTS and temperature-programmed desorption measurements. In addition to confirming that H2 transport is possible at or near mild refrigeration temperatures with these materials, our observations indicate that H2 diffusion is significantly influenced by the glass-transition temperature of both the coating and the liquid matrix. The latter result underscores an additional potential advantage of PLs in tailoring gas diffusion and storage temperatures through the coating composition.},
doi = {10.1021/acs.chemmater.3c02828},
journal = {Chemistry of Materials},
number = 3,
volume = 36,
place = {United States},
year = {Fri Jan 19 00:00:00 EST 2024},
month = {Fri Jan 19 00:00:00 EST 2024}
}
https://doi.org/10.1021/acs.chemmater.3c02828
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