Carbon Dioxide Capture at Nucleophilic Hydroxide Sites in Oxidation-Resistant Cyclodextrin-Based Metal-Organic Frameworks
Carbon capture and utilization or sequestration (CCUS) from industrial point sources and direct air capture (DAC) are like-ly necessary to combat global climate change. Reducing the costs of CCUS and DAC requires next-generation sorbents ca-pable of reversible CO2 capture under realistic conditions....
Main Authors: | , , , , |
---|---|
Other Authors: | , , |
Format: | Other/Unknown Material |
Language: | unknown |
Published: |
American Chemical Society (ACS)
2022
|
Subjects: | |
Online Access: | http://dx.doi.org/10.26434/chemrxiv-2022-f1xz2 https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/623f4d67ab005196229a4279/original/carbon-dioxide-capture-at-nucleophilic-hydroxide-sites-in-oxidation-resistant-cyclodextrin-based-metal-organic-frameworks.pdf |
id |
cracsoc:10.26434/chemrxiv-2022-f1xz2 |
---|---|
record_format |
openpolar |
spelling |
cracsoc:10.26434/chemrxiv-2022-f1xz2 2023-07-30T04:02:56+02:00 Carbon Dioxide Capture at Nucleophilic Hydroxide Sites in Oxidation-Resistant Cyclodextrin-Based Metal-Organic Frameworks Zick, Mary Pugh, Suzi Lee, Jung-Hoon Forse, Alexander Milner, Phillip U.S. Department of Energy National Science Foundation National Science Foundation National Institutes of Health U.S. Department of Energy 2022 http://dx.doi.org/10.26434/chemrxiv-2022-f1xz2 https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/623f4d67ab005196229a4279/original/carbon-dioxide-capture-at-nucleophilic-hydroxide-sites-in-oxidation-resistant-cyclodextrin-based-metal-organic-frameworks.pdf unknown American Chemical Society (ACS) https://creativecommons.org/licenses/by-nc-nd/4.0/ posted-content 2022 cracsoc https://doi.org/10.26434/chemrxiv-2022-f1xz2 2023-07-16T23:30:04Z Carbon capture and utilization or sequestration (CCUS) from industrial point sources and direct air capture (DAC) are like-ly necessary to combat global climate change. Reducing the costs of CCUS and DAC requires next-generation sorbents ca-pable of reversible CO2 capture under realistic conditions. A particular challenge faced by amine-based sorbents—the current leading technology for carbon capture—is poor stability towards O2, which is present in high partial pressures in most emission streams of interest as well as in air. Sorbents containing oxygen-based nucleophiles, such as hydroxide (OH−), can reversibly react with CO2 to form (bi)carbonate (HCO3−) species and should display improved oxidative stabil-ities compared to amine-based materials. Here, we provide gas sorption, spectroscopic, and computational studies sup-porting that CO2 chemisorption in γ-cylodextrin-based metal-organic frameworks (CD-MOFs) occurs via HCO3− formation at nucleophilic OH− sites within the framework pores, rather than via previously proposed pathways involving carbonic acid or alkyl carbonate formation. Of the CD-MOFs studied herein, the new framework KHCO3 CD-MOF possesses rapid and high-capacity CO2 uptake, good thermal, oxidative, and cycling stabilities compared to previously reported materials, and selective CO2 capture under mixed gas conditions in dynamic breakthrough experiments. Because of its low cost and performance under realistic conditions, KHCO3 CD-MOF is a promising new platform for CCUS. More broadly, our work demonstrates that the encapsulation of reactive OH− sites within a porous framework represents a potentially general strategy for the design of oxidation-resistant adsorbents for carbon dioxide capture. Other/Unknown Material Carbonic acid ACS Publications (via Crossref) |
institution |
Open Polar |
collection |
ACS Publications (via Crossref) |
op_collection_id |
cracsoc |
language |
unknown |
description |
Carbon capture and utilization or sequestration (CCUS) from industrial point sources and direct air capture (DAC) are like-ly necessary to combat global climate change. Reducing the costs of CCUS and DAC requires next-generation sorbents ca-pable of reversible CO2 capture under realistic conditions. A particular challenge faced by amine-based sorbents—the current leading technology for carbon capture—is poor stability towards O2, which is present in high partial pressures in most emission streams of interest as well as in air. Sorbents containing oxygen-based nucleophiles, such as hydroxide (OH−), can reversibly react with CO2 to form (bi)carbonate (HCO3−) species and should display improved oxidative stabil-ities compared to amine-based materials. Here, we provide gas sorption, spectroscopic, and computational studies sup-porting that CO2 chemisorption in γ-cylodextrin-based metal-organic frameworks (CD-MOFs) occurs via HCO3− formation at nucleophilic OH− sites within the framework pores, rather than via previously proposed pathways involving carbonic acid or alkyl carbonate formation. Of the CD-MOFs studied herein, the new framework KHCO3 CD-MOF possesses rapid and high-capacity CO2 uptake, good thermal, oxidative, and cycling stabilities compared to previously reported materials, and selective CO2 capture under mixed gas conditions in dynamic breakthrough experiments. Because of its low cost and performance under realistic conditions, KHCO3 CD-MOF is a promising new platform for CCUS. More broadly, our work demonstrates that the encapsulation of reactive OH− sites within a porous framework represents a potentially general strategy for the design of oxidation-resistant adsorbents for carbon dioxide capture. |
author2 |
U.S. Department of Energy National Science Foundation National Science Foundation National Institutes of Health U.S. Department of Energy |
format |
Other/Unknown Material |
author |
Zick, Mary Pugh, Suzi Lee, Jung-Hoon Forse, Alexander Milner, Phillip |
spellingShingle |
Zick, Mary Pugh, Suzi Lee, Jung-Hoon Forse, Alexander Milner, Phillip Carbon Dioxide Capture at Nucleophilic Hydroxide Sites in Oxidation-Resistant Cyclodextrin-Based Metal-Organic Frameworks |
author_facet |
Zick, Mary Pugh, Suzi Lee, Jung-Hoon Forse, Alexander Milner, Phillip |
author_sort |
Zick, Mary |
title |
Carbon Dioxide Capture at Nucleophilic Hydroxide Sites in Oxidation-Resistant Cyclodextrin-Based Metal-Organic Frameworks |
title_short |
Carbon Dioxide Capture at Nucleophilic Hydroxide Sites in Oxidation-Resistant Cyclodextrin-Based Metal-Organic Frameworks |
title_full |
Carbon Dioxide Capture at Nucleophilic Hydroxide Sites in Oxidation-Resistant Cyclodextrin-Based Metal-Organic Frameworks |
title_fullStr |
Carbon Dioxide Capture at Nucleophilic Hydroxide Sites in Oxidation-Resistant Cyclodextrin-Based Metal-Organic Frameworks |
title_full_unstemmed |
Carbon Dioxide Capture at Nucleophilic Hydroxide Sites in Oxidation-Resistant Cyclodextrin-Based Metal-Organic Frameworks |
title_sort |
carbon dioxide capture at nucleophilic hydroxide sites in oxidation-resistant cyclodextrin-based metal-organic frameworks |
publisher |
American Chemical Society (ACS) |
publishDate |
2022 |
url |
http://dx.doi.org/10.26434/chemrxiv-2022-f1xz2 https://chemrxiv.org/engage/api-gateway/chemrxiv/assets/orp/resource/item/623f4d67ab005196229a4279/original/carbon-dioxide-capture-at-nucleophilic-hydroxide-sites-in-oxidation-resistant-cyclodextrin-based-metal-organic-frameworks.pdf |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_rights |
https://creativecommons.org/licenses/by-nc-nd/4.0/ |
op_doi |
https://doi.org/10.26434/chemrxiv-2022-f1xz2 |
_version_ |
1772813826665742336 |