CO2 Capture via Crystalline Hydrogen-Bonded Bicarbonate Dimers

Neil J. Williams; Charles A. Seipp; Flavien M. Brethomé; Ying Zhong Ma; Alexander S. Ivanov; Vyacheslav S. Bryantsev; Michelle K. Kidder; Halie J. Martin; Erick Holguin; Kathleen A. Garrabrant; Radu Custelcean

doi:10.1016/j.chempr.2018.12.025

CO₂ Capture via Crystalline Hydrogen-Bonded Bicarbonate Dimers

Neil J. Williams, Charles A. Seipp, Flavien M. Brethomé, Ying Zhong Ma, Alexander S. Ivanov, Vyacheslav S. Bryantsev, Michelle K. Kidder, Halie J. Martin, Erick Holguin, Kathleen A. Garrabrant, Radu Custelcean

Research output: Contribution to journal › Article › peer-review

76 Scopus citations

Abstract

Limiting global temperature rises is increasingly dependent on the development of energy-efficient carbon-capture methods. Here, we report a simple CO₂-separation cycle using an aqueous bis(iminoguanidine) (BIG) sorbent that reacts with CO₂ and crystallizes into an insoluble bicarbonate salt. X-ray diffraction analysis of the bicarbonate crystals revealed “anti-electrostatic” hydrogen-bonded (HCO₃⁻)₂ dimers, stabilized by guanidinium cations and water. Mild heating of the crystals releases the CO₂ and regenerates the BIG sorbent quantitatively, thereby closing the CO₂-separation cycle. Experimental and computational investigations support a CO₂-release mechanism consisting of surface-initiated low-barrier proton transfer from guanidinium groups to bicarbonate anions with the formation of carbonic acid dimers, followed by CO₂ and H₂O release in the rate-limiting step, with a measured activation energy of 102 ± 12 kJ/mol. The minimum energy required for sorbent regeneration is 151.5 kJ/mol CO₂, which is 24% lower than the regeneration energy of monoethanolamine, a benchmark industrial sorbent.

Original language	English
Pages (from-to)	719-730
Number of pages	12
Journal	Chem
Volume	5
Issue number	3
DOIs	https://doi.org/10.1016/j.chempr.2018.12.025
State	Published - Mar 14 2019

Funding

This research was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. This research used resources of the Oak Ridge Leadership Computing Facility and the Compute and Data Environment for Science at the Oak Ridge National Laboratory, which are supported by the US Department of Energy, Office of Science, under contract no. DE-AC05-00OR22725. This research was supported by the US Department of Energy, Office of Science , Basic Energy Sciences , Chemical Sciences, Geosciences, and Biosciences Division . This research used resources of the Oak Ridge Leadership Computing Facility and the Compute and Data Environment for Science at the Oak Ridge National Laboratory , which are supported by the US Department of Energy, Office of Science, under contract no. DE-AC05-00OR22725 .

Funders	Funder number
U.S. Department of Energy
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Chemical Sciences, Geosciences, and Biosciences Division	DE-AC05-00OR22725

Keywords

SDG13: Climate action
SDG7: Affordable and clean energy
anion clusters
carbon capture
carbonic acid
crystallization
guanidine
hydrogen bonding

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

Access to Document

10.1016/j.chempr.2018.12.025

Cite this

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title = "CO2 Capture via Crystalline Hydrogen-Bonded Bicarbonate Dimers",

abstract = "Limiting global temperature rises is increasingly dependent on the development of energy-efficient carbon-capture methods. Here, we report a simple CO2-separation cycle using an aqueous bis(iminoguanidine) (BIG) sorbent that reacts with CO2 and crystallizes into an insoluble bicarbonate salt. X-ray diffraction analysis of the bicarbonate crystals revealed “anti-electrostatic” hydrogen-bonded (HCO3−)2 dimers, stabilized by guanidinium cations and water. Mild heating of the crystals releases the CO2 and regenerates the BIG sorbent quantitatively, thereby closing the CO2-separation cycle. Experimental and computational investigations support a CO2-release mechanism consisting of surface-initiated low-barrier proton transfer from guanidinium groups to bicarbonate anions with the formation of carbonic acid dimers, followed by CO2 and H2O release in the rate-limiting step, with a measured activation energy of 102 ± 12 kJ/mol. The minimum energy required for sorbent regeneration is 151.5 kJ/mol CO2, which is 24% lower than the regeneration energy of monoethanolamine, a benchmark industrial sorbent.",

keywords = "SDG13: Climate action, SDG7: Affordable and clean energy, anion clusters, carbon capture, carbonic acid, crystallization, guanidine, hydrogen bonding",

author = "Williams, {Neil J.} and Seipp, {Charles A.} and Brethom{\'e}, {Flavien M.} and Ma, {Ying Zhong} and Ivanov, {Alexander S.} and Bryantsev, {Vyacheslav S.} and Kidder, {Michelle K.} and Martin, {Halie J.} and Erick Holguin and Garrabrant, {Kathleen A.} and Radu Custelcean",

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AU - Williams, Neil J.

AU - Seipp, Charles A.

AU - Brethomé, Flavien M.

AU - Ma, Ying Zhong

AU - Ivanov, Alexander S.

AU - Bryantsev, Vyacheslav S.

AU - Kidder, Michelle K.

AU - Martin, Halie J.

AU - Holguin, Erick

AU - Garrabrant, Kathleen A.

AU - Custelcean, Radu

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N2 - Limiting global temperature rises is increasingly dependent on the development of energy-efficient carbon-capture methods. Here, we report a simple CO2-separation cycle using an aqueous bis(iminoguanidine) (BIG) sorbent that reacts with CO2 and crystallizes into an insoluble bicarbonate salt. X-ray diffraction analysis of the bicarbonate crystals revealed “anti-electrostatic” hydrogen-bonded (HCO3−)2 dimers, stabilized by guanidinium cations and water. Mild heating of the crystals releases the CO2 and regenerates the BIG sorbent quantitatively, thereby closing the CO2-separation cycle. Experimental and computational investigations support a CO2-release mechanism consisting of surface-initiated low-barrier proton transfer from guanidinium groups to bicarbonate anions with the formation of carbonic acid dimers, followed by CO2 and H2O release in the rate-limiting step, with a measured activation energy of 102 ± 12 kJ/mol. The minimum energy required for sorbent regeneration is 151.5 kJ/mol CO2, which is 24% lower than the regeneration energy of monoethanolamine, a benchmark industrial sorbent.

AB - Limiting global temperature rises is increasingly dependent on the development of energy-efficient carbon-capture methods. Here, we report a simple CO2-separation cycle using an aqueous bis(iminoguanidine) (BIG) sorbent that reacts with CO2 and crystallizes into an insoluble bicarbonate salt. X-ray diffraction analysis of the bicarbonate crystals revealed “anti-electrostatic” hydrogen-bonded (HCO3−)2 dimers, stabilized by guanidinium cations and water. Mild heating of the crystals releases the CO2 and regenerates the BIG sorbent quantitatively, thereby closing the CO2-separation cycle. Experimental and computational investigations support a CO2-release mechanism consisting of surface-initiated low-barrier proton transfer from guanidinium groups to bicarbonate anions with the formation of carbonic acid dimers, followed by CO2 and H2O release in the rate-limiting step, with a measured activation energy of 102 ± 12 kJ/mol. The minimum energy required for sorbent regeneration is 151.5 kJ/mol CO2, which is 24% lower than the regeneration energy of monoethanolamine, a benchmark industrial sorbent.

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KW - SDG7: Affordable and clean energy

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