Dialing in Direct Air Capture of CO2 by Crystal Engineering of Bisiminoguanidines

Radu Custelcean; Neil J. Williams; Xiaoping Wang; Kathleen A. Garrabrant; Halie J. Martin; Michelle K. Kidder; Alexander S. Ivanov; Vyacheslav S. Bryantsev

doi:10.1002/cssc.202001114

Dialing in Direct Air Capture of CO₂ by Crystal Engineering of Bisiminoguanidines

Radu Custelcean, Neil J. Williams, Xiaoping Wang, Kathleen A. Garrabrant, Halie J. Martin, Michelle K. Kidder, Alexander S. Ivanov, Vyacheslav S. Bryantsev

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

27 Scopus citations

Abstract

Direct air capture (DAC) technologies that extract carbon dioxide from the atmosphere via chemical processes have the potential to restore the atmospheric CO₂ concentration to an optimal level. This study elucidates structure-property relationships in DAC by crystallization of bis(iminoguanidine) (BIG) carbonate salts. Their crystal structures are analyzed by X-ray and neutron diffraction to accurately measure key structural parameters including molecular conformations, hydrogen bonding, and π-stacking. Experimental measurements of key properties, such as aqueous solubilities and regeneration energies and temperatures, are complemented by first-principles calculations of lattice and hydration free energies, as well as free energies of reactions with CO₂, and BIG regenerations. Minor structural modifications in the molecular structure of the BIGs are found to result in major changes in the crystal structures and the aqueous solubilities within the series, leading to enhanced DAC.

Original language	English
Pages (from-to)	6381-6390
Number of pages	10
Journal	ChemSusChem
Volume	13
Issue number	23
DOIs	https://doi.org/10.1002/cssc.202001114
State	Published - Dec 7 2020

Funding

This research was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. The single-crystal neutron diffraction measurements performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE-AC02-05CH11231. This research was supported by the US Department of Energy, Office of Science, Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division. The single‐crystal neutron diffraction measurements performed on TOPAZ used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the Oak Ridge National Laboratory. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract No. DE‐AC02‐05CH11231.

Funders	Funder number
U.S. Department of Energy Office of Science	DE-AC02-05CH11231
US Department of Energy
U.S. Department of Energy	DE‐AC02‐05CH11231
Office of Science
Basic Energy Sciences
Oak Ridge National Laboratory
Chemical Sciences, Geosciences, and Biosciences Division

Keywords

carbon dioxide
crystallization
direct air capture
guanidines
hydrogen bonds

UN SDGs

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

Access to Document

10.1002/cssc.202001114

Cite this

@article{3eaf6413bdb946d593121ad0abf4f9e9,

title = "Dialing in Direct Air Capture of CO2 by Crystal Engineering of Bisiminoguanidines",

abstract = "Direct air capture (DAC) technologies that extract carbon dioxide from the atmosphere via chemical processes have the potential to restore the atmospheric CO2 concentration to an optimal level. This study elucidates structure-property relationships in DAC by crystallization of bis(iminoguanidine) (BIG) carbonate salts. Their crystal structures are analyzed by X-ray and neutron diffraction to accurately measure key structural parameters including molecular conformations, hydrogen bonding, and π-stacking. Experimental measurements of key properties, such as aqueous solubilities and regeneration energies and temperatures, are complemented by first-principles calculations of lattice and hydration free energies, as well as free energies of reactions with CO2, and BIG regenerations. Minor structural modifications in the molecular structure of the BIGs are found to result in major changes in the crystal structures and the aqueous solubilities within the series, leading to enhanced DAC.",

keywords = "carbon dioxide, crystallization, direct air capture, guanidines, hydrogen bonds",

author = "Radu Custelcean and Williams, {Neil J.} and Xiaoping Wang and Garrabrant, {Kathleen A.} and Martin, {Halie J.} and Kidder, {Michelle K.} and Ivanov, {Alexander S.} and Bryantsev, {Vyacheslav S.}",

note = "Publisher Copyright: {\textcopyright} 2020 Wiley-VCH GmbH",

year = "2020",

month = dec,

day = "7",

doi = "10.1002/cssc.202001114",

language = "English",

volume = "13",

pages = "6381--6390",

journal = "ChemSusChem",

issn = "1864-5631",

publisher = "wiley",

number = "23",

}

TY - JOUR

T1 - Dialing in Direct Air Capture of CO2 by Crystal Engineering of Bisiminoguanidines

AU - Custelcean, Radu

AU - Williams, Neil J.

AU - Wang, Xiaoping

AU - Garrabrant, Kathleen A.

AU - Martin, Halie J.

AU - Kidder, Michelle K.

AU - Ivanov, Alexander S.

AU - Bryantsev, Vyacheslav S.

PY - 2020/12/7

Y1 - 2020/12/7

N2 - Direct air capture (DAC) technologies that extract carbon dioxide from the atmosphere via chemical processes have the potential to restore the atmospheric CO2 concentration to an optimal level. This study elucidates structure-property relationships in DAC by crystallization of bis(iminoguanidine) (BIG) carbonate salts. Their crystal structures are analyzed by X-ray and neutron diffraction to accurately measure key structural parameters including molecular conformations, hydrogen bonding, and π-stacking. Experimental measurements of key properties, such as aqueous solubilities and regeneration energies and temperatures, are complemented by first-principles calculations of lattice and hydration free energies, as well as free energies of reactions with CO2, and BIG regenerations. Minor structural modifications in the molecular structure of the BIGs are found to result in major changes in the crystal structures and the aqueous solubilities within the series, leading to enhanced DAC.

AB - Direct air capture (DAC) technologies that extract carbon dioxide from the atmosphere via chemical processes have the potential to restore the atmospheric CO2 concentration to an optimal level. This study elucidates structure-property relationships in DAC by crystallization of bis(iminoguanidine) (BIG) carbonate salts. Their crystal structures are analyzed by X-ray and neutron diffraction to accurately measure key structural parameters including molecular conformations, hydrogen bonding, and π-stacking. Experimental measurements of key properties, such as aqueous solubilities and regeneration energies and temperatures, are complemented by first-principles calculations of lattice and hydration free energies, as well as free energies of reactions with CO2, and BIG regenerations. Minor structural modifications in the molecular structure of the BIGs are found to result in major changes in the crystal structures and the aqueous solubilities within the series, leading to enhanced DAC.

KW - carbon dioxide

KW - crystallization

KW - direct air capture

KW - guanidines

KW - hydrogen bonds

UR - http://www.scopus.com/inward/record.url?scp=85089017199&partnerID=8YFLogxK

U2 - 10.1002/cssc.202001114

DO - 10.1002/cssc.202001114

M3 - Article

C2 - 33411422

AN - SCOPUS:85089017199

SN - 1864-5631

VL - 13

SP - 6381

EP - 6390

JO - ChemSusChem

JF - ChemSusChem

IS - 23

ER -