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Title: Direct air capture of CO 2– topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2)(CO 3)(H 2O) 4

Abstract

Chemical bonding and all intermolecular interactions in the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH 2)(CO 3)(H 2O) 4, recently employed in the direct air capture of CO 2via crystallization, have been analyzed within the framework of the quantum theory of atoms in molecules (QTAIM) based on the experimental electron density derived from X-ray diffraction data obtained at 20 K. Accurate hydrogen positions were included based on an analogous neutron diffraction study at 100 K. Topological features of the covalent bonds demonstrate the presence of multiple bonds of various orders within the PyBIGH 2 2+cation. Strong hydrogen bonds define ribbons comprising carbonate anions and water molecules. These ribbons are linked to stacks of essentially planar dications via hydrogen bonds from the guanidinium moieties and an additional one to the pyridine nitrogen. The linking hydrogen bonds are approximately perpendicular to the anion–water ribbons. The observation of these putative interactions provided motivation to characterize them by topological analysis of the total electron density. Thus, all hydrogen bonds have been characterized by the properties of their (3,-1) bond critical points. Weaker interactions between the PyBIGH 2 2+cations have similarly been characterized. Integrated atomic charges are also reported. A small amount of cocrystallizedmore » hydroxide ion (~2%) was also detected in both the X-ray and neutron data, and included in the multipole model for the electron-density refinement. The small amount of additional H +required for charge balance was not detected in either the X-ray or the neutron data. Here, the results are discussed in the context of the unusually low aqueous solubility of (PyBIGH 2)(CO 3)(H 2O) 4and its ability to sequester atmospheric CO 2.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Toledo, Toledo, OH (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1483904
Alternate Identifier(s):
OSTI ID: 1489578
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Published Article
Journal Name:
IUCrJ
Additional Journal Information:
Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2052-2525
Publisher:
International Union of Crystallography
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; carbon capture; guanidine; X-ray diffraction; neutron diffraction; charge density; topological analysis; crystal engineering; intermolecular interactions; hydrogen bonding; environmental chemistry

Citation Formats

Gianopoulos, Christopher G., Chua, Zhijie, Zhurov, Vladimir V., Seipp, Charles A., Wang, Xiaoping, Custelcean, Radu, and Pinkerton, A. Alan. Direct air capture of CO2– topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH2)(CO3)(H2O)4. United States: N. p., 2019. Web. doi:10.1107/S2052252518014616.
Gianopoulos, Christopher G., Chua, Zhijie, Zhurov, Vladimir V., Seipp, Charles A., Wang, Xiaoping, Custelcean, Radu, & Pinkerton, A. Alan. Direct air capture of CO2– topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH2)(CO3)(H2O)4. United States. doi:10.1107/S2052252518014616.
Gianopoulos, Christopher G., Chua, Zhijie, Zhurov, Vladimir V., Seipp, Charles A., Wang, Xiaoping, Custelcean, Radu, and Pinkerton, A. Alan. Tue . "Direct air capture of CO2– topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH2)(CO3)(H2O)4". United States. doi:10.1107/S2052252518014616.
@article{osti_1483904,
title = {Direct air capture of CO2– topological analysis of the experimental electron density (QTAIM) of the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH2)(CO3)(H2O)4},
author = {Gianopoulos, Christopher G. and Chua, Zhijie and Zhurov, Vladimir V. and Seipp, Charles A. and Wang, Xiaoping and Custelcean, Radu and Pinkerton, A. Alan},
abstractNote = {Chemical bonding and all intermolecular interactions in the highly insoluble carbonate salt of a 2,6-pyridine-bis(iminoguanidine), (PyBIGH2)(CO3)(H2O)4, recently employed in the direct air capture of CO2via crystallization, have been analyzed within the framework of the quantum theory of atoms in molecules (QTAIM) based on the experimental electron density derived from X-ray diffraction data obtained at 20 K. Accurate hydrogen positions were included based on an analogous neutron diffraction study at 100 K. Topological features of the covalent bonds demonstrate the presence of multiple bonds of various orders within the PyBIGH22+cation. Strong hydrogen bonds define ribbons comprising carbonate anions and water molecules. These ribbons are linked to stacks of essentially planar dications via hydrogen bonds from the guanidinium moieties and an additional one to the pyridine nitrogen. The linking hydrogen bonds are approximately perpendicular to the anion–water ribbons. The observation of these putative interactions provided motivation to characterize them by topological analysis of the total electron density. Thus, all hydrogen bonds have been characterized by the properties of their (3,-1) bond critical points. Weaker interactions between the PyBIGH22+cations have similarly been characterized. Integrated atomic charges are also reported. A small amount of cocrystallized hydroxide ion (~2%) was also detected in both the X-ray and neutron data, and included in the multipole model for the electron-density refinement. The small amount of additional H+required for charge balance was not detected in either the X-ray or the neutron data. Here, the results are discussed in the context of the unusually low aqueous solubility of (PyBIGH2)(CO3)(H2O)4and its ability to sequester atmospheric CO2.},
doi = {10.1107/S2052252518014616},
journal = {IUCrJ},
number = 1,
volume = 6,
place = {United States},
year = {2019},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1107/S2052252518014616

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Table 1 Table 1: Experimental details.

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    Works referencing / citing this record:

    CO 2 Capture from Ambient Air by Crystallization with a Guanidine Sorbent
    journal, December 2016

    • Seipp, Charles A.; Williams, Neil J.; Kidder, Michelle K.
    • Angewandte Chemie International Edition, Vol. 56, Issue 4
    • DOI: 10.1002/anie.201610916

    Description of covalent bond orders using the charge density topology
    journal, February 2003

    • Howard, Siân T.; Lamarche, Olivier
    • Journal of Physical Organic Chemistry, Vol. 16, Issue 2
    • DOI: 10.1002/poc.584

    Charge Density Analysis of an Organic Ferroelectric. Croconic Acid: an Experimental and Theoretical Study
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    • Zhurov, Vladimir V.; Pinkerton, A. Alan
    • Zeitschrift für anorganische und allgemeine Chemie, Vol. 639, Issue 11
    • DOI: 10.1002/zaac.201200506

    QTAIMC study of the X–H/H⋯O bond order indices (X=O, N, C) in molecular systems
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    • DOI: 10.1016/j.comptc.2011.06.025

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    • Arnold, O.; Bilheux, J. C.; Borreguero, J. M.
    • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 764
    • DOI: 10.1016/j.nima.2014.07.029

    Direct Capture of CO2 from Ambient Air
    journal, August 2016

    • Sanz-Pérez, Eloy S.; Murdock, Christopher R.; Didas, Stephanie A.
    • Chemical Reviews, Vol. 116, Issue 19, p. 11840-11876
    • DOI: 10.1021/acs.chemrev.6b00173

    Single-crystal, time-of-flight, neutron-diffraction structure of hydrogen cis-diacetyltetracarbonylrhenate, [cis-(OC)4Re(CH3CO)2]H: a metallaacetylacetone molecule
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    • Schultz, Arthur J.; Srinivasan, K.; Teller, Raymond G.
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    • DOI: 10.1021/ja00316a031

    Learning through a portfolio of carbon capture and storage demonstration projects
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    • DOI: 10.1063/1.1501133

    The urgency of the development of CO2 capture from ambient air
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    • Lackner, K. S.; Brennan, S.; Matter, J. M.
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    • DOI: 10.1073/pnas.1108765109

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    Cooperative Jahn-Teller induced phase transition of TbVO4 single crystal structure analyses of the tetragonal high temperature phase and the twinned orthorhombic phase below 33 K
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    A Guide to CO2 Sequestration
    journal, June 2003


    Why Capture CO2 from the Atmosphere?
    journal, September 2009


    Modern possibilities for calculating some properties of molecules and crystals from the experimental electron density
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    • Stash, A. I.; Tsirelson, V. G.
    • Crystallography Reports, Vol. 50, Issue 2
    • DOI: 10.1134/1.1887890