Competitive coadsorption of CO2 with H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 in M-MOF-74 (M = Mg, Co, Ni)

The role of hydrogen bonding

Kui Tan, Sebastian Zuluaga, Qihan Gong, Yuzhi Gao, Nour Nijem, Jing Li, Timo Thonhauser, Yves J. Chabal

Research output: Contribution to journalArticle

65 Citations (Scopus)

Abstract

The importance of coadsorption for applications of porous materials in gas separation has motivated fundamental studies, which have initially focused on the comparison of the binding energies of different gas molecules in the pores (i.e., energetics) and their overall transport. By examining the competitive coadsorption of several small molecules in M-MOF-74 (M = Mg, Co, Ni) with in situ infrared spectroscopy and ab initio simulations, we find that the binding energy at the most favorable (metal) site is not a sufficient indicator for prediction of molecular adsorption and stability in MOFs. Instead, the occupation of the open metal sites is governed by kinetics, whereby the interaction of the guest molecules with the MOF organic linkers controls the reaction barrier for molecular exchange. Specifically, the displacement of CO2 adsorbed at the metal center by other molecules such as H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 is mainly observed for H2O and NH3, even though SO2, NO, and NO2 have higher binding energies (∼70-90 kJ/mol) to metal sites than that of CO2 (38 to 48 kJ/mol) and slightly higher than that of water (∼60-80 kJ/mol). DFT simulations evaluate the barriers for H2O → CO2 and SO2 → CO2 exchange to be ∼13 and 20 kJ/mol, respectively, explaining the slow exchange of CO2 by SO2, compared to water. Furthermore, the calculations reveal that the kinetic barrier for this exchange is determined by the specifics of the interaction of the second guest molecule (e.g., H2O or SO2) with the MOF ligands. Hydrogen bonding of H2O molecules with the nearby oxygen of the organic linker is found to facilitate the positioning of the H2O oxygen atom toward the metal center, thus reducing the exchange barrier. In contrast, SO2 molecules interact with the distant benzene site, away from the metal center, hindering the exchange process. Similar considerations apply to the other molecules, accounting for much easier CO2 exchange for NH3 than for NO, NO2, CH4, O2, and N2 molecules. In this work, critical parameters such as kinetic barrier and exchange pathway are first unveiled and provide insight into the mechanism of competitive coadsorption, underscoring the need of combined studies, using spectroscopic methods and ab initio simulations to uncover the atomistic interactions of small molecules in MOFs that directly influence coadsorption.

Original languageEnglish
Pages (from-to)2203-2217
Number of pages15
JournalChemistry of Materials
Volume27
Issue number6
DOIs
Publication statusPublished - Mar 24 2015

Fingerprint

Hydrogen bonds
Molecules
Metals
Binding energy
Kinetics
Gases
Oxygen
Water
Benzene
Discrete Fourier transforms
Porous materials
Infrared spectroscopy
Ligands
Adsorption
Atoms

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Competitive coadsorption of CO2 with H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 in M-MOF-74 (M = Mg, Co, Ni) : The role of hydrogen bonding. / Tan, Kui; Zuluaga, Sebastian; Gong, Qihan; Gao, Yuzhi; Nijem, Nour; Li, Jing; Thonhauser, Timo; Chabal, Yves J.

In: Chemistry of Materials, Vol. 27, No. 6, 24.03.2015, p. 2203-2217.

Research output: Contribution to journalArticle

Tan, Kui ; Zuluaga, Sebastian ; Gong, Qihan ; Gao, Yuzhi ; Nijem, Nour ; Li, Jing ; Thonhauser, Timo ; Chabal, Yves J. / Competitive coadsorption of CO2 with H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 in M-MOF-74 (M = Mg, Co, Ni) : The role of hydrogen bonding. In: Chemistry of Materials. 2015 ; Vol. 27, No. 6. pp. 2203-2217.
@article{c2a960cda85947d6991b07022f7f7148,
title = "Competitive coadsorption of CO2 with H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 in M-MOF-74 (M = Mg, Co, Ni): The role of hydrogen bonding",
abstract = "The importance of coadsorption for applications of porous materials in gas separation has motivated fundamental studies, which have initially focused on the comparison of the binding energies of different gas molecules in the pores (i.e., energetics) and their overall transport. By examining the competitive coadsorption of several small molecules in M-MOF-74 (M = Mg, Co, Ni) with in situ infrared spectroscopy and ab initio simulations, we find that the binding energy at the most favorable (metal) site is not a sufficient indicator for prediction of molecular adsorption and stability in MOFs. Instead, the occupation of the open metal sites is governed by kinetics, whereby the interaction of the guest molecules with the MOF organic linkers controls the reaction barrier for molecular exchange. Specifically, the displacement of CO2 adsorbed at the metal center by other molecules such as H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 is mainly observed for H2O and NH3, even though SO2, NO, and NO2 have higher binding energies (∼70-90 kJ/mol) to metal sites than that of CO2 (38 to 48 kJ/mol) and slightly higher than that of water (∼60-80 kJ/mol). DFT simulations evaluate the barriers for H2O → CO2 and SO2 → CO2 exchange to be ∼13 and 20 kJ/mol, respectively, explaining the slow exchange of CO2 by SO2, compared to water. Furthermore, the calculations reveal that the kinetic barrier for this exchange is determined by the specifics of the interaction of the second guest molecule (e.g., H2O or SO2) with the MOF ligands. Hydrogen bonding of H2O molecules with the nearby oxygen of the organic linker is found to facilitate the positioning of the H2O oxygen atom toward the metal center, thus reducing the exchange barrier. In contrast, SO2 molecules interact with the distant benzene site, away from the metal center, hindering the exchange process. Similar considerations apply to the other molecules, accounting for much easier CO2 exchange for NH3 than for NO, NO2, CH4, O2, and N2 molecules. In this work, critical parameters such as kinetic barrier and exchange pathway are first unveiled and provide insight into the mechanism of competitive coadsorption, underscoring the need of combined studies, using spectroscopic methods and ab initio simulations to uncover the atomistic interactions of small molecules in MOFs that directly influence coadsorption.",
author = "Kui Tan and Sebastian Zuluaga and Qihan Gong and Yuzhi Gao and Nour Nijem and Jing Li and Timo Thonhauser and Chabal, {Yves J.}",
year = "2015",
month = "3",
day = "24",
doi = "10.1021/acs.chemmater.5b00315",
language = "English",
volume = "27",
pages = "2203--2217",
journal = "Chemistry of Materials",
issn = "0897-4756",
publisher = "American Chemical Society",
number = "6",

}

TY - JOUR

T1 - Competitive coadsorption of CO2 with H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 in M-MOF-74 (M = Mg, Co, Ni)

T2 - The role of hydrogen bonding

AU - Tan, Kui

AU - Zuluaga, Sebastian

AU - Gong, Qihan

AU - Gao, Yuzhi

AU - Nijem, Nour

AU - Li, Jing

AU - Thonhauser, Timo

AU - Chabal, Yves J.

PY - 2015/3/24

Y1 - 2015/3/24

N2 - The importance of coadsorption for applications of porous materials in gas separation has motivated fundamental studies, which have initially focused on the comparison of the binding energies of different gas molecules in the pores (i.e., energetics) and their overall transport. By examining the competitive coadsorption of several small molecules in M-MOF-74 (M = Mg, Co, Ni) with in situ infrared spectroscopy and ab initio simulations, we find that the binding energy at the most favorable (metal) site is not a sufficient indicator for prediction of molecular adsorption and stability in MOFs. Instead, the occupation of the open metal sites is governed by kinetics, whereby the interaction of the guest molecules with the MOF organic linkers controls the reaction barrier for molecular exchange. Specifically, the displacement of CO2 adsorbed at the metal center by other molecules such as H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 is mainly observed for H2O and NH3, even though SO2, NO, and NO2 have higher binding energies (∼70-90 kJ/mol) to metal sites than that of CO2 (38 to 48 kJ/mol) and slightly higher than that of water (∼60-80 kJ/mol). DFT simulations evaluate the barriers for H2O → CO2 and SO2 → CO2 exchange to be ∼13 and 20 kJ/mol, respectively, explaining the slow exchange of CO2 by SO2, compared to water. Furthermore, the calculations reveal that the kinetic barrier for this exchange is determined by the specifics of the interaction of the second guest molecule (e.g., H2O or SO2) with the MOF ligands. Hydrogen bonding of H2O molecules with the nearby oxygen of the organic linker is found to facilitate the positioning of the H2O oxygen atom toward the metal center, thus reducing the exchange barrier. In contrast, SO2 molecules interact with the distant benzene site, away from the metal center, hindering the exchange process. Similar considerations apply to the other molecules, accounting for much easier CO2 exchange for NH3 than for NO, NO2, CH4, O2, and N2 molecules. In this work, critical parameters such as kinetic barrier and exchange pathway are first unveiled and provide insight into the mechanism of competitive coadsorption, underscoring the need of combined studies, using spectroscopic methods and ab initio simulations to uncover the atomistic interactions of small molecules in MOFs that directly influence coadsorption.

AB - The importance of coadsorption for applications of porous materials in gas separation has motivated fundamental studies, which have initially focused on the comparison of the binding energies of different gas molecules in the pores (i.e., energetics) and their overall transport. By examining the competitive coadsorption of several small molecules in M-MOF-74 (M = Mg, Co, Ni) with in situ infrared spectroscopy and ab initio simulations, we find that the binding energy at the most favorable (metal) site is not a sufficient indicator for prediction of molecular adsorption and stability in MOFs. Instead, the occupation of the open metal sites is governed by kinetics, whereby the interaction of the guest molecules with the MOF organic linkers controls the reaction barrier for molecular exchange. Specifically, the displacement of CO2 adsorbed at the metal center by other molecules such as H2O, NH3, SO2, NO, NO2, N2, O2, and CH4 is mainly observed for H2O and NH3, even though SO2, NO, and NO2 have higher binding energies (∼70-90 kJ/mol) to metal sites than that of CO2 (38 to 48 kJ/mol) and slightly higher than that of water (∼60-80 kJ/mol). DFT simulations evaluate the barriers for H2O → CO2 and SO2 → CO2 exchange to be ∼13 and 20 kJ/mol, respectively, explaining the slow exchange of CO2 by SO2, compared to water. Furthermore, the calculations reveal that the kinetic barrier for this exchange is determined by the specifics of the interaction of the second guest molecule (e.g., H2O or SO2) with the MOF ligands. Hydrogen bonding of H2O molecules with the nearby oxygen of the organic linker is found to facilitate the positioning of the H2O oxygen atom toward the metal center, thus reducing the exchange barrier. In contrast, SO2 molecules interact with the distant benzene site, away from the metal center, hindering the exchange process. Similar considerations apply to the other molecules, accounting for much easier CO2 exchange for NH3 than for NO, NO2, CH4, O2, and N2 molecules. In this work, critical parameters such as kinetic barrier and exchange pathway are first unveiled and provide insight into the mechanism of competitive coadsorption, underscoring the need of combined studies, using spectroscopic methods and ab initio simulations to uncover the atomistic interactions of small molecules in MOFs that directly influence coadsorption.

UR - http://www.scopus.com/inward/record.url?scp=84925743169&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84925743169&partnerID=8YFLogxK

U2 - 10.1021/acs.chemmater.5b00315

DO - 10.1021/acs.chemmater.5b00315

M3 - Article

VL - 27

SP - 2203

EP - 2217

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 6

ER -