Adsorption of Carbon Dioxide on Unsaturated Metal Sites in M2(dobpdc) Frameworks with Exceptional Structural Stability and Relation between Lewis Acidity and Adsorption Enthalpy

Ga Young Yoo, Woo Ram Lee, Hyuna Jo, Joonho Park, Jeong Hwa Song, Kwang Soo Lim, Dohyun Moon, Hyun Jung, Juhyung Lim, Sang Soo Han, Yousung Jung, Chang Seop Hong

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

A series of metal-organic frameworks (MOFs) M2(dobpdc) (M=Mn, Co, Ni, Zn; H4dobpdc=4,4′-dihydroxy-1,1′-biphenyl-3,3′-dicarboxylic acid), with a highly dense arrangement of open metal sites along hexagonal channels were prepared by microwave-assisted or simple solvothermal reactions. The activated materials were structurally expanded when guest molecules including CO2 were introduced into the pores. The Lewis acidity of the open metal sites varied in the order MnZn, as confirmed by C=O stretching bands in the IR spectra, which are related to the CO2 adsorption enthalpy. DFT calculations revealed that the high CO2 binding affinity of transition-metal-based M2(dobpdc) is primarily attributable to the favorable charge transfer from CO2 (oxygen lone pair acting as a Lewis base) to the open metal sites (Lewis acid), while electrostatic effects, the underlying factor responsible for the particular order of binding strength observed across different transition metals, also play a role. The framework stability against water coincides with the order of Lewis acidity. In this series of MOFs, the structural stability of Ni2(dobpdc) is exceptional; it endured in water vapor, liquid water, and in refluxing water for one month, and the solid remained intact on exposure to solutions of pH 2-13. The DFT calculations also support the experimental finding that Ni2(dobpdc) has higher chemical stability than the other frameworks.

Original languageEnglish
Pages (from-to)7444-7451
Number of pages8
JournalChemistry - A European Journal
Volume22
Issue number22
DOIs
Publication statusPublished - 2016 May 23

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Acidity
Carbon Dioxide
Adsorption
Enthalpy
Metals
Discrete Fourier transforms
Transition metals
Water
Lewis Bases
Lewis Acids
Dicarboxylic Acids
Chemical stability
Steam
Stretching
Charge transfer
Electrostatics
Microwaves
Static Electricity
Oxygen
Molecules

Keywords

  • carbon dioxide capture
  • density functional calculations
  • Lewis acids
  • metal-organic frameworks
  • solvothermal synthesis

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Adsorption of Carbon Dioxide on Unsaturated Metal Sites in M2(dobpdc) Frameworks with Exceptional Structural Stability and Relation between Lewis Acidity and Adsorption Enthalpy. / Yoo, Ga Young; Lee, Woo Ram; Jo, Hyuna; Park, Joonho; Song, Jeong Hwa; Lim, Kwang Soo; Moon, Dohyun; Jung, Hyun; Lim, Juhyung; Han, Sang Soo; Jung, Yousung; Hong, Chang Seop.

In: Chemistry - A European Journal, Vol. 22, No. 22, 23.05.2016, p. 7444-7451.

Research output: Contribution to journalArticle

Yoo, Ga Young ; Lee, Woo Ram ; Jo, Hyuna ; Park, Joonho ; Song, Jeong Hwa ; Lim, Kwang Soo ; Moon, Dohyun ; Jung, Hyun ; Lim, Juhyung ; Han, Sang Soo ; Jung, Yousung ; Hong, Chang Seop. / Adsorption of Carbon Dioxide on Unsaturated Metal Sites in M2(dobpdc) Frameworks with Exceptional Structural Stability and Relation between Lewis Acidity and Adsorption Enthalpy. In: Chemistry - A European Journal. 2016 ; Vol. 22, No. 22. pp. 7444-7451.
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AU - Park, Joonho

AU - Song, Jeong Hwa

AU - Lim, Kwang Soo

AU - Moon, Dohyun

AU - Jung, Hyun

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AU - Han, Sang Soo

AU - Jung, Yousung

AU - Hong, Chang Seop

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AB - A series of metal-organic frameworks (MOFs) M2(dobpdc) (M=Mn, Co, Ni, Zn; H4dobpdc=4,4′-dihydroxy-1,1′-biphenyl-3,3′-dicarboxylic acid), with a highly dense arrangement of open metal sites along hexagonal channels were prepared by microwave-assisted or simple solvothermal reactions. The activated materials were structurally expanded when guest molecules including CO2 were introduced into the pores. The Lewis acidity of the open metal sites varied in the order MnZn, as confirmed by C=O stretching bands in the IR spectra, which are related to the CO2 adsorption enthalpy. DFT calculations revealed that the high CO2 binding affinity of transition-metal-based M2(dobpdc) is primarily attributable to the favorable charge transfer from CO2 (oxygen lone pair acting as a Lewis base) to the open metal sites (Lewis acid), while electrostatic effects, the underlying factor responsible for the particular order of binding strength observed across different transition metals, also play a role. The framework stability against water coincides with the order of Lewis acidity. In this series of MOFs, the structural stability of Ni2(dobpdc) is exceptional; it endured in water vapor, liquid water, and in refluxing water for one month, and the solid remained intact on exposure to solutions of pH 2-13. The DFT calculations also support the experimental finding that Ni2(dobpdc) has higher chemical stability than the other frameworks.

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