A computational study of the interaction of C2 hydrocarbons with CuBTC

Rui Afonso, Jordi Toda, José R.B. Gomes, Michael Fischer, Christopher Campbell, Miguel Jorge

Research output: Contribution to journalArticle

Abstract

The adsorptions of ethane, ethene, and ethyne over the coordinatively unsaturated sites (CUS) of copper (II) benzene-1,3,5-tricarboxylate (CuBTC) were studied by means of density functional theory (DFT), using both cluster or periodic models. Exchange-correlation functionals from different rungs of the Jacobs ladder of the DFT were used and energies were corrected for the basis superposition error either through extrapolation to the complete basis set limit or upon the consideration of the Counterpoise method. From the calculated data, it was found that the adsorbate to CUS distances decrease in the order ethane > ethene ≈ ethyne and that the strength of adsorption increase in the order ethane to ethyne to ethene. The energies of interactions of ethene and ethyne with the CUS of CuBTC are approximately the double of that calculated for ethane. The calculated adsorption energies and geometries are in very satisfactory agreement with the available experimental results. The results of topological analyses confirm that the unsaturated bonds of ethene and ethyne form open shell like bonds with the CUS while interaction with ethane have predominant closed shell character.
Original languageEnglish
Number of pages27
JournalComputational Materials Science
Publication statusAccepted/In press - 25 Nov 2019

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Acetylene
Ethane
Hydrocarbons
Adsorption
ethane
hydrocarbons
Density Functional
Shell
Energy
Interaction
Limit Set
adsorption
interactions
Density functional theory
Extrapolation
Copper
Superposition
density functional theory
Ladders
Closed

Keywords

  • HKUST-1
  • adsorption
  • separation
  • density functional theory
  • cluster models
  • periodic models
  • copper paddlewheel

Cite this

Afonso, R., Toda, J., Gomes, J. R. B., Fischer, M., Campbell, C., & Jorge, M. (Accepted/In press). A computational study of the interaction of C2 hydrocarbons with CuBTC. Computational Materials Science.
Afonso, Rui ; Toda, Jordi ; Gomes, José R.B. ; Fischer, Michael ; Campbell, Christopher ; Jorge, Miguel. / A computational study of the interaction of C2 hydrocarbons with CuBTC. In: Computational Materials Science. 2019.
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A computational study of the interaction of C2 hydrocarbons with CuBTC. / Afonso, Rui; Toda, Jordi; Gomes, José R.B.; Fischer, Michael; Campbell, Christopher; Jorge, Miguel.

In: Computational Materials Science, 25.11.2019.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A computational study of the interaction of C2 hydrocarbons with CuBTC

AU - Afonso, Rui

AU - Toda, Jordi

AU - Gomes, José R.B.

AU - Fischer, Michael

AU - Campbell, Christopher

AU - Jorge, Miguel

PY - 2019/11/25

Y1 - 2019/11/25

N2 - The adsorptions of ethane, ethene, and ethyne over the coordinatively unsaturated sites (CUS) of copper (II) benzene-1,3,5-tricarboxylate (CuBTC) were studied by means of density functional theory (DFT), using both cluster or periodic models. Exchange-correlation functionals from different rungs of the Jacobs ladder of the DFT were used and energies were corrected for the basis superposition error either through extrapolation to the complete basis set limit or upon the consideration of the Counterpoise method. From the calculated data, it was found that the adsorbate to CUS distances decrease in the order ethane > ethene ≈ ethyne and that the strength of adsorption increase in the order ethane to ethyne to ethene. The energies of interactions of ethene and ethyne with the CUS of CuBTC are approximately the double of that calculated for ethane. The calculated adsorption energies and geometries are in very satisfactory agreement with the available experimental results. The results of topological analyses confirm that the unsaturated bonds of ethene and ethyne form open shell like bonds with the CUS while interaction with ethane have predominant closed shell character.

AB - The adsorptions of ethane, ethene, and ethyne over the coordinatively unsaturated sites (CUS) of copper (II) benzene-1,3,5-tricarboxylate (CuBTC) were studied by means of density functional theory (DFT), using both cluster or periodic models. Exchange-correlation functionals from different rungs of the Jacobs ladder of the DFT were used and energies were corrected for the basis superposition error either through extrapolation to the complete basis set limit or upon the consideration of the Counterpoise method. From the calculated data, it was found that the adsorbate to CUS distances decrease in the order ethane > ethene ≈ ethyne and that the strength of adsorption increase in the order ethane to ethyne to ethene. The energies of interactions of ethene and ethyne with the CUS of CuBTC are approximately the double of that calculated for ethane. The calculated adsorption energies and geometries are in very satisfactory agreement with the available experimental results. The results of topological analyses confirm that the unsaturated bonds of ethene and ethyne form open shell like bonds with the CUS while interaction with ethane have predominant closed shell character.

KW - HKUST-1

KW - adsorption

KW - separation

KW - density functional theory

KW - cluster models

KW - periodic models

KW - copper paddlewheel

M3 - Article

JO - Computational Materials Science

JF - Computational Materials Science

SN - 0927-0256

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