A new model for predicting adsorption of polar molecules in MOFs with unsaturated metal sites

Christopher Campbell, José R.B. Gomes, Michael Fischer, Miguel Jorge

Research output: Contribution to journalArticle

4 Citations (Scopus)

Abstract

Large-scale computational screening has the potential to translate the tailorability of metal-organic frameworks (MOFs) into actual applications, but requires the availability of accurate forcefields. Unfortunately, conventional molecular models fail to correctly describe interactions of adsorbates with coordinatively unsaturated sites (CUS) present in a large number of MOFs. Here, we confirm the failure of these models for a prototypical polar adsorbate, carbon monoxide, and show that simply adjusting their parameters leads to poor agreement with experiment isotherms when outside the fitting conditions. Building upon our previous work on non-polar hydrocarbons, we propose a new approach that combines quantum mechanical Density Functional Theory (DFT) with Monte Carlo simulations to rigorously account for specific interactions at the CUS. By explicitly including electrostatic interactions and employing accurate DFT functionals that describe dispersion interactions, our modeling approach becomes generally applicable to both polar and non-polar molecules. We demonstrate that this CUS model leads to substantial improvement in carbon monoxide adsorption isotherm predictions, and correctly captures the coordination binding mechanism. Furthermore, the model retains the transferability demonstrated in our previous work. This paper represents a major stepping stone in the development of a robust, transferable and generally applicable approach to describe the complex interactions between gas molecules and CUS, with great potential for use in large scale screening studies.
LanguageEnglish
Pages3544–3553
Number of pages10
JournalJournal of Physical Chemistry Letters
Volume9
Issue number12
DOIs
Publication statusPublished - 10 Jun 2018

Fingerprint

Metals
Adsorption
Molecules
Adsorbates
Carbon Monoxide
Carbon monoxide
Density functional theory
Screening
Hydrocarbons
Coulomb interactions
Adsorption isotherms
Isotherms
Gases
Availability
Experiments

Keywords

  • nanomaterials
  • MOFs
  • density function theory

Cite this

Campbell, Christopher ; Gomes, José R.B. ; Fischer, Michael ; Jorge, Miguel. / A new model for predicting adsorption of polar molecules in MOFs with unsaturated metal sites. In: Journal of Physical Chemistry Letters. 2018 ; Vol. 9, No. 12. pp. 3544–3553.
@article{bf8812a6fdac4bf39f65445682c95a27,
title = "A new model for predicting adsorption of polar molecules in MOFs with unsaturated metal sites",
abstract = "Large-scale computational screening has the potential to translate the tailorability of metal-organic frameworks (MOFs) into actual applications, but requires the availability of accurate forcefields. Unfortunately, conventional molecular models fail to correctly describe interactions of adsorbates with coordinatively unsaturated sites (CUS) present in a large number of MOFs. Here, we confirm the failure of these models for a prototypical polar adsorbate, carbon monoxide, and show that simply adjusting their parameters leads to poor agreement with experiment isotherms when outside the fitting conditions. Building upon our previous work on non-polar hydrocarbons, we propose a new approach that combines quantum mechanical Density Functional Theory (DFT) with Monte Carlo simulations to rigorously account for specific interactions at the CUS. By explicitly including electrostatic interactions and employing accurate DFT functionals that describe dispersion interactions, our modeling approach becomes generally applicable to both polar and non-polar molecules. We demonstrate that this CUS model leads to substantial improvement in carbon monoxide adsorption isotherm predictions, and correctly captures the coordination binding mechanism. Furthermore, the model retains the transferability demonstrated in our previous work. This paper represents a major stepping stone in the development of a robust, transferable and generally applicable approach to describe the complex interactions between gas molecules and CUS, with great potential for use in large scale screening studies.",
keywords = "nanomaterials, MOFs, density function theory",
author = "Christopher Campbell and Gomes, {Jos{\'e} R.B.} and Michael Fischer and Miguel Jorge",
note = "This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.",
year = "2018",
month = "6",
day = "10",
doi = "10.1021/acs.jpclett.8b00967",
language = "English",
volume = "9",
pages = "3544–3553",
journal = "Journal of Physical Chemistry Letters",
issn = "1948-7185",
publisher = "American Chemical Society",
number = "12",

}

A new model for predicting adsorption of polar molecules in MOFs with unsaturated metal sites. / Campbell, Christopher; Gomes, José R.B.; Fischer, Michael; Jorge, Miguel.

In: Journal of Physical Chemistry Letters, Vol. 9, No. 12, 10.06.2018, p. 3544–3553.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A new model for predicting adsorption of polar molecules in MOFs with unsaturated metal sites

AU - Campbell, Christopher

AU - Gomes, José R.B.

AU - Fischer, Michael

AU - Jorge, Miguel

N1 - This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited.

PY - 2018/6/10

Y1 - 2018/6/10

N2 - Large-scale computational screening has the potential to translate the tailorability of metal-organic frameworks (MOFs) into actual applications, but requires the availability of accurate forcefields. Unfortunately, conventional molecular models fail to correctly describe interactions of adsorbates with coordinatively unsaturated sites (CUS) present in a large number of MOFs. Here, we confirm the failure of these models for a prototypical polar adsorbate, carbon monoxide, and show that simply adjusting their parameters leads to poor agreement with experiment isotherms when outside the fitting conditions. Building upon our previous work on non-polar hydrocarbons, we propose a new approach that combines quantum mechanical Density Functional Theory (DFT) with Monte Carlo simulations to rigorously account for specific interactions at the CUS. By explicitly including electrostatic interactions and employing accurate DFT functionals that describe dispersion interactions, our modeling approach becomes generally applicable to both polar and non-polar molecules. We demonstrate that this CUS model leads to substantial improvement in carbon monoxide adsorption isotherm predictions, and correctly captures the coordination binding mechanism. Furthermore, the model retains the transferability demonstrated in our previous work. This paper represents a major stepping stone in the development of a robust, transferable and generally applicable approach to describe the complex interactions between gas molecules and CUS, with great potential for use in large scale screening studies.

AB - Large-scale computational screening has the potential to translate the tailorability of metal-organic frameworks (MOFs) into actual applications, but requires the availability of accurate forcefields. Unfortunately, conventional molecular models fail to correctly describe interactions of adsorbates with coordinatively unsaturated sites (CUS) present in a large number of MOFs. Here, we confirm the failure of these models for a prototypical polar adsorbate, carbon monoxide, and show that simply adjusting their parameters leads to poor agreement with experiment isotherms when outside the fitting conditions. Building upon our previous work on non-polar hydrocarbons, we propose a new approach that combines quantum mechanical Density Functional Theory (DFT) with Monte Carlo simulations to rigorously account for specific interactions at the CUS. By explicitly including electrostatic interactions and employing accurate DFT functionals that describe dispersion interactions, our modeling approach becomes generally applicable to both polar and non-polar molecules. We demonstrate that this CUS model leads to substantial improvement in carbon monoxide adsorption isotherm predictions, and correctly captures the coordination binding mechanism. Furthermore, the model retains the transferability demonstrated in our previous work. This paper represents a major stepping stone in the development of a robust, transferable and generally applicable approach to describe the complex interactions between gas molecules and CUS, with great potential for use in large scale screening studies.

KW - nanomaterials

KW - MOFs

KW - density function theory

UR - https://pubs.acs.org/journal/jpclcd

U2 - 10.1021/acs.jpclett.8b00967

DO - 10.1021/acs.jpclett.8b00967

M3 - Article

VL - 9

SP - 3544

EP - 3553

JO - Journal of Physical Chemistry Letters

T2 - Journal of Physical Chemistry Letters

JF - Journal of Physical Chemistry Letters

SN - 1948-7185

IS - 12

ER -