Heats of Adsorption of N2, CO, Ar, and CH4 versus Coverage on the Zr-Based MOF NU-1000: Measurements and DFT Calculations

Graeme O. Vissers; Wei Zhang; Oscar E. Vilches; Wei Guang Liu; Haoyu S. Yu; Donald G. Truhlar; Charles T. Campbell

doi:10.1021/acs.jpcc.8b12263

Heats of Adsorption of N₂, CO, Ar, and CH₄ versus Coverage on the Zr-Based MOF NU-1000: Measurements and DFT Calculations

Graeme O. Vissers, Wei Zhang, Oscar E. Vilches, Wei Guang Liu, Haoyu S. Yu, Donald G. Truhlar, Charles T. Campbell

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

7 Scopus citations

Abstract

Equilibrium adsorption isotherms at very low coverage (0 to ∼0.1 monolayer) have been measured for four simple gases, N₂, CO, Ar, and CH₄, at several temperatures above 98 K on the metal-organic framework (MOF) NU-1000 (which has Zr₆(μ₃-OH)₄(μ₃-O)₄(OH)₄(OH₂)₄ nodes linked by pyrenes with -COO^- end groups). From these, the differential isosteric heats of adsorption (Q_st) were determined versus coverage. These were compared to density functional calculations of the adsorption enthalpies on different sites, assuming that they are filled in a sequential order from the strongest to weakest binding. This comparison shows excellent quantitative agreement on the trends for the four gases, as well as reasonable agreement in the absolute magnitude of the adsorption energies. This agreement indicates that the sites predicted by the density functional calculations to be populated at different coverages for the different gases are correct, thus further increasing our understanding of adsorption on this prototype MOF.

Original language	English (US)
Pages (from-to)	6586-6591
Number of pages	6
Journal	Journal of Physical Chemistry C
Volume	123
Issue number	11
DOIs	https://doi.org/10.1021/acs.jpcc.8b12263
State	Published - Mar 21 2019

Bibliographical note

Funding Information:
This work was supported by DOE-OBES Chemical Sciences Division under grant #DE-FG02-96ER14630 and as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DESC0012702. Initial funding for O.E.V.’s contributions to this project was provided by NSF DMR 1206208. We gratefully thank J. T. Hupp and O. K. Farha of Northwestern University for kindly providing the NU-1000 samples and discussing the manuscript.

Publisher Copyright:
© Copyright 2019 American Chemical Society.

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@article{845760bae9644633a89cedc2d0716aec,

title = "Heats of Adsorption of N2, CO, Ar, and CH4 versus Coverage on the Zr-Based MOF NU-1000: Measurements and DFT Calculations",

abstract = "Equilibrium adsorption isotherms at very low coverage (0 to ∼0.1 monolayer) have been measured for four simple gases, N2, CO, Ar, and CH4, at several temperatures above 98 K on the metal-organic framework (MOF) NU-1000 (which has Zr6(μ3-OH)4(μ3-O)4(OH)4(OH2)4 nodes linked by pyrenes with -COO- end groups). From these, the differential isosteric heats of adsorption (Qst) were determined versus coverage. These were compared to density functional calculations of the adsorption enthalpies on different sites, assuming that they are filled in a sequential order from the strongest to weakest binding. This comparison shows excellent quantitative agreement on the trends for the four gases, as well as reasonable agreement in the absolute magnitude of the adsorption energies. This agreement indicates that the sites predicted by the density functional calculations to be populated at different coverages for the different gases are correct, thus further increasing our understanding of adsorption on this prototype MOF.",

author = "Vissers, {Graeme O.} and Wei Zhang and Vilches, {Oscar E.} and Liu, {Wei Guang} and Yu, {Haoyu S.} and Truhlar, {Donald G.} and Campbell, {Charles T.}",

note = "Funding Information: This work was supported by DOE-OBES Chemical Sciences Division under grant #DE-FG02-96ER14630 and as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DESC0012702. Initial funding for O.E.V.{\textquoteright}s contributions to this project was provided by NSF DMR 1206208. We gratefully thank J. T. Hupp and O. K. Farha of Northwestern University for kindly providing the NU-1000 samples and discussing the manuscript. Publisher Copyright: {\textcopyright} Copyright 2019 American Chemical Society.",

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T1 - Heats of Adsorption of N2, CO, Ar, and CH4 versus Coverage on the Zr-Based MOF NU-1000

T2 - Measurements and DFT Calculations

AU - Vissers, Graeme O.

AU - Zhang, Wei

AU - Vilches, Oscar E.

AU - Liu, Wei Guang

AU - Yu, Haoyu S.

AU - Truhlar, Donald G.

AU - Campbell, Charles T.

N1 - Funding Information: This work was supported by DOE-OBES Chemical Sciences Division under grant #DE-FG02-96ER14630 and as part of the Inorganometallic Catalysis Design Center, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award DESC0012702. Initial funding for O.E.V.’s contributions to this project was provided by NSF DMR 1206208. We gratefully thank J. T. Hupp and O. K. Farha of Northwestern University for kindly providing the NU-1000 samples and discussing the manuscript. Publisher Copyright: © Copyright 2019 American Chemical Society.

PY - 2019/3/21

Y1 - 2019/3/21

N2 - Equilibrium adsorption isotherms at very low coverage (0 to ∼0.1 monolayer) have been measured for four simple gases, N2, CO, Ar, and CH4, at several temperatures above 98 K on the metal-organic framework (MOF) NU-1000 (which has Zr6(μ3-OH)4(μ3-O)4(OH)4(OH2)4 nodes linked by pyrenes with -COO- end groups). From these, the differential isosteric heats of adsorption (Qst) were determined versus coverage. These were compared to density functional calculations of the adsorption enthalpies on different sites, assuming that they are filled in a sequential order from the strongest to weakest binding. This comparison shows excellent quantitative agreement on the trends for the four gases, as well as reasonable agreement in the absolute magnitude of the adsorption energies. This agreement indicates that the sites predicted by the density functional calculations to be populated at different coverages for the different gases are correct, thus further increasing our understanding of adsorption on this prototype MOF.

AB - Equilibrium adsorption isotherms at very low coverage (0 to ∼0.1 monolayer) have been measured for four simple gases, N2, CO, Ar, and CH4, at several temperatures above 98 K on the metal-organic framework (MOF) NU-1000 (which has Zr6(μ3-OH)4(μ3-O)4(OH)4(OH2)4 nodes linked by pyrenes with -COO- end groups). From these, the differential isosteric heats of adsorption (Qst) were determined versus coverage. These were compared to density functional calculations of the adsorption enthalpies on different sites, assuming that they are filled in a sequential order from the strongest to weakest binding. This comparison shows excellent quantitative agreement on the trends for the four gases, as well as reasonable agreement in the absolute magnitude of the adsorption energies. This agreement indicates that the sites predicted by the density functional calculations to be populated at different coverages for the different gases are correct, thus further increasing our understanding of adsorption on this prototype MOF.

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