Understanding the H 2 Sorption Trends in the M-MOF-74 Series (M = Mg, Ni, Co, Zn)

Handle URI:
http://hdl.handle.net/10754/600130
Title:
Understanding the H 2 Sorption Trends in the M-MOF-74 Series (M = Mg, Ni, Co, Zn)
Authors:
Pham, Tony; Forrest, Katherine A.; Banerjee, Rahul; Orcajo, Gisela; Eckert, Juergen; Space, Brian
Abstract:
© 2014 American Chemical Society. Electronic structure calculations and simulations of H2 sorption were performed in four members of the M-MOF-74 series: Mg-MOF-74, Ni-MOF-74, Co-MOF-74, and Zn-MOF-74. Notable differences were observed in the partial charge and polarizability of the metal ions derived from the electronic structure calculations. The modeling parameters obtained from the electronic structure calculations were found to influence certain features in the experimentally observed H2 sorption trends in the M-MOF-74 series. The simulations were performed with the inclusion of explicit many-body polarization, which was required to reproduce the experimental H2 sorption observables (i.e., sorption isotherms and isosteric heats of adsorption (Qst)) and the H2-metal interaction in all four MOFs using classical molecular simulation. Consistent with experimental measurements, the simulations captured the following trend for the H2-metal interaction strength: Ni-MOF-74 > Co-MOF-74 > Mg-MOF-74 > Zn-MOF-74. The calculations revealed that stronger H2-metal interactions within the M-MOF-74 series corresponded to shorter H2-metal distances and higher induced dipoles on the metal-sorbed H2 molecules. In addition, it was observed that there was a strong correlation between the H2-metal interaction and the polarization contribution. Although Mg-MOF-74 has the highest calculated partial charge for the metal ion within the series, the Mg2+ ion has a very low polarizability compared to the other M2+ ions; this explains why the H2-metal interaction in this MOF is weaker compared to those for Ni-MOF-74 and Co-MOF-74. The sterics interactions, reflected in the crystal structure for all four MOFs, also played a role for the observed H2 sorption trends. Zn-MOF-74 has the lowest H2 uptakes and Qst within the series due to an unfavorable geometric environment for the Zn2+ ions within the ZnO5 clusters. Lastly, the two-dimensional quantum rotational levels were calculated for the H2-metal interaction in all four MOFs using the potential energy function employed herein and the calculated transitions were in good agreement with the corresponding peaks that were observed in the experimental inelastic neutron scattering (INS) spectra for the respective MOFs. This observation serves both to provide atomistic resolution to the spectroscopic experiments and to validate the molecular force field.
Citation:
Pham T, Forrest KA, Banerjee R, Orcajo G, Eckert J, et al. (2015) Understanding the H 2 Sorption Trends in the M-MOF-74 Series (M = Mg, Ni, Co, Zn) . The Journal of Physical Chemistry C 119: 1078–1090. Available: http://dx.doi.org/10.1021/jp510253m.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
KAUST Grant Number:
FIC/2010/06
Issue Date:
15-Jan-2015
DOI:
10.1021/jp510253m
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
B.S. acknowledges the National Science Foundation (Award No. CHE-1152362), the computational resources that were made available by a XSEDE Grant (No. TG-DMR090028), and the use of the services provided by Research Computing at the University of South Florida. This publication is also based on work supported by Award No. FIC/2010/06, made by the King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support.
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorPham, Tonyen
dc.contributor.authorForrest, Katherine A.en
dc.contributor.authorBanerjee, Rahulen
dc.contributor.authorOrcajo, Giselaen
dc.contributor.authorEckert, Juergenen
dc.contributor.authorSpace, Brianen
dc.date.accessioned2016-02-28T06:43:19Zen
dc.date.available2016-02-28T06:43:19Zen
dc.date.issued2015-01-15en
dc.identifier.citationPham T, Forrest KA, Banerjee R, Orcajo G, Eckert J, et al. (2015) Understanding the H 2 Sorption Trends in the M-MOF-74 Series (M = Mg, Ni, Co, Zn) . The Journal of Physical Chemistry C 119: 1078–1090. Available: http://dx.doi.org/10.1021/jp510253m.en
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/jp510253men
dc.identifier.urihttp://hdl.handle.net/10754/600130en
dc.description.abstract© 2014 American Chemical Society. Electronic structure calculations and simulations of H2 sorption were performed in four members of the M-MOF-74 series: Mg-MOF-74, Ni-MOF-74, Co-MOF-74, and Zn-MOF-74. Notable differences were observed in the partial charge and polarizability of the metal ions derived from the electronic structure calculations. The modeling parameters obtained from the electronic structure calculations were found to influence certain features in the experimentally observed H2 sorption trends in the M-MOF-74 series. The simulations were performed with the inclusion of explicit many-body polarization, which was required to reproduce the experimental H2 sorption observables (i.e., sorption isotherms and isosteric heats of adsorption (Qst)) and the H2-metal interaction in all four MOFs using classical molecular simulation. Consistent with experimental measurements, the simulations captured the following trend for the H2-metal interaction strength: Ni-MOF-74 > Co-MOF-74 > Mg-MOF-74 > Zn-MOF-74. The calculations revealed that stronger H2-metal interactions within the M-MOF-74 series corresponded to shorter H2-metal distances and higher induced dipoles on the metal-sorbed H2 molecules. In addition, it was observed that there was a strong correlation between the H2-metal interaction and the polarization contribution. Although Mg-MOF-74 has the highest calculated partial charge for the metal ion within the series, the Mg2+ ion has a very low polarizability compared to the other M2+ ions; this explains why the H2-metal interaction in this MOF is weaker compared to those for Ni-MOF-74 and Co-MOF-74. The sterics interactions, reflected in the crystal structure for all four MOFs, also played a role for the observed H2 sorption trends. Zn-MOF-74 has the lowest H2 uptakes and Qst within the series due to an unfavorable geometric environment for the Zn2+ ions within the ZnO5 clusters. Lastly, the two-dimensional quantum rotational levels were calculated for the H2-metal interaction in all four MOFs using the potential energy function employed herein and the calculated transitions were in good agreement with the corresponding peaks that were observed in the experimental inelastic neutron scattering (INS) spectra for the respective MOFs. This observation serves both to provide atomistic resolution to the spectroscopic experiments and to validate the molecular force field.en
dc.description.sponsorshipB.S. acknowledges the National Science Foundation (Award No. CHE-1152362), the computational resources that were made available by a XSEDE Grant (No. TG-DMR090028), and the use of the services provided by Research Computing at the University of South Florida. This publication is also based on work supported by Award No. FIC/2010/06, made by the King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support.en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleUnderstanding the H 2 Sorption Trends in the M-MOF-74 Series (M = Mg, Ni, Co, Zn)en
dc.typeArticleen
dc.identifier.journalThe Journal of Physical Chemistry Cen
dc.contributor.institutionUniversity of South Florida Tampa, Tampa, United Statesen
dc.contributor.institutionNational Chemical Laboratory India, Pune, Indiaen
dc.contributor.institutionUniversidad Rey Juan Carlos, Mostoles, Spainen
kaust.grant.numberFIC/2010/06en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.