Gaining Insights on the H2–Sorbent Interactions: Robust soc-MOF Platform as a Case Study

Handle URI:
http://hdl.handle.net/10754/622295
Title:
Gaining Insights on the H2–Sorbent Interactions: Robust soc-MOF Platform as a Case Study
Authors:
Cairns, Amy; Eckert, Juergen; Wojtas, Lukasz; Thommes, Matthias; Wallacher, Dirk; Georgiev, Peter A.; Forster, Paul M.; Belmabkhout, Youssef ( 0000-0001-9952-5007 ) ; Ollivier, Jacques; Eddaoudi, Mohamed ( 0000-0003-1916-9837 )
Abstract:
We report on the synthesis and gas adsorption properties (i.e., Ar and H2) of four robust 3-periodic metal–organic frameworks (MOFs) having the targeted soc topology. These cationic MOFs are isostructural to the parent indium-based MOF, In-soc-MOF-1a (for NO3–), previously reported by us, and likewise are constructed from the assembly of rigid μ3-oxygen-centered trinuclear metal carboxylate clusters, [M3O(O2C−)6], where M = In3+ or Fe3+. Each inorganic trinuclear molecular building block (MBB), generated in situ, is bridged by six 3,3′,5,5′-azobenzenetetracarboxylate (ABTC4–) ligands to give the extended (4,6)-connected MOF, soc-MOF. In our previous work, we confirmed that the parent soc-MOF, i.e., In-soc-MOF-1a, possesses unique structural characteristics (e.g., vacant In binding sites and narrow pores with higher localized charge density), which led to exceptional hydrogen (H2) storage capabilities. Therefore, charged MOFs with soc topology can be viewed collectively as an ideal prototypical platform to examine the impact of specific structural parameters on H2–MOF interactions via systematic gas adsorption studies. We infer that enhanced binding of molecular H2 is primarily governed by the presence and type of vacant metal centers (i.e., Fe was shown to exhibit stronger H2–MOF interactions at low H2 loading compared to the In analogues). These findings are evident from the associated isosteric heat of adsorption (Qst) at low loadings and inelastic neutron scattering (INS) experiments of the rotational transitions of sorbed H2, as well as, temperature-programmed desorption (TPD) studies (for a select compound). The importance of localized charge density is also highlighted, where the extra-framework nitrate anions in the Fe-soc-MOF-1a (for NO3–) facilitate enhanced binding affinities as compared to the chloride analogue.
KAUST Department:
Advanced Membranes and Porous Materials Research Center; Functional Materials Design, Discovery and Development (FMD3); Physical Sciences and Engineering (PSE) Division
Citation:
Cairns AJ, Eckert J, Wojtas L, Thommes M, Wallacher D, et al. (2016) Gaining Insights on the H2–Sorbent Interactions: Robust soc-MOF Platform as a Case Study. Chemistry of Materials 28: 7353–7361. Available: http://dx.doi.org/10.1021/acs.chemmater.6b02817.
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
Issue Date:
18-Sep-2016
DOI:
10.1021/acs.chemmater.6b02817
Type:
Article
ISSN:
0897-4756; 1520-5002
Sponsors:
Research reported in this publication was supported by King Abdullah University of Science and Technology (KAUST). We gratefully acknowledge the financial support of the DOE-BES (DE0FG02-07ER4670). We also acknowledge the Advanced Light Source which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
Is Supplemented By:
Cairns, A. J., Eckert, J., Wojtas, L., Thommes, M., Wallacher, D., Georgiev, P. A., … Eddaoudi, M. (2016). CCDC 1408397: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j8k5j; DOI:10.5517/ccdc.csd.cc1j8k5j; HANDLE:http://hdl.handle.net/10754/624508; Cairns, A. J., Eckert, J., Wojtas, L., Thommes, M., Wallacher, D., Georgiev, P. A., … Eddaoudi, M. (2016). CCDC 1408398: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j8k6k; DOI:10.5517/ccdc.csd.cc1j8k6k; HANDLE:http://hdl.handle.net/10754/624509; Cairns, A. J., Eckert, J., Wojtas, L., Thommes, M., Wallacher, D., Georgiev, P. A., … Eddaoudi, M. (2016). CCDC 1408399: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j8k7l; DOI:10.5517/ccdc.csd.cc1j8k7l; HANDLE:http://hdl.handle.net/10754/624510; Cairns, A. J., Eckert, J., Wojtas, L., Thommes, M., Wallacher, D., Georgiev, P. A., … Eddaoudi, M. (2016). CCDC 1408400: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j8k8m; DOI:10.5517/ccdc.csd.cc1j8k8m; HANDLE:http://hdl.handle.net/10754/624511
Additional Links:
http://pubs.acs.org/doi/full/10.1021/acs.chemmater.6b02817
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Functional Materials Design, Discovery and Development (FMD3)

Full metadata record

DC FieldValue Language
dc.contributor.authorCairns, Amyen
dc.contributor.authorEckert, Juergenen
dc.contributor.authorWojtas, Lukaszen
dc.contributor.authorThommes, Matthiasen
dc.contributor.authorWallacher, Dirken
dc.contributor.authorGeorgiev, Peter A.en
dc.contributor.authorForster, Paul M.en
dc.contributor.authorBelmabkhout, Youssefen
dc.contributor.authorOllivier, Jacquesen
dc.contributor.authorEddaoudi, Mohameden
dc.date.accessioned2017-01-02T09:08:24Z-
dc.date.available2017-01-02T09:08:24Z-
dc.date.issued2016-09-18en
dc.identifier.citationCairns AJ, Eckert J, Wojtas L, Thommes M, Wallacher D, et al. (2016) Gaining Insights on the H2–Sorbent Interactions: Robust soc-MOF Platform as a Case Study. Chemistry of Materials 28: 7353–7361. Available: http://dx.doi.org/10.1021/acs.chemmater.6b02817.en
dc.identifier.issn0897-4756en
dc.identifier.issn1520-5002en
dc.identifier.doi10.1021/acs.chemmater.6b02817en
dc.identifier.urihttp://hdl.handle.net/10754/622295-
dc.description.abstractWe report on the synthesis and gas adsorption properties (i.e., Ar and H2) of four robust 3-periodic metal–organic frameworks (MOFs) having the targeted soc topology. These cationic MOFs are isostructural to the parent indium-based MOF, In-soc-MOF-1a (for NO3–), previously reported by us, and likewise are constructed from the assembly of rigid μ3-oxygen-centered trinuclear metal carboxylate clusters, [M3O(O2C−)6], where M = In3+ or Fe3+. Each inorganic trinuclear molecular building block (MBB), generated in situ, is bridged by six 3,3′,5,5′-azobenzenetetracarboxylate (ABTC4–) ligands to give the extended (4,6)-connected MOF, soc-MOF. In our previous work, we confirmed that the parent soc-MOF, i.e., In-soc-MOF-1a, possesses unique structural characteristics (e.g., vacant In binding sites and narrow pores with higher localized charge density), which led to exceptional hydrogen (H2) storage capabilities. Therefore, charged MOFs with soc topology can be viewed collectively as an ideal prototypical platform to examine the impact of specific structural parameters on H2–MOF interactions via systematic gas adsorption studies. We infer that enhanced binding of molecular H2 is primarily governed by the presence and type of vacant metal centers (i.e., Fe was shown to exhibit stronger H2–MOF interactions at low H2 loading compared to the In analogues). These findings are evident from the associated isosteric heat of adsorption (Qst) at low loadings and inelastic neutron scattering (INS) experiments of the rotational transitions of sorbed H2, as well as, temperature-programmed desorption (TPD) studies (for a select compound). The importance of localized charge density is also highlighted, where the extra-framework nitrate anions in the Fe-soc-MOF-1a (for NO3–) facilitate enhanced binding affinities as compared to the chloride analogue.en
dc.description.sponsorshipResearch reported in this publication was supported by King Abdullah University of Science and Technology (KAUST). We gratefully acknowledge the financial support of the DOE-BES (DE0FG02-07ER4670). We also acknowledge the Advanced Light Source which is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/full/10.1021/acs.chemmater.6b02817en
dc.titleGaining Insights on the H2–Sorbent Interactions: Robust soc-MOF Platform as a Case Studyen
dc.typeArticleen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.contributor.departmentFunctional Materials Design, Discovery and Development (FMD3)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChemistry of Materialsen
dc.contributor.institutionDepartment of Chemistry, University of South Florida, 4202 East Fowler Avenue (CHE205), Tampa, Florida 33620, United Statesen
dc.contributor.institutionQuantachrome Instruments, 1900 Corporate Drive, Boynton Beach, Florida 33426, United Statesen
dc.contributor.institutionSample Environment Department (NP-ASE), Helmholtz-Zentrum Berlin für Materialien und Energie, Hahn-Meitner-Platz 1, D-14109 Berlin, Germanyen
dc.contributor.institutionDepartment of Structural Chemistry, University of Milan, 21 Via G. Venzian, I-20133 Milano, Italyen
dc.contributor.institutionDepartment of Chemistry and Biochemistry, University of Nevada, Box 454330, Las Vegas, Nevada 89154, United Statesen
dc.contributor.institutionInstitut Laue-Langevin, Grenoble, 38042 Cedex, Franceen
kaust.authorCairns, Amyen
kaust.authorBelmabkhout, Youssefen
kaust.authorEddaoudi, Mohameden
dc.relation.isSupplementedByCairns, A. J., Eckert, J., Wojtas, L., Thommes, M., Wallacher, D., Georgiev, P. A., … Eddaoudi, M. (2016). CCDC 1408397: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j8k5jen
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j8k5jen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624508en
dc.relation.isSupplementedByCairns, A. J., Eckert, J., Wojtas, L., Thommes, M., Wallacher, D., Georgiev, P. A., … Eddaoudi, M. (2016). CCDC 1408398: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j8k6ken
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j8k6ken
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624509en
dc.relation.isSupplementedByCairns, A. J., Eckert, J., Wojtas, L., Thommes, M., Wallacher, D., Georgiev, P. A., … Eddaoudi, M. (2016). CCDC 1408399: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j8k7len
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j8k7len
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624510en
dc.relation.isSupplementedByCairns, A. J., Eckert, J., Wojtas, L., Thommes, M., Wallacher, D., Georgiev, P. A., … Eddaoudi, M. (2016). CCDC 1408400: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j8k8men
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j8k8men
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624511en
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.