Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon

Handle URI:
http://hdl.handle.net/10754/623681
Title:
Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon
Authors:
Berke, Heinz; Barman, Smair; Remhof, Arndt; Koitz, Ralph; Iannuzzi, Marcella; Blacque, Olivier; Yan, Yigang; Fox, Thomas; Hutter, Jürg; Züttel, Andreas
Abstract:
We report a novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation utilizing gaseous diborane. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature leading to the development of an unusual borenium type species (-NH=BH2+) ion-paired with hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the -iminodiborane ((--NHB2H5) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Berke H, Barman S, Remhof A, Koitz R, Iannuzzi M, et al. (2017) Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon. Chemistry - A European Journal. Available: http://dx.doi.org/10.1002/chem.201702013.
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
11-May-2017
DOI:
10.1002/chem.201702013
Type:
Article
ISSN:
0947-6539
Sponsors:
Funding from the Swiss National Science Foundation (SNSF), University of Zurich and generous computing resources from the University of Zurich are gratefully acknowledged.
Additional Links:
http://onlinelibrary.wiley.com/doi/10.1002/chem.201702013/abstract
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBerke, Heinzen
dc.contributor.authorBarman, Smairen
dc.contributor.authorRemhof, Arndten
dc.contributor.authorKoitz, Ralphen
dc.contributor.authorIannuzzi, Marcellaen
dc.contributor.authorBlacque, Olivieren
dc.contributor.authorYan, Yigangen
dc.contributor.authorFox, Thomasen
dc.contributor.authorHutter, Jürgen
dc.contributor.authorZüttel, Andreasen
dc.date.accessioned2017-05-22T06:58:04Z-
dc.date.available2017-05-22T06:58:04Z-
dc.date.issued2017-05-11en
dc.identifier.citationBerke H, Barman S, Remhof A, Koitz R, Iannuzzi M, et al. (2017) Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon. Chemistry - A European Journal. Available: http://dx.doi.org/10.1002/chem.201702013.en
dc.identifier.issn0947-6539en
dc.identifier.doi10.1002/chem.201702013en
dc.identifier.urihttp://hdl.handle.net/10754/623681-
dc.description.abstractWe report a novel strategy for post-synthesis amine borane functionalization of MOFs under gas-solid phase transformation utilizing gaseous diborane. The covalently confined amine borane derivative decorated on the framework backbone is stable when preserved at low temperature, but spontaneously liberates soft chemical hydrogen at room temperature leading to the development of an unusual borenium type species (-NH=BH2+) ion-paired with hydroborate anion. Furthermore, the unsaturated amino borane (-NH=BH2) and the -iminodiborane ((--NHB2H5) were detected as final products. A combination of DFT based molecular dynamics simulations and solid state NMR spectroscopy, utilizing isotopically enriched materials, were undertaken to unequivocally elucidate the mechanistic pathways for H2 liberation.en
dc.description.sponsorshipFunding from the Swiss National Science Foundation (SNSF), University of Zurich and generous computing resources from the University of Zurich are gratefully acknowledged.en
dc.publisherWiley-Blackwellen
dc.relation.urlhttp://onlinelibrary.wiley.com/doi/10.1002/chem.201702013/abstracten
dc.rightsThis is the peer reviewed version of the following article: Post-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenon, which has been published in final form at http://doi.org/10.1002/chem.201702013. This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.en
dc.titlePost-synthesis amine borane functionalization of metal-organic framework and its unusual chemical hydrogen release phenomenonen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalChemistry - A European Journalen
dc.eprint.versionPost-printen
dc.contributor.institutionUniversity of Zurich; Department of Chemistry; Winterthurerstrasse 190 8057 Zurich SWITZERLANDen
dc.contributor.institutionEmpa, Materials Sciences and Technology Department of Mobility, Environment and Energy Divison “Hydrogen and Energy’’ Überlandstrasse 129, 8600 Dübendorfen
dc.contributor.institutionInterdisciplinary Nanoscience Center (iNANO), Aarhus University, DK-8000 Aarhus C, Denmarken
dc.contributor.institutionEPFL Valais Wallis, EPFL SB ISIC LMER, Rue de l'Industrie 17, CH-1951 Sionen
kaust.authorBarman, Smairen
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