Probing Adsorption Interactions in Metal-Organic Frameworks using X-ray Spectroscopy.
We explore the local electronic signatures of molecular adsorption at coordinatively unsaturated binding sites in the metal-organic framework Mg-MOF-74 using X-ray spectroscopy and first-principles calculations. In situ measurements at the Mg K-edge reveal distinct pre-edge absorption features assoc...
| Publicado en: | Journal of the American Chemical Society Vol. 135; no. 48; pp. 18183 - 18191 |
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| Autores principales: | , , , , , , , |
| Formato: | Artículo |
| Publicado: |
American Chemical Society
12/4/2013
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=93312306&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 93312306 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 12/4/2013 vid: 135 iid: 48 pid: 997 pub: American Chemical Society artinfo: ui: 93312306 10.1021/ja408972f ppf: 18183 ppct: 8 formats: tig: atl: Probing Adsorption Interactions in Metal-Organic Frameworks using X-ray Spectroscopy. aug: au: Drisdell, Walter S. Poloni, Roberta McDonald, Thomas M. Long, Jeffrey R. Smit, Berend Neaton, Jeffrey B. Prendergast, David Kortright, Jeffrey B. affil: Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States Department of Chemical and Biomolecular Engineering, University of California, Berkeley, California 94720-1460, United States Department of Chemistry, University of California, Berkeley, California 94720-1460, United States Laboratoire de Science et Ingénierie des Matériaux et Procédés (SIMaP), UMR CNRS 5266, Grenoble-INP, BP 75, 38402 Saint Martin d'Hères Cedex, France su: Binding sites X-ray spectroscopy Dimethylformamide Density functional theory Vibrational spectra sug: subj: Binding sites X-ray spectroscopy Dimethylformamide Density functional theory Vibrational spectra ab: We explore the local electronic signatures of molecular adsorption at coordinatively unsaturated binding sites in the metal-organic framework Mg-MOF-74 using X-ray spectroscopy and first-principles calculations. In situ measurements at the Mg K-edge reveal distinct pre-edge absorption features associated with the unique, open coordination of the Mg sites which are suppressed upon adsorption of CO and N,N'-dimethylformamide. Density functional theory shows that these spectral changes arise from modifications of local symmetry around the Mg sites upon gas uptake and are strongly dependent on the metal-adsorbate binding strength. The expanded MOF Mg(dobpdc) displays the same behavior upon adsorption of CO and N,N'-dimethylethylenediamine. Similar sensitivity to local symmetry is expected for any open metal site, making X-ray spectroscopy an ideal tool for examining adsorption in such MOFs. Qualitative agreement between ambient-temperature experimental and 0 K theoretical spectra is good, with minor discrepancies thought to result from framework vibrational motion. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2013 holdings: @attributes: islocal: N |
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