Polyoxometalate-Based Metal Organic Frameworks (POMOFs): Structural Trends, Energetics, and High Electrocatalytic Efficiency for Hydrogen Evolution Reaction.
The grafting of the triangular 1,3,S-benzene tricarboxylate linkers (denoted trim) on tetrahedral e-Keggin polyoxometalates (POMs) capped by Zn(II) ions, formed in situ under hydrothermal conditions, has generated three novel POM-based metal organic frameworks (POMOFs). (ThA)[PMoMo4O(OH)4Z] [C}-13(C...
| Publicado en: | Journal of the American Chemical Society Vol. 133; no. 34; pp. 13363 - 13375 |
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| Autores principales: | , , , , , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
8/31/2011
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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=66622139&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 66622139 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: 8/31/2011 vid: 133 iid: 34 pid: 997 pub: American Chemical Society artinfo: ui: 66622139 10.1021/ja201165c ppf: 13363 ppct: 12 formats: tig: atl: Polyoxometalate-Based Metal Organic Frameworks (POMOFs): Structural Trends, Energetics, and High Electrocatalytic Efficiency for Hydrogen Evolution Reaction. aug: au: Nohra, Brigitte Moll, Hani El Albelo, L. Marleny Rodriguez Mialane, Pierre Marrot, Jérôme Mellot-Draznieks, Caroline O'Keeffe, Michael Biboum, Rosa Ngo Lemaire, Joel Keita, Bineta Nadjo, L. Louis Dolbecq, Anne affil: Institut Lavoisier de Versailles, UMR 8180, Université de Versailles Saint-Quentin en Yvelines, 45 Avenue des Etats-Unis, 78035 Versailles cedex, France Zeolite Engineering Laboratory, Institute of Materials Research and Engineering (IMRE), University of Havana, Havana, 10400, Cuba Laboratoire de Chimie et Biologie des Métaux, Université Joseph Fourier, Grenoble, Centre National de La Recherche Scientifique, Unite Mixte de Recherche 5249, CEA, DSV/IRTSV, 17 rue des Martyrs, F-38054, Grenoble cedex 9, France Department of Chemistry and Biochemistry, Arizona State University, Tempe, Arizona 85287, United States Laboratoire de Chiniie Physique Groupe d'Electrochimie et de Photoélectrochimie Groupe Ions en Phase Gazeuse, UMR 8000, CNRS, Université Paris-Sud, Bâtiment 350, 91405 Orsay cedex, France su: Trimellitic anhydride Tetrahedral coordinates Polyoxometalates Ions Electrodes Electrocatalysis Linkers (Computer programs) sug: subj: Trimellitic anhydride Tetrahedral coordinates Polyoxometalates Ions Electrodes Electrocatalysis Linkers (Computer programs) ab: The grafting of the triangular 1,3,S-benzene tricarboxylate linkers (denoted trim) on tetrahedral e-Keggin polyoxometalates (POMs) capped by Zn(II) ions, formed in situ under hydrothermal conditions, has generated three novel POM-based metal organic frameworks (POMOFs). (ThA)[PMoMo4O(OH)4Z] [C}-13(COO)HO (e(trim)413) is a 3D open-framework built of molecular Keggin units connected by trim linkers, with channels occupied by tetrabutylammonium (TBA) counterions. e(trim) is a novel (3,4)-connected net, named ofp for open-framework polyoxometalate, and computer simulations have been used to evaluate its relative stability in comparison with ctnand bor-like polymorphs, showing the stability of this novel phase directly related to its greatest density. A computational study was also undertaken with the aim of locating TBA molecules, the positions of which could not be deduced from single crystal X-ray diffraction, and further rationalizes their structure directing role. In (TBA)[PMo"Mo"O(OH)Zn] [CH(Coo)] (e(trim)), the building unit is not the molecular Keggin but a dimerized form of this POM. Their connection via trim linkers generates a 3D framework with channels filled by TBA cations. In (TBA)[PMo\TsMowo(OH)zn][cH(coo)].HO ([e(trim)]δ), zigzag chains are connected via the organic linkers, forming 2D grids. Modified electrodes were fabricated by direct adsorption of the POMOFs on glassy carbon or entrapment in carbon paste (CPE). A remarkable electrocatalytic hydrogen evolution reaction (HER) was detected with a yield greater than 95%, and a turnover number as high as 1.2 x l0 was obtained after S h. The reported POMOF-based electrodes are more active than platinum, with a roughly 260 mV anodic shift. Finally, the electrocatalytic activities of ϵ(trim)/CPE electrodes in various XC1 (x = Li, Na, K, Cs) media have been studied. This allowed us to detect a cation effect and propose an electrocatalytic mechanistic pathway for the HER. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2011 holdings: @attributes: islocal: N |
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