Structural Transformations and Adsorption of Fuel-Related Gases of a Structurally Responsive Nickel Phosphonate Metal--Organic Framework, Ni-STA-12.
The structure of the nickel N,N′-piperazinebismethylenephosphonate, Ni-STA-12 (St. Andrews porous material-12), has been determined in the hydrated (NiL∙8HO, L = OPCHNCHNCHPO), partially dehydrated (NiL∙2HO), and fully dehydrated (NiL) forms from high-resolution synchrotron X-ray powder diffraction....
| Publicado en: | Journal of the American Chemical Society Vol. 130; no. 47; pp. 15967 - 15982 |
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| Autores principales: | , , , , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
11/26/2008
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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=35614370&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 35614370 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: 11/26/2008 vid: 130 iid: 47 pid: 997 pub: American Chemical Society artinfo: ui: 35614370 10.1021/ja804936z ppf: 15967 ppct: 15 formats: tig: atl: Structural Transformations and Adsorption of Fuel-Related Gases of a Structurally Responsive Nickel Phosphonate Metal--Organic Framework, Ni-STA-12. aug: au: Miller, Stuart A. Pearce, Gordon M. Wright, Paul A. Bonino, Francesca Chavan, Sachin Bordiga, Silvia Margiolaki, Irene Guillou, Nathalie Férey, Gérard Bourrelly, Sandrine Llewellyn, Philip L. affil: School of Chemistry, University of St Andrews, Purdie Building, North Haugh, St Andrews, Fife, KY16 9ST U.K. Department of Inorganic, Physical and Materials Chemistry and NIS Centre of Excellence and INSTM Centro di Riferimento, University of Turin, Via P Giuria 7, 1-10125 Turin, Italy European Synchrotron Radiation Facility, F-38043 Grenoble, France Institut Lavoisier, Université de Versailles St-Quentin en Yvelines--CNRS, UMR 8180, 45, Avenue des Etats-Unis, 78035 Versailles cedex, France Laboratoire Chimie Provence, Universités d'Aix-Marseille I, II & III--CNRS, UMR 6264, Centre de Saint Jérôme, 13397 Marseille cedex 20, France su: Adsorption (Chemistry) Separation (Technology) Surface chemistry Structural frames Spectrum analysis Atmospheric temperature Chemical structure Physical & theoretical chemistry sug: subj: Adsorption (Chemistry) Separation (Technology) Surface chemistry Structural frames Spectrum analysis Atmospheric temperature Chemical structure Physical & theoretical chemistry ab: The structure of the nickel N,N′-piperazinebismethylenephosphonate, Ni-STA-12 (St. Andrews porous material-12), has been determined in the hydrated (NiL∙8HO, L = OPCHNCHNCHPO), partially dehydrated (NiL∙2HO), and fully dehydrated (NiL) forms from high-resolution synchrotron X-ray powder diffraction. The framework structures of NiL∙8HO and NiL∙2HO are almost identical (R¯3, a = 27.8342(1) Å, c= 6.2421(2) Å; R¯3, a = 27.9144(1) Å, c= 6.1655(2) Å) with additional physisorbed water of the as-prepared Ni-STA-12 present in an ordered hydrogen-bonded network in the channels. Ab initio structure solution of the fully dehydrated solid indicates it has changed symmetry to triclinic (PL a = 6.03475(5) Å, b = 14.9157(2) Å, c 16.1572(2) Å, α = 1 12.5721(7)°, β = 95.7025(11)°, γ = 96.4950(11)°) as a result of a topotactic structural rearrangement. The fully dehydrated solid possesses permanent porosity with elliptical channels 8 Å × 9 Å in free diameter. The structural change results from the loss of water coordinated to the nickel cations, so that the nickel coordination changes from edge-sharing octahedral NiON to edge- and corner-sharing five-fold NiON. During this change, two out of three phosphonate groups rotate to become fully coordinated to nickel cations, leaving the remainder of the phosphonate groups coordinated to nickel cations by two oxygen atoms and with a P=O bond projecting into the channels. This transformation, which is completely reversible, causes substantial changes in both vibrational and electronic properties as shown by IR, Raman and UV-visible spectroscopies. Complementary adsorption, calorimetric, and infrared studies of the probe adsorbates H, CO, and CO reveal the presence of several distinct adsorption sites in the solid, which are attributed to their interactions with nickel cations which are weak Lewis acid sites, as well as with P=O groups that project into the pores. At 304 K, the adsorption isotherms and enthalpies of adsorption on dehydrated Ni-STA-12 have been measured for CO and CH: Ni-STA-12 gives adsorption uptakes of CO of 2.5 mmol g at 1 bar, an uptake ca. 10 times that of CH. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2008 holdings: @attributes: islocal: N |
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