Guest Molecule-Responsive Functional Calcium Phosphonate Frameworks for Tuned Proton Conductivity.
We report the synthesis, structural characterization, and functionality (framework interconversions together with proton conductivity) of an open-framework hybrid that combines Ca ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). Ca[(HOPCHCOOH)][(HOPCH(COO)H)...
| Publicado en: | Journal of the American Chemical Society Vol. 136; no. 15; pp. 5731 - 5740 |
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| Autores principales: | , , , , , , , , , , , |
| Formato: | Artículo |
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American Chemical Society
4/16/2014
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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=96121678&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 96121678 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: 4/16/2014 vid: 136 iid: 15 pid: 997 pub: American Chemical Society artinfo: ui: 96121678 10.1021/ja500356z ppf: 5731 ppct: 9 formats: tig: atl: Guest Molecule-Responsive Functional Calcium Phosphonate Frameworks for Tuned Proton Conductivity. aug: au: Bazaga-García, Montse Colodrero, Rosario M. P. Papadaki, Maria Garczarek, Piotr Zoń, Jerzy Olivera-Pastor, Pascual Losilla, Enrique R. León-Reina, Laura Aranda, Miguel A. G. Choquesillo-Lazarte, Duane Demadis, Konstantinos D. Cabeza, Aurelio affil: Departamento de Quimica Inorganica, Universidad de Malaga, Campus Teatinos s/n, Malaga 29071, Spain Crystal Engineering, Growth and Design Laboratory, Department of Chemistry, University of Crete, Voutes Campus, Crete, GR-71003, Greece Department of Medicinal Chemistry and Microbiology, Faculty of Chemistry, 50-370 Wroclaw, Poland Department of Thermodynamics, Institute of Heat Engineering and Mechanics, Faculty of Mechanical and Power Engineering, Wroclaw University of Technology, 27 Wybrzeże Wyspiańskiego, 50-370 Wroclaw, Poland Servicios Centrales de Apoyo a la Investigatión, SCAI, Universidad de Málaga, Campus Teatinos s/n, 29071-Málaga, Spain CELLS-ALBA Synchrotron, Carretera BP 1413, Km. 3.3, E-08290 Cerdanyola, Barcelona, Spain Laboratorio de Estudios Cristalográficos, IACT-CSIC, Granada, Spain su: Proton conductivity Calcium ions Adsorption (Chemistry) Molecular structure of water Ligands (Chemistry) sug: subj: Proton conductivity Calcium ions Adsorption (Chemistry) Molecular structure of water Ligands (Chemistry) ab: We report the synthesis, structural characterization, and functionality (framework interconversions together with proton conductivity) of an open-framework hybrid that combines Ca ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). Ca[(HOPCHCOOH)][(HOPCH(COO)H)(HO)]-5HO (Ca-PiPh-tA-I) is obtained by slow crystallization at ambient conditions from acidic (pH ≈ 3) aqueous solutions. It possesses a high water content (both Ca coordinated and in the lattice), and importantly, it exhibits water-filled ID channels. At 75 °C, Ca-PiPhtA-I is partially dehydrated and exhibits a crystalline diffraction pattern that can be indexed in a monoclinic cell with parameters close to the pristine phase. Rietveld refinement was carried out for the sample heated at 75 °C, Ca-PiPhtA-II, using synchrotron powder X-ray diffraction data, which revealed the molecular formula Ca[(HOPCHCOOH)][(HOPCH(COO)H)(HO)]. All connectivity modes of the "parent" Ca-PiPhtA-I framework are retained in Ca-PiPhtA-II. Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous NH) a new derivative is obtained (Ca-PiPhtA-NH) containing 7 NH and 16 HO molecules according to elemental and thermal analyses. Ca-PiPhtA-NH exhibits a complex X-ray diffraction pattern with peaks at 15.3 and 13.0 A that suggest partial breaking and transformation of the parent pillared structure. Although detailed structural identification of Ca-PiPhtA-NH was not possible, due in part to nonequilibrium adsorption conditions and the lack of crystallinity, FT-IR spectra and DTA-TG analysis indicate profound structural changes compared to the pristine Ca-PiPhtA-I. At 98% RH and T = 24 °C, proton conductivity, a, for Ca-PiPhtA-I is 5.7 × 10 S-cm. It increases to 1.3 × 10 S-cm upon activation by preheating the sample at 40 °C for 2 h followed by water equilibration at room temperature under controlled conditions. Ca-PiPhtA-NH exhibits the highest proton conductivity, 6.6 × 10 S-cm, measured at 98% RH and T = 24 °C. Activation energies (E) for proton transfer in the above-mentioned frameworks range between 0.23 and 0.4 eV, typical of a Grothuss mechanism of proton conduction. These results underline the importance of internal H-bonding networks that, in turn, determine conductivity properties of hybrid materials. It is highlighted that new proton transfer pathways may be created by means of cavity "derivatization" with selected guest molecules resulting in improved proton conductivity. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2014 holdings: @attributes: islocal: N |
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