Ultraporous, Water Stable, and Breathing Zirconium-Based Metal-Organic Frameworks with ftw Topology.

"Breathing" metal-organic frameworks (MOFs) are an emerging class of soft porous crystals (SPCs) with potential for high working capacity for gas storage applications. However, most breathing MOFs have low stability and/or low surface area. Here we report a water-stable, high surface area, breathing...

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Publicado en:Journal of the American Chemical Society Vol. 137; no. 40; pp. 13183 - 13191
Autores principales: Deria, Pravas, Gómez-Gualdrón, Diego A., Bury, Wojciech, Schaef, Herbert T., Wang, Timothy C., Thallapally, Praveen K., Sarjeant, Amy A., Snurr, Randall Q., Hupp, Joseph T., Farha, Omar K.
Formato: Artículo
Publicado: American Chemical Society 10/14/2015
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 10/14/2015
      vid: 137
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      pub: American Chemical Society
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        111336954
        10.1021/jacs.5b08860
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        atl: Ultraporous, Water Stable, and Breathing Zirconium-Based Metal-Organic Frameworks with ftw Topology.
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        au:
          Deria, Pravas
          Gómez-Gualdrón, Diego A.
          Bury, Wojciech
          Schaef, Herbert T.
          Wang, Timothy C.
          Thallapally, Praveen K.
          Sarjeant, Amy A.
          Snurr, Randall Q.
          Hupp, Joseph T.
          Farha, Omar K.
        affil:
          Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States
          Department ofChemical and Biological Engineering, Northwestern University, Evanston, Illinois 60208, United States
          Department of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664 Warsaw, Poland
          Pacific Northwest National Laboratory, Richland, Washington 99352, United States
          Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 22254, Saudi Arabia
      su:
        Zirconium compounds synthesis
        Metal-organic frameworks
        Density functional theory
        Gas storage
        Porphyrin synthesis
        X-ray diffraction
      sug:
        subj:
          Zirconium compounds synthesis
          Metal-organic frameworks
          Density functional theory
          Gas storage
          Porphyrin synthesis
          X-ray diffraction
      ab: "Breathing" metal-organic frameworks (MOFs) are an emerging class of soft porous crystals (SPCs) with potential for high working capacity for gas storage applications. However, most breathing MOFs have low stability and/or low surface area. Here we report a water-stable, high surface area, breathing MOF of ftw topology, NU-1105. While Zr-oxo clusters as nodes introduce water stability in NU-1105, its high surface area and breathing character stem from its pyrene-based tetracarboxylate (Py-FP) linkers, in which the fluorene units (F) in the FP "arms" play a key role in promoting breathing behavior. During gas sorption studies, the "closed pore" (cp) ↔ "open pore" (op) transition of NU-1105 occurs at a propane pressure of ~3 bar. At 1 bar, NU-1105 is in its cp form and adsorbs less propane than it would in its op form, highlighting improved working capacity. In situ powder X-ray diffraction during propane sorption was used to track the cp ↔ op transition, and molecular modeling was used to elucidate the structure of the op and cp forms of NU-1105. According to TD-DFT calculations, the proposed conformations of the Py-FP linkers in the op and cp forms are consistent with the measured excitation and emission spectra of the op and cp forms of NU-1105. Similar structural transitions are also observed in the porphyrinic MOF NU-1104 depending on the identity of the porphyrin core; we observed breathing behavior if the constituent Por-PTP linker is nonmetalated.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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          year: 2015
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