Further Investigation of the Effect of Framework Catenation on Hydrogen Uptake in Metal--Organic Frameworks.

Hydrogen-sorption studies have been carried out for the catenation isomer pairs of PCN-6 and PCN-6′ (both have the formula of Cu(TATB), where TATB represents 4,4′,4″-s-triazine-2,4,6-triyltribenzoate with a formula of CHNO). Inelastic neutron scattering (INS) studies reveal that the initial sites oc...

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Publicado en:Journal of the American Chemical Society Vol. 130; no. 47; pp. 15896 - 15903
Autores principales: Shengqian Ma, Eckert, Juergen, Forster, Paul M., Ji Woong Yoon, Young Kyu Hwang, Jong-San Chang, Collier, Christopher D., Parise, John B., Hong-Cai Zhou
Formato: Artículo
Publicado: American Chemical Society 11/26/2008
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Acceso en línea:Ver este registro en EBSCOhost
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      dt: 11/26/2008
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      pub: American Chemical Society
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        10.1021/ja803492q
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        atl: Further Investigation of the Effect of Framework Catenation on Hydrogen Uptake in Metal--Organic Frameworks.
      aug:
        au:
          Shengqian Ma
          Eckert, Juergen
          Forster, Paul M.
          Ji Woong Yoon
          Young Kyu Hwang
          Jong-San Chang
          Collier, Christopher D.
          Parise, John B.
          Hong-Cai Zhou
        affil:
          Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012
          Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, IL 60439
          Materials Research Laboratory, University of California, Santa Barbara, California 93106
          Department for Chemistry, University of Nevada, Las Vegas, Nevada 89154
          Catalysis Center for Molecular Engineering, Korea Research Institute of Chemical Technology (KRICT), Jang-dong 100, Yuseong-Gu, daejon 305-600, Korea
          Mineral Physics Institute, Stony Brook University, Stony Brook, New York 11794
      su:
        Hydrogen spectra
        Absorption
        Separation (Technology)
        Surface chemistry
        Structural frames
        Structural analysis (Engineering)
      sug:
        subj:
          Hydrogen spectra
          Absorption
          Separation (Technology)
          Surface chemistry
          Structural frames
          Structural analysis (Engineering)
      ab: Hydrogen-sorption studies have been carried out for the catenation isomer pairs of PCN-6 and PCN-6′ (both have the formula of Cu(TATB), where TATB represents 4,4′,4″-s-triazine-2,4,6-triyltribenzoate with a formula of CHNO). Inelastic neutron scattering (INS) studies reveal that the initial sites occupied by adsorbed H are the open Cu centers of the paddlewheel units with comparable interaction energies in the two isomers. At high H loadings, where the H molecules adsorb mainly on or around the organic linkers, the interaction is found to be substantially stronger in catenated PCN-6 than in noncatenated PCN-6′, leading to much higher H uptake in the isomer with catenation. Hydrogen sorption measurements at pressures up to 50 bar demonstrate that framework catenation can be favorable for the enhancement of hydrogen adsorption. For example, the excess hydrogen uptake of PCN-6 is 72 mg/g (6.7 wt %) at 77 K/50 bar or 9.3 mg/g (0.92 wt %) at 298 K/50 bar, respectively, and that for PCN-6′ is 42 mg/g (4.0 wt %) at 77 K/50 bar or 4.0 mg/g (0.40 wt %) at 298 K/50 bar. Importantly, PCN-6 exhibits a total hydrogen uptake of 95 mg/g (8.7 wt %) (corresponding to a total volumetric value of 53.0 g/L, estimated based on crystallographic density) at 77 K/50 bar and 15 mg/g (1.5 wt %) at 298 K/50 bar. Significantly, the expected usable capacity of PCN-6 is as high as 75 mg/g (or 41.9 g/L) at 77 K, if a recharging pressure of 1.5 bar is assumed.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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