Flexible and hydrophobic Zn-based metal-organic framework

Research output: Contribution to journalResearch articleContributedpeer-review

Contributors

  • Ines Maria Hauptvogel - , TUD Dresden University of Technology (Author)
  • Ralf Biedermann - , TUD Dresden University of Technology (Author)
  • Nicole Klein - , Chair of Inorganic Chemistry I (Author)
  • Irena Senkovska - , Chair of Inorganic Chemistry I (Author)
  • Amandine Cadiau - , TUD Dresden University of Technology (Author)
  • Dirk Wallacher - , Helmholtz Centre Berlin for Materials and Energy (Author)
  • Ralf Feyerherm - , Helmholtz Centre Berlin for Materials and Energy (Author)
  • Stefan Kaskel - , Chair of Inorganic Chemistry I (Author)

Abstract

A zinc-based metal-organic framework Zn2(adb)2(dabco) ·4.5 DMF (K) (DUT-30(Zn), DUT = Dresden University of Technology, adb = 9,10-anthracene dibenzoate, dabco =1,4-diazabicyclo[2.2.2]octane, DMF = N,N-dimethylformamide) was synthesized using a solvothermal route. This MOF exhibits six crystallographic guest dependent phases. Two of them were characterized via single crystal X-ray analysis. The as-synthesized phase K crystallizes in the orthorhombic space group Fmmm, with a = 9.6349(9), b = 26.235(3), and c = 28.821(4) Å and consists of two interpenetrated pillar-layer networks with pcu topology. When the substance loses 0.5 DMF molecules per formula unit, a phase transition from the kinetic phase K to a thermodynamic phase T occurs. Zn2(adb)2(dabco) ·4 DMF (T) crystallizes in the tetragonal space group I4/mmm, with a = 19.5316(8) and c = 9.6779(3) Å. During the evacuation the DUT-30(Zn) undergoes again the structural transformation to A. The activated compound A shows the gate pressure effect in the low pressure region of nitrogen physisorption isotherm and has a BET surface area of 960 m2g-1 and a specific pore volume of 0.43 cm3 g-1. Furthermore, DUT-30(Zn) exhibits a hydrogen storage capacity of 1.12 wt % at 1 bar, a CO2 uptake of 200 cm3 g-1 at-78 °C and 0.9 bar, and a n-butane uptake of 3.0 mmol·g-1 at 20 °C. The N 2 adsorption process was monitored in situ via X-ray powder diffraction using synchrotron radiation. A low temperature induced transformation of phase A to phase V could be observed if the compound was cooled under vacuum to-196 °C. A further crystalline phase N could be identified if the framework was filled with nitrogen at-196 °C. Additionally, the treatment of activated phase A with water leads to the new phase W.

Details

Original languageEnglish
Pages (from-to)8367-8374
Number of pages8
JournalInorganic chemistry
Volume50
Issue number17
Publication statusPublished - 5 Sept 2011
Peer-reviewedYes

Keywords