Influence of As-Formed Metal-Oxide in Non-Activated Water-Unstable Organometallic Framework Pores as Hydrolysis Delay Agent: Interplay Between Experiments and DFT Modeling

  • Mehrzad Arjmandi
  • Mahdi Pourafshari ChenarEmail author
  • Majid Peyravi
  • Mohsen Jahanshahi


In this work, a new strategy to increase the stability of humid-unstable MOFs in humid environment has been investigated. Among many known humid-unstable MOFs, MOF-5 has been selected due to its unique properties. The present work quantifies the influence of exposure to humid environment on the properties of MOF-5 as a function of relative humidity, exposure time and activation process. The activated and non-activated MOF-5 s are directly compared considering their humid stability for the first time. The properties examined include PXRD, TGA, SEM, and BET surface area. Moreover, the water adsorption isotherms are obtained using a gravimetric method at 22 °C using RH up to 87% and both A-MOF-5 and NA-MOF-5 showed type V isotherm. According to the results obtained, water vapor adsorption on NA-MOF-5 starts faster than that of A-MOF-5. Also, the uptake saturation of water vapor on NA-MOF-5 is about 80% higher than that of A-MOF-5. According to results obtained, in contrast to A-MOF-5, the water adsorbed in NA-MOF-5 will not lead to hydrolysis. Prior to exposure, the calculated BET surface area for A-MOF-5 and NA-MOF-5 was 2460 and 1134 m2/g, respectively. For A-MOF-5, after exposure times of up to 72 h, the BET surface area in RH = 45% reduced to about 1220 m2/g, and in RH = 65%, because of the destruction of the crystal structure, surprisingly it reduced to 36 m2/g. Also, for NA-MOF-5, relatively small changes in BET surface area were observed for exposure times of up to 72 h (RH = 45 and 65%). According to experimental results, deformation of A-MOF-5 after 72 h exposure to RH = 65% is quite obvious and the initial structure of A-MOF-5 is not recovered even by re-activation process. The results of BET surface area for activated NA-MOF-5 indicate that the high quality of MOF-5 can be obtained by activation of final humidity exposed NA-MOF-5. According to DFT-based computational results, the as-formed ZnO will act as a delayed species for hydrolysis and destruction of the NA-MOF-5 structure.


MOF-5 H2ZnO Adsorption Activation DFT 



The authors acknowledge Iran Nanotechnology Initiative Council for financial support.

Supplementary material

10904_2018_977_MOESM1_ESM.docx (426 kb)
Supplementary material 1 (DOCX 426 KB)


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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Chemical Engineering Department, Faculty of EngineeringFerdowsi University of MashhadMashhadIran
  2. 2.Research Center of Membrane Processes and Membrane, Faculty of EngineeringFerdowsi University of MashhadMashhadIran
  3. 3.Membrane Research Group, Nanotechnology Research InstituteBabol Noshirvani University of TechnologyBabolIran

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