Facile synthesis of morphology and size-controlled zirconium metal-organic framework UiO-66: the role of hydrofluoric acid in crystallization

Yitong Han, Min Liu, Keyan Li, Yi Zuo, Yingxu Wei, Shutao Xu, Guoliang Zhang, Chunshan Song, Zongchao Zhang, Xinwen Guo

Research output: Contribution to journalArticle

68 Scopus citations

Abstract

UiO-66 with crystal size ranging from hundreds of nanometers to a few micrometers and with cubic and cuboctahedral morphologies were synthesized. Crystal size and morphology varied with the additive amount of hydrofluoric acid and the concentration of reactants (ZrCl4 and H2BDC) during solvothermal synthesis. According to energy dispersive spectrometry (EDS) and 19F MAS NMR measurements, the fluorine ions directly bonded to Zr in the SBUs (secondary building units) in the MOF framework due to their strongest electronegativity. The bonding of the fluorine ions and Zr not only compensated for the charge imbalance of the framework caused by missing linkers but also competed with the linkers to coordinate with the Zr metal centers, thereby controlling the processes of nucleation and growth of the UiO-66 crystals. The samples were further characterized by scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and Ar sorption isotherms, showing that the introduction of fluorine enhanced the thermostability and porosity of UiO-66.

Original languageEnglish (US)
Pages (from-to)6434-6440
Number of pages7
JournalCrystEngComm
Volume17
Issue number33
DOIs
StatePublished - Jul 16 2015

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

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