Ionic liquid accelerates the crystallization of Zr-based metal–organic frameworks

The Zr-based metal–organic frameworks are generally prepared by solvothermal procedure. To overcome the slow kinetics of nucleation and crystallization of Zr-based metal–organic frameworks is of great interest and challenging. Here, we find that an ionic liquid as solvent can significantly accelerate the formation of Zr-based metal–organic frameworks at room temperature. For example, the reaction time is shortened to 0.5 h in 1-hexyl-3-methylimidazolium chloride for Zr-based metal–organic framework formation, while that in the conventional solvent N,N-dimethylformamide needs at least 120 h. The reaction mechanism was investigated in situ by 1H nuclear magnetic resonance, spectroscopy synchrotron small angle X-ray scattering and X-ray absorption fine structure. This rapid, low-energy, and facile route produces Zr-based metal–organic framework nanoparticles with small particle size, missing-linker defects and large surface area, which can be used as heterogeneous catalysts for Meerwein–Ponndorf–Verley reaction. Crystallization kinetics of metal-organic frameworks in conventional organic solvents are usually very slow. Here, the authors show that an ionic liquid medium accelerates considerably the formation of Zr-based metal-organic frameworks that are active catalysts in the Meerwein-Ponndorf-Verley reaction.

• Publication year

  2017

• Venue

  Nature Communications

• Publication date

  2017-08-02

• Fields of study

  Medicine, Materials Science, Chemistry

• Identifiers
  DOI 10.1038/s41467-017-00226-yPMID 28765542PMCID 5539316
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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  2017influential reference
• Linker Installation: Engineering Pore Environment with Precisely Placed Functionalities in Zirconium MOFs.

  2016cited by this paper
• Small Angle X-ray Scattering for Nanoparticle Research.

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  2016cited by this paper
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  2016cited by this paper
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  2016cited by this paper
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