Controlled Formation of Hierarchical Metal-Organic Frameworks Using CO2-Expanded Solvent Systems

Huan V. Doan, Yanan Fang, Bingqing Yao, Zhili Dong, Timothy J. White, Asel Sartbaeva, Ulrich Hintermair, Valeska P. Ting

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It is shown that a crystalline metal-organic framework (HKUST-1) can be rapidly synthesized from a DMSO/MeOH solution with greatly reduced amounts of organic solvents using a supercritical CO2 (scCO2) solvent expansion technique. The precursor solution is stable for months under ambient conditions, and CO2-driven MOF (metal-organic framework) crystallization is achieved under mild conditions (40 °C, 40-100 bar) with excellent reproducibility. As the degree of liquid-phase expansion drives MOF nucleation and growth, the crystallite size and overall yield can be tuned by adjusting the CO2 pressure. Furthermore, scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and gas sorption analyses showed that, in the presence of scCO2, HKUST-1 crystallites with a hierarchical pore structure are generated through a postcrystallization etching process. These findings demonstrate that scCO2 is a time- and material-efficient route to MOF synthesis with a high level of control over the crystallization process for accessing tailored material properties.

Original languageEnglish
Pages (from-to)7887-7893
Number of pages7
JournalACS Sustainable Chemistry and Engineering
Issue number9
Early online date27 Jul 2017
Publication statusPublished - 5 Sept 2017


  • Expanded liquid phases
  • Hierarchical porosity
  • HKUST-1
  • Metal-organic frameworks
  • Supercritical CO

ASJC Scopus subject areas

  • General Chemistry
  • Environmental Chemistry
  • General Chemical Engineering
  • Renewable Energy, Sustainability and the Environment


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