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

Research output: Contribution to journalArticle

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Abstract

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
Volume5
Issue number9
Early online date27 Jul 2017
DOIs
Publication statusPublished - 5 Sep 2017

Fingerprint

Carbon Monoxide
Metals
metal
Crystallization
crystallization
Electron gas
etching
Crystallite size
Pore structure
High resolution transmission electron microscopy
Dimethyl Sulfoxide
Crystallites
Organic solvents
nucleation
Sorption
transmission electron microscopy
Etching
Materials properties
Nucleation
sorption

Keywords

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

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry
  • Chemical Engineering(all)
  • Renewable Energy, Sustainability and the Environment

Cite this

Controlled Formation of Hierarchical Metal-Organic Frameworks Using CO2-Expanded Solvent Systems. / Doan, Huan V.; Fang, Yanan; Yao, Bingqing; Dong, Zhili; White, Timothy J.; Sartbaeva, Asel; Hintermair, Ulrich; Ting, Valeska P.

In: ACS Sustainable Chemistry and Engineering, Vol. 5, No. 9, 05.09.2017, p. 7887-7893.

Research output: Contribution to journalArticle

Doan, Huan V. ; Fang, Yanan ; Yao, Bingqing ; Dong, Zhili ; White, Timothy J. ; Sartbaeva, Asel ; Hintermair, Ulrich ; Ting, Valeska P. / Controlled Formation of Hierarchical Metal-Organic Frameworks Using CO2-Expanded Solvent Systems. In: ACS Sustainable Chemistry and Engineering. 2017 ; Vol. 5, No. 9. pp. 7887-7893.
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