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.
- Expanded liquid phases
- Hierarchical porosity
- Metal-organic frameworks
- Supercritical CO
ASJC Scopus subject areas
- Environmental Chemistry
- Chemical Engineering(all)
- Renewable Energy, Sustainability and the Environment
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Person: Research & Teaching, Researcher