Progress in Aerosol-Based Synthesis of Metal-organic Framework (MOF) Particles in Supercritical CO2
IGOR NOVOSSELOV,
University of Washington Abstract Number: 554
Working Group: Nanoparticles and Materials Synthesis
AbstractThe high surface areas and tunable porous structures of Metal-Organic Framework (MOF) materials offer desirable capabilities in a wide range of applications. One challenge to the widespread use of MOFs is a lack of large-scale manufacturing synthesis processes. The aerosol-based method allows for rapid single-step synthesis and activation of MOFs. We present an overview of a novel method of continuous synthesis of MOF in supercritical carbon dioxide (scCO2) environment. The rapid mixing of precursors into scCO2 provides a single-phase environment that enhances heat and mass transfer during the synthesis. The method synthesized the zirconium-based MOF UiO-66 at a production rate of 104 g/h [1]. Synthesis of UiO-66 was confirmed via SEM images, powder X-ray diffraction (PXRD) spectra, and physisorption analysis. Additionally, testing showed that this method could be used to activate as well as continuously synthesize MOF materials. Additionally, the method was applied to synthesize other MOFs: HKUST-1 [2] and SBMOF-1, demonstrating the practicality of continuous flow scCO2 MOF synthesis. BET area and particle size can be optimized by manipulating reactor operating temperatures and CO2 fraction in the reactor. The best quality MOFs were obtained when conditions for a single-phase supercritical mixture were met. The method results in rapid reaction time (<3s), can be easily scaled, and it allows for the recovery of effluent and unreacted material, which is challenging in hydrothermal and supercritical water-based systems.
[1] E. G. Rasmussen, J. Kramlich, and I. V. Novosselov, "Scalable Continuous Flow Metal–Organic Framework (MOF) Synthesis Using Supercritical CO2," ACS Sustainable Chemistry & Engineering, vol. 8, no. 26, pp. 9680-9689, 2020/07/06 2020, doi: 10.1021/acssuschemeng.0c01429.
[2] E. G. Rasmussen, J. Kramlich, and I. V. Novosselov, "Synthesis of metal-organic framework HKUST-1 via tunable continuous flow supercritical carbon dioxide reactor," Chem. Eng. J., vol. 450, p. 138053, 2022/12/15/ 2022, doi: https://doi.org/10.1016/j.cej.2022.138053.