Fluorinated Monodisperse Microporous Microspheres: Formation Mechanism, Assembly, and Molecular Separation

The construction of monodisperse microporous organic microspheres is deemed a challenging issue, primarily due to the difficulty in achieving both high microporosity and uniformity within the microspheres. In this study, a series of fluorinated monodisperse microporous microspheres are fabricated by solvothermal precipitation polymerization. The resulting fluorous methacrylate-based microspheres achieved higher than 400 m²/g surface area, along with a yield of over 90% for the microspheres. Through comprehensive characterization and simulation methods, we discovered that the introduction of fluorous methacrylate monomers at high loading levels is the key factor contributing to the formation of the microporosity within the microspheres. The controlled temperature profile was found to be advantageous for achieving a high yield of microspheres and increased uniformity. Two-dimensional assemblies of these fluorinated microsphere arrays exhibited superhydrophobicity, superolephilicity, and water sliding angles below 10°. Furthermore, a three-dimensional assembly of the fluorinated microporous microsphere in a chromatographic column demonstrated significant improvement in the separation of Engelhardt agent compared to commercial columns. Our work offers a novel approach to constructing fluorinated monodisperse microporous microspheres for advanced applications.