In situ growth of octa-phenyl polyhedral oligomeric silsesquioxane nanocages over fluorinated graphene nanosheets: super-wetting coatings for oil and organic sorption†

Abstract

Superhydrophobic surfaces offer significant advantages through their hierarchical micro/nanostructures, which create optimal surface roughness and low surface energy, making the development of robust surfaces essential for enhancing their physical and chemical stability. Here, we introduce in situ growth of octa-phenyl polyhedral oligomeric silsesquioxane (O-Ph-POSS) nanocages over multi-layered fluorinated graphene (FG) nanosheets through hydrolysis/condensation of phenyl triethoxysilane in an alkaline medium to produce a robust POSS–FG superhydrophobic hybrid. The efficient in situ growth of O-Ph-POSS nanocages over FG nanosheets was confirmed by FT-IR spectroscopy, PXRD, SEM, TEM, TG analysis, ²⁹Si NMR spectroscopy, N₂ adsorption–desorption isotherms and XP spectroscopy. The as-synthesized O-Ph-POSS over FG becomes superhydrophobic with a water contact angle (WCA) of 152 ± 2° and a surface free energy (SFE) of 5.6 mJ m⁻². As a result of the superhydrophobic property and robust nature of the POSS nanocage, O-Ph-POSS over FG nanosheets revealed the absorption capability for oils/organic solvents ranging from 200 to 500 wt% and were applied to coat onto the polyurethane (PU) sponge to effectively separate various oils and organic solvents from water mixtures, achieving separation efficiencies between 90% and 99%. Importantly, O-Ph-POSS-FG@Sponge still retained a separation efficiency of over 95% even after 25 separation cycles for hexane spill in water. The sponge efficiently separates toluene and chloroform using a vacuum pump, achieving flux rates of up to 20 880 and 12 184 L m⁻² h⁻¹, respectively. Weather resistance tests of O-Ph-POSS-FG@Sponge, prepared at intervals of 1 week and 1 year, showed that aged samples retained similar WCA values to freshly prepared sponges, confirming their long-term durability and performance. Mechanical stability assessments indicated that O-Ph-POSS-FG@Sponge maintained superhydrophobic properties, with WCA values of 151 ± 2° for tape peeling and emery paper treatments and 150 ± 2° for knife cutting, highlighting its excellent stability under physical deformation. Additionally, leveraging the exceptional resistance of O-Ph-POSS, the superhydrophobic O-Ph-POSS-FG@Sponge exhibited excellent stability and durability, even under supercooled and hot conditions during oil/water separation. Optical microscopy analysis of O/W and W/O emulsions, both stabilized by a surfactant, revealed complete droplet separation, further confirming the O-Ph-POSS-FG@Sponge's effectiveness for emulsion separation applications. The present work provides a straightforward method for the large-scale production of robust, superhydrophobic materials suitable for cleaning up oil spills on water surfaces.