Designing Robust Superhydrophobic Materials for Inhibiting Nucleation of Clathrate Hydrates by Imitating Glass Sponges.

Superhydrophobic surfaces are suggested to deal with hydrate blockage because they can greatly reduce adhesion with the formed hydrates. However, they may promote the formation of fresh hydrate nuclei by inducing an orderly arrangement of water molecules, further aggravating hydrate blockage and meanwhile suffering from their fragile surfaces. Here, inspired by glass sponges, we report a robust anti-hydrate-nucleation superhydrophobic three-dimensional (3D) porous skeleton, perfectly resolving the conflict between inhibiting hydrate nucleation and superhydrophobicity. The high specific area of the 3D porous skeleton ensures an increase in terminal hydroxyl (inhibitory groups) content without damaging the superhydrophobicity, achieving the inhibition to fresh hydrates and antiadhesion to formed hydrates. Molecular dynamics simulation results indicate that terminal hydroxyls on a superhydrophobic surface can inhibit the formation of hydrate cages by disordering the arrangement of water molecules. And experimental data prove that the induction time of hydrate formation was prolonged by 84.4% and the hydrate adhesive force was reduced by 98.7%. Furthermore, this porous skeleton still maintains excellent inhibition and antiadhesion properties even after erosion for 4 h at 1500 rpm. Therefore, this research paves the way toward developing novel materials applied in the oil and gas industry, carbon capture and storage, etc.