Fabrication of Biomimetical TiO2@PVDF Composite Membrane with Omniphobicity via In-Situ Growth and Its Anti-Fouling Performance

Abstract

Commercial hydrophobic membranes encounter severe problems such as membrane wetting and membrane fouling under extreme conditions, which affect membrane separation performance. To enhance the anti-fouling abilities of hydrophobic membranes, a composite membrane with omniphobic characteristics was fabricated successfully in this paper. Titanium dioxide (TiO2) nanoparticles were in-situ grown via the hydrothermal synthesis method, and then fluorosilane with low surface energy was grafted on polyvinylidene fluoride (PVDF) membranes. Subsequently, the morphologies, chemical compositions, wetting properties and structural parameters of composite membranes were characterized systematically. Various contaminants were added to the feed to investigate the anti-fouling and anti-wetting performances of the composite membrane in membrane distillation tests. The results showed that butyl titanate was first hydrolyzed to form titanium hydroxide (Ti(OH)4) and then it was dehydrated to form TiO2 in the hydrothermal environment. TiO2 crystals continued to grow and formed rough morphology with micro-nano synergistic distribution, which is similar to a “sunflower” disk composed of cubic clusters and nanopillars. Meanwhile, fluorosilane successfully was grafted onto TiO2. The contact angles of deionized water, 0.4 mM sodium dodecyl sulfate (SDS) solution and 0.2% v/v mineral oil emulsion on the composite membrane surface were 167.3°, 162.0° and 158.5°, respectively, endowing the composite membrane with excellent omniphobic features. In direct contact membrane distillation (DCMD) tests, the composite membrane exhibited a relatively stable membrane permeate flux, and the salt rejection rate almost reached 100%. The mixture, consisting of inorganic salts, organic substances, surfactants and oil emulsions, was used as feed. In contrast, the commercial PVDF membrane flux decreased drastically and even dropped to 0 due to the membrane fouling and wetting. As for the pristine PVDF membrane, the membrane surface was covered with pollutants and membrane pores were blocked. Therefore, it was proved that the omniphobic composite membrane possesses outstanding anti-fouling and anti-wetting performance.