Preparation of Robust Superhydrophobic Halloysite Clay Nanotubes via Mussel-Inspired Surface Modification

In this study, a novel and convenient bio-inspired modification strategy was used to create stable superhydrophobic structures on halloysite clay nanotubes (HNTs) surfaces. The polydopamine (PDA) nanoparticles can firmly adhere on HNTs surfaces in a mail environment of pH 8.5 via the oxidative self-polymerization of dopamine and synthesize a rough nano-layer assisted with vitamin M, which provides a catechol functional platform for the secondary reaction to graft hydrophobic long-chain alkylamine for preparation of hierarchical micro/nano structures with superhydrophobic properties. The micromorphology, crystal structure, and surface chemical composition of the resultant superhydrophobic HNTs were characterized by field emission scanning electron (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The as-formed surfaces exhibited outstanding superhydrophobicity with a water contact angle (CA) of 156.3 +/- 2.3 degrees, while having little effect on the crystal structures of HNTs. Meanwhile, the resultant HNTs also showed robust stability that can conquer various harsh conditions including strong acidic/alkaline solutions, organic solvents, water boiling, ultrasonic cleaning, and outdoor solar radiation. In addition, the novel HNTs exhibited excellent packaged capabilities of phase change materials (PCMs) for practical application in thermal energy storage, which improved the mass fractions by 22.94% for stearic acid and showed good recyclability. These HNTs also exhibited good oil/water separation ability. Consequently, due to the superior merits of high efficiency, easy operation, and non-toxicity, this bionic surface modification approach may make HNTs have great potentials for extensive applications.