Sub-nanoscale Surface Engineering of TiO₂Nanoparticles by Molecular Layer Deposition of Poly(ethylene terephthalate) for Suppressing Photoactivity and Enhancing Dispersibility

In this work, we report molecular layer deposition (MLD) of ultrathin poly(ethylene terephthalate) (PET) films on gram-scale batches of ultrafine particles for the first time. TiO2 P25 nanoparticles (NPs) are coated up to 50 cycles in an atmospheric-pressure fluidized-bed reactor at 150 °C using terephthaloyl chloride and ethylene glycol as precursors. Ex-situ diffuse reflectance infrared Fourier transform spectroscopy, thermogravimetric analysis, and transmission electron microscopy show the linear growth at 0.05 nm/cycle of uniform and conformal PET films, which are unattainable with conventional wet-phase approaches. The sub-nanoscale and nanoscale PET films not only suppress the photocatalytic activity of TiO2 NPs by hindering the access of water and reactant molecules to the TiO2 surface but also improve the dispersibility of TiO2 NPs in both organic and aqueous media. Still, the bulk optical properties, electronic structure, and surface area of TiO2 are essentially unaffected by the MLD process. This study demonstrates the industrial relevance of MLD to simultaneously suppress the photoactivity and enhance the dispersibility of commercial TiO2 P25 nanopowders, which is crucial for their use for example as UV-screening agents in sunscreens and as white pigments in paints. Moreover, by rapidly modifying the surface properties of particles in a controlled manner at the sub-nanometer scale, particle MLD can serve many other applications ranging from nanofluids to emulsions to polymer nanocomposites.