Preparation of TiO2-based hollow microspheres by spray drying and their use as novel active pigments for photocatalytic coatings

The use of TiO2 nanoparticles in organic-based photocatalytic coatings imposes several challenges: poor activity under visible light, binder photo-degradation, need for UV activation and toxicity concerns. Here we present a scalable two-step synthesis route to prepare TiO2-based hollow microspheres (HoS) as alternative photocatalyst to commercial TiO2 nanoparticles. The hollow microspheres of TiO2 or WO3-doped TiO2 (3 mol% WO3) are synthesized via template-assisted spray-drying followed by calcination. The structure and composition of the powders are characterized and their photocatalytic performance is assessed using methylene blue photodegradation under UV irradiation as model reaction. XRD analysis reveals the presence of anatase and TiO2(B) phases, indicating the heterostructured nature of the samples. The results of the dye photo-degradation tests confirm the photocatalytic functionality of the TiO2-based HoS. Moreover, the introduction of WO3 (TiO2/WO3 HoS) leads to an enhancement of the performance, approaching that of commercial (Aeroxide P25, similar to 21 nm) nanoparticles. The most active TiO2/WO3 HoS are incorporated into an acrylic formulation and the resulting coatings tested towards pollutant abatement under UV light. A coating containing P25 nanoparticles undergoes an activation process where binder degradation leads to increased TiO2 exposure and a rise in catalytic activity but possibly at the expense of coating stability. By contrast TiO2/WO3 HoS-acrylic coatings exhibit catalytic activity similar to the initial activity of P25 containing coatings, but does not cause the same partial binder photo-degradation.