Easily Recoverable, Micrometer-Sized TiO2 Hierarchical Spheres Decorated with Cyclodextrin for Enhanced Photocatalytic Degradation of Organic Micropollutants

Micrometer-sized titanium dioxide hierarchical spheres (TiO2-HS) were assembled from nanosheets to address two common limitations of photocatalytic water treatment: (1) inefficiency associated with scavenging of oxidation capacity by nontarget water constituents and (2) energy-intensive separation and recovery of the photocatalyst slurry. These micrometer-sized spheres are amenable to low-energy separation, and over 99% were recaptured from both batch and continuous flow reactors using microfiltration. Using nanosheets as building blocks resulted in a large specific surface area-3 times larger than that of commercially available TiO2 powder (Evonik P25). Anchoring food-grade cyclodextrin onto TiO2-HS (i.e., CD-TiO2-HS) provided hydrophobic cavities to entrap organic contaminants for more effective utilization of photocatalytically generated reactive oxygen species. CD-TiO2-HS removed over 99% of various contaminants with dissimilar hydrophobicity (i.e., bisphenol A, bisphenol S, 2-naphthol, and 2,4-dichlorophenol) within 2 h under a low-intensity UVA input (3.64 × 10-6 einstein/L/s). As with other catalyst (including TiO2 slurry), periodic replacement or replenishment would be needed to maintain high treatment efficiency (e.g., we demonstrate full reactivation through simple reanchoring of CD). Nevertheless, this task would be offset by significant savings in photocatalyst separation. Thus, CD-TiO2-HS is an attractive candidate for photocatalytic water and wastewater treatment of recalcitrant organic pollutants.