Hydraulic retention time governed the micro/nanostructures of titanium-incorporated diatoms and their photocatalytic activity

Titanium (Ti)-incorporated diatoms are promising biomaterials to photodegrade micropollutants such as pharmaceuticals and personal care products (PPCPs). Hydraulic retention time (HRT) is a key parameter for diatom cultivation and the incorporation of titanium into diatom frustules. This study assessed how HRT governs the micro/nanostructures, titania content and distribution, and the photocatalytic activity of titanium-incorporated diatom frustules. We cultivated a diatom strain Stephanodiscus hantzschii using a feed solution containing titanium(IV) in membrane bioreactors (MBRs) at a solids retention time (SRT) of 10 d and staged HRTs from 24 to 12 and to 6 h. The decrease in HRT reduced the porosity of diatom frustules but increased their silicon and titania contents. When the HRT decreased from 24 to 12 and to 6 h, the specific surface areas of the diatom decreased from 37.65 ± 3.19 to 31.53 ± 3.71 and to 18.43 ± 2.69 m2 g−1 frustules, while the titanium contents increased from 53 ± 14 to 71 ± 9 and to 85 ± 13 mg Ti g−1 frustules. The increase in the influent flow rates of the MBRs with decreasing HRTs likely enhanced nutrient diffusion inside the diatom valve pores, facilitating the uptake and incorporation of silicon and titanium. The titanium-incorporated frustules were effective in removing two representative PPCPs, bisphenol A (BPA) and N,N-Diethyl-meta-toluamide (DEET), from water. As photocatalytic activity depends on the amount of titanium, decreasing the HRT substantially increased the photocatalytic activity of the titanium-incorporated frustules. In batch tests under ultraviolet light, frustules from the diatom cultivated at HRTs of 24, 12, and 6 h had the pseudo-first-order removal (mainly through photodegradation) rate constants of BPA of 0.376, 0.456, and 0.683 h−1, respectively. Under the same experimental condition, the pseudo-first-order removal rate constants of DEET by the frustules cultivated at HRTs of 24, 12, and 6 h increased from 0.270 to 0.330 and to 0.480 h−1, respectively.