Photodegradation of steroid hormone micropollutants with palladium-porphyrin coated porous PTFE of varied morphological and optical properties

In flow-through reactors, the photodegradation rate can be improved by enhancing contact and increasing the photocatalyst loading. Both can be attained with a higher surface-to-volume ratio. While previous studies focused on thin membranes (30 - 130 µm) with small pore sizes of 20 - 650 nm, this work employed poly(tetrafluoroethylene) (PTFE) supports, of which pore sizes are in the order of 10 µm, while the porosities and thicknesses are variable (22.5 - 45.3 % and 0.2 - 3 mm, respectively). These porous materials were anticipated to allow a higher loading of porphyrin photosensitisers and better light penetration for subsequent photodegradation of steroid hormone micropollutants via singlet oxygen (¹O₂) generation. The reactor surface refers to the surface within the PTFE pores, while the reactor volume is the total void space inside these pores. The surface-to-volume ratios between 10⁵ and 10⁶ m²/m³ are higher than those of typical microreactors (10³ to 10⁴ m²/m³). The weighted average light transmittance varied from 38 % with the thinnest and most porous support to 4.8 % with the thickest support. Good light penetration combined with minimal absorption by PTFE enhanced the light utilisation of the porphyrins when coated in the porous supports. Changes in the support porosity of the coated supports minimally affected steroid hormone removal, because the collision frequency in the very large pores remained relatively constant. However, varying the support thickness, porphyrin loading (0.3 - 7.7 μmol/g), and water flux (150 - 3000 L/m².h), hence the resulting hydraulic residence time, influenced the collision frequency and steroid hormone removal. Results showed that the supports did not outperform membranes most likely because the larger pore size in the former limited contact between the hormones and ¹O₂. From photostability testing of the pristine supports, perfluoroalkyl substances (PFAS) released from the supports were found at 10 - 300 ng/L concentrations during accelerated ageing. While PFAS formation was detectable, the quantities during water treatment operations would be extremely low. In summary, this study elucidates the capability and limitations of porous supports coated with photosensitisers to remove waterborne micropollutants.