Photoelectrocatalytic degradation of organophosphate esters using tio₂ electrodes produced from 3d-printed ti...

3D printed electrode substrates with novel geometries may significantly improve the efficacy of photoelectrocatalysis for degradation of recalcitrant pollutants such as organophosphate flame retardants (OPFRs). However, the 3D printed substrates often have an irregular topology that can lead to a less uniform arrangement of nanotubes following anodisation. This study investigated the effect of polishing 3D-printed Ti substrates prior to anodisation to form TiO₂ nanotube array electrodes, and their subsequent applicability for photoelectrocatalytic treatment of OPFRs in water matrices. Polished and non-polished electrodes exhibited differences in morphology in terms of average roughness, (0.38 and 3.10 µm, respectively), leading to more uniform TiO₂ nanotubes of the former. Water contact angle measurements revealed the non-polished electrode was super-hydrophilic and the polished electrode hydrophilic (water contact angles of 6.4˚ and 16.1˚, respectively). Despite these differences, the polished and non-polished electrodes exhibited very similar electrochemical responses. In fact, the purity and electrical conductivity of water matrices affected the photoelectrocatalytic performance more than the electrode morphology. The purified water (PW) matrix facilitated the highest degradation/removal of OPFRs, compared to tap water matrices. In particular, individual OPFR degradation levels in PW were 74% ± 9, 37% ± 10, 33% ± 9, 31% ± 11 and 3% ± 5 for triphenyl phosphate, tris(butyl) phosphate, tris(isobutyl) phosphate, tris(2-butoxyethyl) phosphate and tris(2-chloroisopropyl) phosphate, respectively. The removal of OPFRs was relative to their reactivity to hydroxyl radicals, which was higher for the aryl then alkyl straight-chain and then chlorinated compounds. This study reveals that polishing of electrode substrates is not required for the preparation of effective photoelectrocatalytic reactors to treat recalcitrant pollutants (e.g. OPFRs), Importantly, future development of novel high-profile 3D printed electrode will not be hindered by the requirement to polish the substrates prior to anodisation.