Solar photo-degradation of aniline with rGO/TiO₂ composites and persulfate

The solar photodegradation of aniline using reduced graphene oxide-based composites (rGO/TiO₂) and different electron acceptors such as H₂O₂ and persulfate (PS) has been studied. To this end, an innovative self-sufficient drum reactor (operating with solar irradiation and artificial UV light) has been employed. The role of radicals and the new graphene morphology is evaluated. Finally, changes in the degradation/mineralization mechanism are explained according to intermediates evolution (obtained from mass spectroscopy). In the Solar/rGO/TiO₂/H₂O₂ system, hydroxyl radicals react with the reduced graphene oxide (rGO) producing oxidized rGO (OrGO). The process creates new pores increasing surface area favouring adsorption. Also, other radicals such as superoxide or singlet oxygen are also formed, affecting the degradation mechanism. The hole reacts with adsorbed aniline to form the aniline-radical-cation. Nitrosobenzene is then formed with the active participation of superoxide radical anion, finally yielding azobenzene. It was found that the addition of 2.5% wt of rGO increases mineralization from 0 to 14% during the solar stage after 120 min, reaching 82.5% when lamps are switched on after 240 min. On the other hand, activation of PS with UV-C light is a very efficient process, since aniline is wholly degraded in 10-20 min depending on PS initial concentration, reaching a high mineralization degree close to 90% in 120 min. During this process, degradation occurs in a very different route, via the formation of phenol. In the first stage (t < 25 min), sulfate radical is the primary oxidant involved to yield benzoquinone. In a second step (t > 25 min), hydroxyl radicals play the leading role to reach C₂-C₆ organic acids.