Experimental measurement and modelling of reactive species generation in TiO2 nanoparticle photocatalysis

The generation of reactive species in titanium dioxide (TiO2) nanoparticle photocatalysis was assessed in a laboratory scale setup, in which P25 Aeroxide TiO2 suspensions were photoactivated by means of UV-A radiation. Photogenerated holes and hydroxyl radicals were monitored over time by observing their selective reaction with probe compounds, iodide and terephthalic acid, respectively. TiO2 aggregate size and structure were characterized over the reaction time. Reactive species quenching was then described by a model, accounting for radiative phenomena, TiO2 nanoparticle aggregation and kinetic reactions. The interaction between iodide and photogenerated holes was influenced by iodide adsorption on TiO2 surface, described by a Langmuir–Hinshelwood mechanism, whose parameters were studied as a function of TiO2 concentration and irradiation time. Iodide oxidation was effectively simulated by modelling the reaction volume as a completely stirred two-dimensional domain, in which irradiation phenomena were described by a two-flux model and the steady state for reactive species was assumed. The kinetic parameters for iodide adsorption and oxidation were estimated and successfully validated in a different experimental setup. The same model was adapted to describe the oxidation of terephthalic acid by hydroxyl radicals. The kinetic parameters for terephthalic acid oxidation were estimated and validated, while the issues in investigating the interaction mechanisms among the involved species have been discussed. The sensitivity of operating parameters on model response was assessed and the most relevant parameters were highlighted