Photocatalysis of Volatile Organic Compounds in water: Towards a deeper understanding of the role of cyclodextrins in the photodegradation of toluene over titanium dioxide

Abstract

Hypothesis: Cyclodextrin-assisted photodegradation of toluene was investigated in water in the presence of a photo-irradiated commercial titanium dioxide photocatalyst. It was expected that cyclodextrins could form water-soluble supramolecular host/guest complexes with the toluene and thus promote the approach of the pollutant on the TiO2 surface and enhance the phototocatalytic oxidation efficiency.

Experiments: Photodegradation kinetics of toluene were investigated under UV-C and near-visible light radiation in aqueous suspensions of TiO2. Impact of cyclodextrin (CD) on the photocatalytic efficiency of TiO2 was evaluated with different cyclodextrins: α-CD, β-CD, γ-CD and RAME-β-CD. Host-guest association constants were determined by static headspace gas chromatography and affinity of cyclodextrins for the TiO2 surface by isothermal adsorption studies. Issue of the cyclodextrin stability during the degradation process was examined using Total Organic Carbon, NMR and MALDI-TOF analyses.

Findings: Toluene could be fully mineralized by TiO2 in water within hours, even if the presence of cyclodextrin caused a delay in the photodegradation process. The chemical nature of cyclodextrins was found to exert a significant influence on the extent of inhibitory effect, which was discussed in terms of balance between solubilization efficiency, substrate protection and coverage of active sites of TiO2 by competitive adsorption. The cyclodextrin degradation was also studied and discussed.

Keywords: Adsorption; Cyclodextrins; Inclusion complex; Photocatalysis; Toluene.