Interaction of Phenolic Compounds with Functionalized TiO2: Enhanced Catechol Adsorption and Cooperative Phenol Adsorption

A commercial TiO2 sample functionalized with 3-aminopropyltrimethoxysilane (APTMS) and 4-carboxyphenylboronic acid (CPBA), has been previously proposed as a suitable photocatalyst to perform selective photocatalytic degradation of pollutants in aqueous streams, while avoiding the oxidation of valuable catechol simultaneously present in the reacting medium. In the present study, we highlight the adsorption mechanisms underlying the higher affinity of catechol, compared to phenol, with the surface of modified TiO2, quantitatively justifying the photocatalytic selective degradation results previously obtained. Moreover, a cooperative adsorption mechanism of phenol onto the TiO2 sample modified with APTMS has been for the first time observed. The resulting sigmoidal adsorption isotherms, satisfactorily fitted with the Hill model, could be attributed to the enhanced surface hydrophobicity and, more importantly, to alterations of the folding of APTMS molecules on the TiO2 surface occurring upon increasing the concentration of the phenolic compounds. Photocatalytic tests revealed that the existence of boronate groups on the surface of TiO2 hinders the photocatalytic degradation of catechol and facilitates a swifter oxidation of phenol. These findings confirm the potential for selective photocatalytic degradation, in line with modern conceptions of innovative and environmentally sustainable wastewater treatments.