Nitrate radical formation and reaction with limonene by TiO2 photocatalysis: A kinetic study

The oxidative cleavage and the epoxidation of the endocyclic double bond of limonene can be performed in irradiated suspensions of TiO2 because of the formation of nitrate radical species deriving from the hole-induced oxidation of nitrate ions. The reaction is boosted by electron acceptors such as silver ions or in the presence of silver nanoparticles at the surface of TiO2. A thorough kinetic analysis of the reaction performances under several experimental conditions provided a set of kinetic constants, which characterise the elementary steps of this complex reaction. In particular, for the first time an evaluation of the kinetics of the formation of nitrate radicals in heterogeneous photocatalysis has been provided. Moreover, the effect of silver ions in solution and of silver nanoparticles at the surface of TiO2 could be quantitatively estimated. The developed set of kinetic equations satisfactorily predict the experimental data under several experimental conditions and can be used as the starting point of reactor design activities, in view of a future scale-up of the process. Moreover, the successful fitting of the model corroborates the proposed reaction mechanism, and provides fundamental insights on the elementary reaction steps.