Reactivity of Ti(IV) species hosted in TS-1 towards H₂O₂–H₂O solutions investigated by ab initio cluster and periodic approaches combined with experimental XANES and EXAFS data: a review and new highlights

This work is intended to underline how the most-advanced experimental and theoretical physical chemistry tools must be used synergistically to understand the reactivity of Ti–silicalite-1 (TS-1) in an important number of low-temperature oxidation reactions with aqueous H₂O₂ as the oxidant. Literature results are carefully reviewed and accompanied with new, unpublished highlights of both experimental and computational origin. The first part of this work is devoted to a discussion of the defective nature of the material and to the synergic role played by Si vacancies and Ti insertion in the framework. A summary of the experimental Ti–K-edge EXAFS and XANES literature concerning the activated material in vacuo conditions is then presented and compared to the corresponding Ti geometries obtained by ab initio calculations. From such a comparison, the excellent agreement between experiment and theory is evident. A very good agreement is also obtained for the interaction with water and ammonia. For both H₂O and NH₃, the agreement is due to the possibility to perform experiments in which the probe molecule is dosed from the gas phase, thus allowing to reach the 1 : 1 (or 1 : 2) ratio between the adsorbing Ti sites and the adsorbed molecule. Then, interaction with hydrogen peroxide is discussed, underlining the problems faced in reaching a common view between experimental and theoretical results, owing to the difficulties both in performing experiments where anhydrous H₂O₂ is dosed on TS-1, and in taking into account the role played by the aqueous medium in the reactivity of Ti(IV) centres toward H₂O₂ using ab initio calculations. Only once such difficulties have been overcome, by increasing the complexities of both experiments and ab initio models, is a joint-view finally obtained. Where needed, comparison with other experimental results (X-ray and neutron diffraction, NMR, IR, Raman, UV-vis and resonant Raman) is made.