The Role of the TiO2 Surface in Heterogeneous Photocatalytic Reactions: Mechanistic and Kinetic Implications

Abstract

TiO2 photocatalysis has been extensively studied over the last three decades. The output of this research effort is an increasing fundamental understanding of the phenomena involved in the process and the successful application of photocatalytic technological devices in different areas such as environmental purification, renewable energy production, and design of materials with “self cleaning” properties. However, the scientific community in the field of photocatalysis recognizes that several fundamentals issues still remain unclear. In the 80 and 90’s decades several reaction mechanisms and kinetic models were proposed for the interpretation of the large body of experimental data concerning TiO2-assisted photooxidation reactions. Despite the huge advance in the fundamental knowledge of these topics that was achieved, several assumptions taken as truths by the scientific community were challenged by the findings of surface science studies on TiO2 crystals reported in the first decade of this century. These findings brought new insights into the surface chemistry of TiO2. It was demonstrated that the TiO2 catalyst can not be considered just as particles devoid of surface structure. Conversely, the chemical structure of the catalyst surface and its interaction with molecules in the reaction media is a determinant factor to understand the events triggered by TiO2 excitation. This PhD thesis is aimed at elucidating some alternative interpretations of kinetics and mechanisms of photocatalytic oxidation reactions taking into account the aforementioned novel insights. This task has been addressed by a comprehensive analysis of the scientific literature on the topic of surface chemistry of TiO2 and by an experimental study comprising TiO2-surface/substrate interactions, their relationship with kinetics of photooxidation reactions, and mechanistic issues related to photocatalytic oxidation of several model compounds. The above issues are discussed in detail in four published articles and three manuscripts that will be submitted for publication in the near future. The results reported here confirm the crucial role of the TiO2 surface in the mechanisms and the kinetics of interfacial charge transfer in photocatalytic reactions. Specifically, the role of TiO2 surface lattice oxygens in the reaction mechanism was elucidated. Moreover, it was found that the mechanism of interfacial charge transfer strongly depends on the degree of electronic interaction between the semiconductor surface and the organic substrate to be photooxidized. The above findings provide new ideas to the current scientific debate around fundamental issues of TiO2 photocatalysis. On the other hand, the new insights into the kinetics and mechanisms of photocatalytic reactions reported here can provide more rational strategies for the development of more efficient photocatalysts for practical applications.

Date of Award	16 Sept 2013
Original language	English
Supervisor	Jose Peral Perez (Director)