Robert Bericat Vadell: Plasmon mediated photo-redox catalysis: From fundamentals to reactions

Abstract

The synthesis of most chemicals relevant to industrial processes requires at least one catalytic step. The goods and products derived from these processes have played a fundamental role in shaping our social structure and continue to be essential for sustaining it. However, a major challenge in many of the catalytic methods currently used in the chemical industry is their reliance on high temperatures and pressures, making them energy-intensive. Recently, new catalytic strategies capable of operating under milder and more efficient conditions have been developed. 

One such strategy is photocatalysis, which has emerged as a promising alternative to conventional catalytic methods. In photocatalysis, the catalytic reactions are driven by light, reducing the need for energy demanding conditions. Among the various photocatalysts under investigation, those based on plasmonic particles have garnered considerable attention. These materials benefit from strong light absorption and high spectral tunability, making them particularly interesting for catalytic applications.

After a brief review of the basic principles of plasmonic phenomena and their role in plasmonic photocatalytic systems, the results of this thesis are presented in three chapters. Each chapter addresses specific aspects of plasmonic photocatalysis, some of which are still under investigation. The first chapter examines the effect of temperature on hole transfer from a plasmonic particle to the p-type semiconductor copper iodide, and delves into the unusual response of this semiconductor to photoexcitation. The second chapter explores an approach to integrate the advantages of plasmonic-based and molecular-based photocatalytic systems through the functionalization of plasmonic particles with thiolate ligands. Finally, the third chapter reviews a plasmonic photocatalytic system with the potential to mitigate the photothermal effects inherent in plasmonic excitation.