Photoinduced Oxidation Reactions at the Air–Water Interface

Chemistry on water is a fascinating area of research. The surface of water and the interfaces between water and air or hydrophobic media represent asymmetric environments with unique properties that lead to unexpected solvation effects on chemical and photochemical processes. Indeed, the features of interfacial reactions differ, often drastically, from those of bulk-phase reactions. In this Perspective, we focus on photoinduced oxidation reactions, which have attracted enormous interest in recent years because of their implications in many areas of chemistry, including atmospheric and environmental chemistry, biology, electrochemistry, and solar energy conversion. We have chosen a few representative examples of photoinduced oxidation reactions to focus on in this Perspective. Although most of these examples are taken from the field of atmospheric chemistry, they were selected because of their broad relevance to other areas. First, we outline a series of processes whose photochemistry generates hydroxyl radicals. These OH precursors include reactive oxygen species, reactive nitrogen species, and sulfur dioxide. Second, we discuss processes involving the photooxidation of organic species, either directly or via photosensitization. The photochemistry of pyruvic acid and fatty acid, two examples that demonstrate the complexity and versatility of this kind of chemistry, is described. Finally, we discuss the physicochemical factors that can be invoked to explain the kinetics and thermodynamics of photoinduced oxidation reactions at aqueous interfaces and analyze a number of challenges that need to be addressed in future studies.