Kinetic Analysis and <i>Operando</i> Spectroscopy for Revealing Microscopic Reaction Mechanisms on Photocatalyst Surfaces

Photocatalysis enables redox reactions to proceed non-thermally under ambient conditions, offering a low-energy alternative to conventional thermocatalytic processes. Traditionally, it has been assumed that oxidation occurs exclusively at the semiconductor surface via photogenerated holes, while reduction takes place on metal cocatalysts that capture photogenerated electrons. However, the absence of microscopic insights into the detailed reaction mechanism has hindered rational design of catalysts. To address this, we employed kinetic analysis and operando infrared spectroscopy to directly monitor reactive species under reaction conditions. Our investigations reveal that metal cocatalysts also play a crucial role in oxidation by interacting with photogenerated holes, contrary to traditional understanding. Moreover, the reactive electrons are not located within the metal cocatalysts but are shallowly trapped in in-gap states of the semiconductor surface at their periphery. These findings redefine the concept of catalytic active sites and provide a basis for designing more efficient photocatalytic systems.