Investigation of the Kinetics of a Surface Photocatalytic Reaction in Two Dimensions with Surface‐enhanced Raman Scattering

Heterogeneous catalysis is a surface phenomenon. Yet, though the catalysis itself takes place on surfaces, the reactants and products rapidly take the form of another physical state, as either a liquid or a gas. Catalytic reactions within a self‐assembled monolayer are confined within two dimensions, as the molecules involved do not leave the surface. Surface‐enhanced Raman spectroscopy is an ideal technique to probe these self‐assembled monolayers as it gives molecular information in a measured volume limited to the surface. We show how surface‐enhanced Raman spectroscopy can be used to determine the reaction kinetics of a two‐dimensional reaction. As a proof of principle, we study the photocatalytic reduction of p‐nitrothiophenol. A study of the reaction rate and dilution effects leads to the conclusion that a dimerization must take place as one of the reaction steps.