Investigation of the kinetics of a surface photocatalytic reaction in two dimensions with surface-enhanced Raman scattering

Abstract

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. We plough the surface and scatter: Surface-enhanced Raman spectroscopy can be used to determine the reaction kinetics of surface reactions within self-assembled monolayers. As a proof of principle we have chosen to 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.