Electrocatalysis and self assembly at solid/liquid interfaces studied by nonlinear optical spectroscopy

Abstract

Reactions and surface functionalization's at fluid interfaces play a major role in electrocatalysis and in molecular self-assembly on surfaces where they can dominate both microscopic and macroscopic properties and their functions. Increasing our level of understanding on the chemistry of fluid interfaces is, therefore, of great importance. Prerequisite to master this challenge is to identify reaction mechanisms at interfaces or the kinetics and structures that form during self-assembly. That is why surface-specific nonlinear optical spectroscopies like sum-frequency generation (SFG) and second-harmonic scattering (SHS) have gained considerable attention for characterization of surfaces and interfaces in equilibrium but also far from equilibrium conditions. In this contribution, we discuss the use SFG and SHG for research in electrocatalysis where we concentrate on CO and ethanol oxidation as well as on CO2 reduction reactions, but also show that nonlinear optical spectroscopies can be powerful tools to address the structure of self-assembled monolayers and their formation on solid surfaces.