Visualizing Phase Boundaries with Electrogenerated Chemiluminescence

Reactivity at phase boundaries is central to many areas of chemistry, from synthesis to heterogeneous catalysis. New tools are necessary to gain a more detailed understanding of processes occurring at these boundaries. We describe a series of experiments to visualize phase boundaries using electrogenerated chemiluminescence (ECL) on glassy carbon electrodes. By taking advantage of the solubilities of the ECL luminophore and the coreactant in different liquid phases, we demonstrate that the interface of various phases (i.e., the boundaries formed between a water microdroplet, 1,2-dichloroethane, and a glassy carbon electrode and the boundaries formed between an oxygen bubble, water, and a glassy carbon electrode) can be evaluated. We measured microdroplet contact radii, the three-phase boundary thickness, and growth dynamics of electrogenerated O-2 bubbles. These experimental tools and the fundamental knowledge they yield will find applications in biology, nanoscience, synthesis, and energy storage and conversion, where understanding phase boundary chemistry is essential.