Femtoliter oil droplets act as CO2 micropumps for uninterrupted electrochemiluminescence at the water|oil interface

Abstract

Interfacial effects are well-known to significantly alter chemical reactivity, especially in confined environments, where the surface to volume ratio increases. Here, we observed an inhomogeneity in the electrogenerated chemiluminescence (ECL) intensity decrease over time in a multiphasic system composed of femtoliter water droplets entrapping femtoliter volumes of the 1,2-dichloroethane (DCE) continuous phase. In usual electrochemiluminescence (ECL) reactions involving an ECL chromophore and oxalate ([C2O4]2−), the build-up of CO2 diminishes the ECL signal with time because of bubble formation. We hypothesised that relative solubilities of chemical species in these environments play a dramatic role in interfacial reactivity. Water droplets, loaded with the ECL luminophore [Ru(bpy)3]2+ and the coreactant [C2O4]2− were allowed to stochastically collide and adsorb at the surface of a glassy carbon macroelectrode. When water droplets coalesce on the surface, they leave behind femtoliter droplets of the DCE phase (inclusions). We report the surprising finding that the addition of multiple interfaces, due to the presence of continuous phase’s femtoliter inclusions, allows sustained ECL over time after successive potential applications at the triple-phase boundary between water droplet|electrode|DCE inclusion. When femtoliter droplets of DCE form on the electrode surface, bright rings of ECL are observed during the simultaneous oxidation of [Ru(bpy)3]2+ and [C2O4]2−. Control experiments and finite element modelling allowed us to propose that these rings arise because CO2 that is generated near the 1,2-dichloroethane droplet partitions in due to relative solubility of CO2 in 1,2-dichloroethane and builds up and/or is expelled at the top of the droplet. The small droplets of the DCE phase act as micropumps, pumping away carbon dioxide from the interface. These results highlight the unexpected point that confined microenvironments and their geometry can tune chemical reactions of industrial importance and fundamental interest.