Through-Space Electrochemiluminescence Reveals Bubble Forces at Remote Phase Boundaries.

Abstract

Several groups have reported on the curious chemistry and reaction acceleration in confined volumes. These complex multiphase systems most closely resemble natural processes, and new measurement tools are necessary to probe chemistry in such environments. Generally, electrochemiluminescence (ECL) reports on processes immediately near (within a few micrometers) the electrode surface. Here, we introduce through-space ECL, reporting on dynamics of processes far away (100s of μm) from the electrode surface. We achieved this by collecting reflected ECL light. During the heterogeneous oxidation of C2O42- in an aqueous phase adjacent to a 1,2-dichlorethane droplet, CO2 accumulates in the 1,2-dichloroethane droplet. Upon buildup, we demonstrate that a CO2 bubble forms in the nonaqueous phase and is surprisingly trapped at the water|1,2-dichloroethane interface and continues to grow. The co-oxidation of tris(bipyridine)ruthenium(II) in the aqueous phase lights up the electrode surface and reflects off the edges of the bubble, revealing the bubble growth over time even when the bubble is fractions of a millimeter from the surface. We extend our results to quantifying bubble forces at the water-oil interface at remote distances from the electrode surface.