Highlighting the operating regimes of microchannel electrodes under laminar flow: Mapping of photoluminescence and electrochemiluminescence through semi-transparent electrodes

Abstract

Semi-transparent platinum electrodes were designed and optimized to implement photoluminescence (PL) and electrochemiluminescence (ECL) in microchannels under flow conditions. The luminescence properties of tris(2,2′-bipyridyl)ruthenium(II) (Ru(bpy)₃²⁺) were used to map steady-state emitted light through semi-transparent microchannel electrodes. Several diffusive-convective regimes were thus imposed in order to experimentally highlight the operating conditions of the electrodes, in particular the active zones at their upstream edges contributing to the Faradaic current. PL and ECL profiles were established on the electrode surfaces as a function of flow rate. The PL profiles confirmed the control of the process by mass transport. The data were validated by numerical simulations within the limits of experimental accuracy. ECL emission in presence of the co-reactant tri-n-propylamine (TPA) was also limited by mass transport. However, in comparison the characteristics of the ECL profiles demonstrated the complexity of the underlying mechanism involving Ru(bpy)₃²⁺ regeneration and TPA consumption.