Real-Time Convolutional Voltammetry Enhanced by Energetic (Hot) Electrons and Holes on a Surface Plasmon Waveguide Electrode.

Surface plasmon polaritons (SPPs) propagating along a waveguide working electrode are sensitive to changes in the local refractive index, which follow changes in the concentration of reduced and oxidized species near the working electrode. The real-time response of the output optical power from a waveguide working electrode is proportional to the time convolution of the electrochemical current density, precluding the need to compute the latter a posteriori via numerical integration. Convolutional voltammetry yields complementary results to conventional voltammetry and can be used to determine the diffusion constant, bulk concentration, and the number of transferred electrons of electroactive species. The theoretical optical response of a waveguide working electrode is derived and validated experimentally via chronoamperometry and cyclic voltammetry measurements under low power SPP excitation, for various concentrations of potassium ferricyanide in potassium nitrate electrolyte at various scan rates. Increasing the SPP power induces a regime where the SPPs no longer act solely as a probe of electrochemical activity, but also as a pump creating energetic electrons and holes via absorption in the working electrode. In this regime, the transfer of energetic carriers (electrons and holes) to the redox species dominates the electrochemical current density, which becomes significantly enhanced relative to equilibrium conditions (low SPP power). In this regime the output optical power remains proportional to the time convolution of the current density, even with the latter significantly enhanced by the transfer of energetic carriers.