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Plasmonic catalysis holds promise for opening new reaction pathways inaccessible thermally or for improving the efficiency of chemical processes. We report a gold stripe waveguide along which infrared (λ 0 ~ 1350 nanometers) surface plasmon polaritons (SPPs) propagate, operating simultaneously as an electrochemical working electrode. Cyclic voltammograms obtained under SPP excitation enable oxidative processes involving energetic holes to be investigated separately from reductive processes involving energetic electrons. Under SPP excitation, redox currents increase by 10×, redox potentials decrease by ~2× and split in correlation with photon energy, and the charge transfer resistance drops by ~2× as measured using electrochemical impedance spectroscopy. The temperature of the working electrode was monitored in situ, ruling out thermal effects. Chronoamperometry measurements with SPPs modulated at 600 hertz yield a commensurately modulated current response, ruling out thermally enhanced mass transport. Our observations indicate opening of optically controlled nonequilibrium redox channels associated with energetic carrier transfer to the redox species.

Small; lithographically-defined and closely-spaced metallic features of dimensions and separation in the micrometer range are of strong interest as working and counter electrodes in compact electrochemical sensing devices. Such micro-electrode systems can be integrated with microfluidics and optical biosensors, such as surface plasmon waveguide biosensors, to enable multi-modal sensing strategies. We investigate lithographically-defined gold and platinum micro-electrodes experimentally, via cyclic voltammetry (CV) measurements obtained at various scan rates and concentrations of potassium ferricyanide as the redox species, in potassium nitrate as the supporting electrolyte. The magnitude of the double-layer capacitance is estimated using the voltammograms. Concentration curves for potassium ferricyanide are extracted from our CV measurements as a function of scan rate, and could be used as calibration curves from which an unknown concentration of potassium ferricyanide in the range of 0.5–5 mM can be determined. A blind test was done to confirm the validity of the calibration curve. The diffusion coefficient of potassium ferricyanide is also extracted from our CV measurements by fitting to the Randles–Sevcik equation (D = 4.18 × 10−10 m2/s). Our CV measurements were compared with measurements obtained using macroscopic commercial electrodes, yielding good agreement and verifying that the shape of our CV curves do not depend on micro-electrode geometry (only on area). We also compare our CV measurements with theoretical curves computed using the Butler–Volmer equation, achieving essentially perfect agreement while extracting the rate constant at zero potential for our redox species (ko = 10−6 m/s). Finally, we demonstrate the importance of burn-in to stabilize electrodes from the effects of electromigration and grain reorganization before use in CV measurements, by comparing with results obtained with as-deposited electrodes. Burn-in (or equivalently, annealing) of lithographic microelectrodes before use is of general importance to electrochemical sensing devices

Surface plasmon polaritons (SPPs) are optical surface waves propagating along a metal surface. They exhibit attributes such as field enhancement and sub-wavelength localization, which make them attractive for surface sensing, as they are heavily exploited in surface plasmon biosensors. Electrochemistry also occurs on metal surfaces, and electrochemical techniques are also commonly applied in biosensors. As metal surfaces are integral in both, it is natural to combine these techniques into a single platform. Motivations include: (i) realising a multimodal biosensor (electrochemical and optical), (ii) using SPPs to probe the electrochemical double layer or to probe electrochemical activity, thus revealing complementary information on redox reactions, or (iii) using SPPs to pump electrochemical reactions by creating non-equilibrium energetic electrons and holes in a working electrode through the absorption of SPPs thereon. The latter is of interest as it may yield novel redox reaction pathways (i.e., plasmonic electrocatalysis).

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