Potential-Dependent Temporal Dynamics of CO Surface Concentration in Electrocatalytic CO 2 Reduction.

Beyond the identity and structure of an intermediate, changes in its concentration on and near the electrode surface with time are a critical component to understand and improve selectivity and reactivity in electrochemical transformations. We apply pulsed-potential electrochemical Raman scattering microscopy to measure the potential-dependent temporal evolution of CO formed during electrocatalytic CO 2 reduction in acetonitrile on Ag electrodes. At driving potentials positive of the onset potential as determined by cyclic voltammetry, CO accumulates on the electrode surface at time scales longer than 1 s. Near the ensemble onset potential, CO resides on the electrode surface for approximately 100 ms. At potentials known to evolve CO from the electrode surface, CO remains adsorbed on the electrode for less than 10 ms. The time scales accessible in our strategy are nearly 3 orders of magnitude faster than transient Raman or infrared measurements, allowing direct measurement of the temporal evolution of intermediates.