In Situ Confocal Raman Microscopy of Redox Polymer Films on Bulk Electrode Supports

A spectroelectrochemical cell is described that enables confocal Raman microscopy studies of electrode-supported films. The confocal probe volume (∼1 μm³) was treated as a fixed-volume reservoir for the observation of potential-induced changes in chemical composition at microscopic locations within an ∼20 μm thickness layer of a redox polymer cast onto a 3 mm diameter carbon disk electrode. Using a Raman system with high collection efficiency and wavelength reproducibility, spectral subtraction achieved excellent rejection of background interferences, opening opportunities for measuring within micrometer-scale thickness redox films on widely available, low-cost, and conventional carbon disk electrodes. The cell performance and spectral difference technique are demonstrated in experiments that detect transformations of redox-active molecules exchanged into electrode-supported ionomer membranes. The in situ measurements were sensitive to changes in the film oxidation state and swelling/deswelling of the polymer framework in response to the uptake and discharge of charge-compensating electrolyte ions. The studies lay a foundation for confocal Raman microscopy as a quantitative in situ probe of processes within electrode-immobilized redox polymers under development for a range of applications, including electrosynthesis, energy conversion, and chemical sensing.