Rotating ring-disk voltammetry: Diagnosis of catalytic activity of metallic copper catalysts toward CO2 electroreduction

Abstract

Using the rotating ring (platinum)—disk (glassy carbon) electrode methodology, electrocatalytic activity of the microstructured copper centers (imbedded within the polyvinylpyrrolidone polymer matrix and deposited onto the glassy carbon disk electrode) has been monitored during electroreduction of carbon dioxide both in acid (HClO4) and neutral (KHCO3) media as well as diagnosed (at Pt ring) with respect to formation of the electroactive products. Combination of the stripping-type and rotating ring-disk voltammetric approaches has led to the observation that, regardless the overlapping reduction phenomena, the reduction of carbon dioxide at copper catalyst is, indeed, operative and coexists with hydrogen evolution reaction. Using the fundamental concepts of surface electrochemistry and analytical voltammetry, the reaction products (thrown onto the platinum ring electrode) could be considered and identified as adsorbates (on Pt) under conditions of the stripping-type oxidation experiment. Judging from the potentials at which the stripping voltammetric peaks appear in neutral CO2-saturated KHCO3 (pH 6.8), formic acid or carbon monoxide seem to be the most likely reaction products or intermediates. The proposed methodology also permits correlation between the CO2 electroreduction products and the potentials applied to the disk electrode. By performing the comparative stripping-type voltammetric experiments in acid medium (HClO4 at pH 1) with the adsorbates of formic acid, ethanol and acetaldehyde (on Pt ring), it can be rationalized that, although C2H5OH or CH3CHO are very likely CO2-reduction electroactive products, formation of some HCOOH, CH3OH or even CO cannot be excluded.