Mechanistic studies of pyridinium electrochemistry: alternative chemical pathways in the presence of CO2.

Protonated heterocyclic amines, such as pyridinium, have been utilized as catalysts in the electrocatalytic reduction of carbon dioxide. While these represent a new and exciting class of electrocatalysts, the details of the mechanism and faradaic processes occurring in solution are unclear. We report a series of cyclic voltammetry experiments involving Pt, Ag, Au, and Cu electrodes, under both aqueous and nonaqueous conditions, directed towards gaining an improved mechanistic understanding of pyridinium electrochemistry. Surface-enhanced Raman (SER) spectroelectrochemistry was also performed on Cu film-over-nanosphere electrodes in order to identify adsorbed species. It was found that the reduction potential of pyridinium (-0.58 V vs. SCE) and its electrochemical reversibility are unique features of platinum electrodes. In contrast, the reduction potentials on Ag, Au, and Cu electrodes are ∼400 mV more negative than Pt in both the presence and the absence of CO2. SER spectroelectrochemistry of pyridinium solutions shows no evidence for a pyridinium radical or a pyridinium ion. Increased cathodic current in the presence of CO2 is only detected at scan rates less than 10 mV s(-1) in aqueous solutions. The addition of CO2 resulted in a shift in the potential for the hydrogen evolution reaction. Pyridinium electrochemistry was observed under nonaqueous conditions; however no increase in cathodic current was observed when CO2 was added to the solution. Based on this set of results it is concluded that the reduction potential of pyridinium is surface dependent, CO2 acts as a pseudo-reserve of H(+), and pyridinium and CO2 create an alternative mechanism for hydrogen evolution.