Electrocatalytic Carbon Dioxide Activation: The Rate‐Determining Step of Pyridinium‐Catalyzed CO 2 Reduction

The reactivity of reduced pyridinium with CO 2 was investigated as a function of catalyst concentration, temperature, and pressure at platinum electrodes. Concentration experiments show that the catalytic current measured by cyclic voltammetry increases linearly with pyridinium and CO 2 concentrations; this indicates that the rate‐determining step is first order in both. The formation of a carbamate intermediate is supported by the data presented. Increased electron density at the pyridyl nitrogen upon reduction, as calculated by DFT, favors a Lewis acid/base interaction between the nitrogen and the CO 2 . The rate of the known side reaction, pyridinium coupling to form hydrogen, does not vary over the temperature range investigated and had a rate constant of 2.5  M −1  s −1 . CO 2 reduction followed Arrhenius behavior and the activation energy determined by electrochemical simulation was (69±10) kJ mol −1 .