• carbon dioxide;
  • catalysis;
  • electrochemistry;
  • energy conversion;
  • pyridinium


The reactivity of reduced pyridinium with CO2 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 CO2 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 CO2. 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. CO2 reduction followed Arrhenius behavior and the activation energy determined by electrochemical simulation was (69±10) kJ mol−1.