Electrocatalytic carbon dioxide activation: The rate-determining step of pyridinium-catalyzed CO2 reduction

Amanda J. Morris, Robert T. McGibbon, Andrew Bruce Bocarsly

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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 2.5M-1s-1. CO2 reduction followed Arrhenius behavior and the activation energy determined by electrochemical simulation was (69±10)a kJmol-1.

Original languageEnglish (US)
Pages (from-to)191-196
Number of pages6
Issue number2
StatePublished - Feb 18 2011

All Science Journal Classification (ASJC) codes

  • General Chemical Engineering
  • General Energy
  • General Materials Science
  • Environmental Chemistry


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


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