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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117 Scopus citations

Abstract

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
JournalChemSusChem
Volume4
Issue number2
DOIs
StatePublished - Feb 18 2011

All Science Journal Classification (ASJC) codes

  • Environmental Chemistry
  • Chemical Engineering(all)
  • Materials Science(all)
  • Energy(all)

Keywords

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

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