Journal
CHEMSUSCHEM
Volume 4, Issue 2, Pages 191-196Publisher
WILEY-BLACKWELL
DOI: 10.1002/cssc.201000379
Keywords
carbon dioxide; catalysis; electrochemistry; energy conversion; pyridinium
Funding
- Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences of the U.S. Department of Energy [DE-SC0002133]
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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 2.5 M-1 S-1. CO2 reduction followed Arrhenius behavior and the activation energy determined by electrochemical simulation was (69 +/- 10) kJ mol(-1).
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