The DOI matches its Crossref record.
Electrocatalytic Carbon Dioxide Activation: The Rate‐Determining Step of Pyridinium‐Catalyzed CO2 Reduction
Abstract
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.
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“From both theoretical and experimental studies, the adsorption and activation steps are the most critical of the CO2 electroreduction process not only due to the high thermodynamic stability of the neutral CO2 molecule, but also the requirement of a large amount of energy for breaking the kinetic barrier [62], conside…”
Background
Metadata
- Authors
- Morris, A. J., McGibbon, R. T., & Bocarsly, A. B.
- Venue
- ChemSusChem
- Publisher
- Wiley
- Published
- 2011-02-16
- Volume
- 4
- Issue
- 2
- Pages
- 191-196
- ISSN
- 1864-5631 (ISSN-L)
- 1864-564X
- OpenAlex
- W2119942754
- Cited by
- 161
- References
- 0
- FWCI
- 7.09
- Type
- journal article
- Language
- en
- Open access
- closed
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