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Mechanistic Insights into the Electrochemical Reduction of CO2 Catalyzed by Iron Cyclopentadienone Complexes
journal contribution
posted on 2018-09-20, 17:43 authored by Elisabeth Oberem, Arend F. Roesel, Alonso Rosas-Hernández, Tobias Kull, Steffen Fischer, Anke Spannenberg, Henrik Junge, Matthias Beller, Ralf Ludwig, Michael Roemelt, Robert FranckeIn
a previous paper we have demonstrated that the easily-synthesized
class of iron(0) cyclopentadienone complexes constitutes a promising
catalyst platform for the electrochemical conversion of CO2 to CO and H2O. One of the unusual features of these catalysts
is that catalysis proceeds efficiently in aprotic electrolytes in
the absence of acidic additives. Herein we present a detailed study
of the underlying catalytic mechanisms. Using a combination of FTIR
spectroelectrochemistry, DFT calculations, and nonelectrochemical
control experiments, we have identified a number of catalytic intermediates
including the active species and the product of catalyst deactivation.
On the basis of these insights, we have carried out digital simulations
in order to decipher the voltammetric profiles of the iron(0) cyclopentadienones.
Further control experiments revealed that the anodic oxidation of
the electrolyte constitutes the terminal proton source for the formation
of CO and H2O. Taken together, our results suggest a competition
between two coexisting catalytic pathways, one of which proceeds via
a hitherto unknown Fe–Fe dimer as an active species.
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Keywords
electrochemical conversioncontrol experimentscyclopentadienoneanodic oxidationCO 2Iron Cyclopentadienone ComplexesElectrochemical Reductionacidic additivesMechanistic Insightsterminal proton sourcevoltammetric profilesnonelectrochemical control experimentsH 2 Ocatalyst deactivationcatalysis proceedsFTIR spectroelectrochemistryaprotic electrolyteseasily-synthesized classcatalyst platformspeciesDFT calculationsCO 2 Catalyzed
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