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  4. Electrochemical CO2 and Proton Reduction by a Co(dithiacyclam) Complex
 
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2020
Journal Article
Titel

Electrochemical CO2 and Proton Reduction by a Co(dithiacyclam) Complex

Abstract
While [Ni(cyclam)]2+ and [Ni(dithiacyclam)]2+ complexes were shown to be potent electrocatalysts for the CO2 conversion, their respective Co complexes hitherto received only little attention. Herein, we report on the CoII complexes of the cyclam and dithiacyclam platform, describe their synthesis and reveal their rich solvent dependent coordination chemistry. We show that sulfur implementation into the cyclam moiety leads to a switch from a low spin CoII complex in [Co(cyclam)]2+ to a high spin form in [Co(dithiacyclam)]2+. Notably, while both complexes are capable to perform the reduction of CO2 to CO, H2 formation is generally preferred. Along this line, the complexes were shown to enable proton reduction from acetic acid. However, in comparison to [Co(cyclam)]2+, the altered electronics make [Co(dithiacyclam)]2+ complexes prone to deposit on the glassy carbon working electrode over time leading to an overall low faradaic efficiency for the reduction of protons or CO2.
Author(s)
Iffland, Linda
Ruhr-Universität Bochum
Siegmund, Daniel
Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik UMSICHT
Apfel, Ulf-Peter
Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik UMSICHT
Zeitschrift
Zeitschrift für anorganische und allgemeine Chemie
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DOI
10.1002/zaac.201900356
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Language
English
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Fraunhofer-Institut für Umwelt-, Sicherheits- und Energietechnik UMSICHT
Tags
  • Dithiacyclam

  • cobalt

  • electrocatalysis

  • carbon dioxide

  • hydrogen

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