Mediated Inner‐Sphere Electron Transfer Induces Homogeneous Reduction of CO2 via Through‐Space Electronic Conjugation

2021 ◽  
Author(s):  
Shelby L. Hooe ◽  
Juan J. Moreno ◽  
Amelia G. Reid ◽  
Emma N. Cook ◽  
Charles Machan
Keyword(s):  
Electron Transfer ◽  
Homogeneous Reduction ◽  
Inner Sphere ◽  
Reduction Of Co2

scholarly journals Mediated Inner-Sphere Electron Transfer Induces Homogeneous Reduction of CO2 via Through-Space Electronic Conjugation

2021 ◽  
Author(s):  
Shelby L. Hooe ◽  
Juan Moreno ◽  
Amelia Reid ◽  
Emma Cook ◽  
Charles Machan
Keyword(s):  
Electron Transfer ◽  
Renewable Energy ◽  
Transition State ◽  
High Activity ◽  
Renewable Energy Sources ◽  
Value Added ◽  
Energy Sources ◽  
Electrocatalytic Reduction ◽  
Homogeneous Reduction ◽  
Reduction Of Co2

The electrocatalytic reduction of CO<sub>2</sub> is an appealing method for converting renewable energy sources into value-added chemical feedstocks. We report a co-electrocatalytic system for the reduction of CO<sub>2</sub> to CO comprised of a molecular Cr complex and dibenzothiophene-5,5-dioxide (DBTD) as a redox mediator which achieves high activity (TOF = 1.51-2.84 x 10<sup>5</sup> s<sup>–1</sup>) and quantitative selectivity. Under aprotic or protic conditions, DBTD produces a co-electrocatalytic response with <b>1</b> by coordinating <i>trans</i> to the site of CO<sub>2</sub> binding and mediating electron transfer from the electrode with quantitative efficiency for CO. This assembly is reliant on through-space electronic conjugation between the <i>π</i> frameworks of DBTD and the bpy fragment of the catalyst ligand, with contributions from dispersive interactions and weak sulfone coordination. The resulting interaction stabilizes a key intermediate in a new aprotic catalytic pathway and lowers the energy of the rate-determining transition state under protic conditions. To the best of our knowledge through-space electronic conjugation has not been explored in molecular electrocatalytic systems.<br>

scholarly journals RuIII(edta) complexes as molecular redox catalysts in chemical and electrochemical reduction of dioxygen and hydrogen peroxide: inner-sphere versus outer-sphere mechanism

RSC Advances ◽  
2021 ◽  
Vol 11 (35) ◽  
pp. 21359-21366
Author(s):  
Debabrata Chatterjee ◽  
Marta Chrzanowska ◽  
Anna Katafias ◽  
Maria Oszajca ◽  
Rudi van Eldik
Keyword(s):  
Hydrogen Peroxide ◽  
Electron Transfer ◽  
Electrochemical Reduction ◽  
Molecular Oxygen ◽  
Outer Sphere ◽  
Transfer Processes ◽  
Edta Complexes ◽  
Inner Sphere ◽  
Electron Transfer Processes ◽  
Sphere Mechanism

[RuII(edta)(L)]2–, where edta4– =ethylenediaminetetraacetate; L = pyrazine (pz) and H2O, can reduce molecular oxygen sequentially to hydrogen peroxide and further to water by involving both outer-sphere and inner-sphere electron transfer processes.

Bioelectrochemical reduction of CO2 to CH4 via direct and indirect extracellular electron transfer by a hydrogenophilic methanogenic culture

2010 ◽  
Vol 101 (9) ◽  
pp. 3085-3090 ◽  
Author(s):  
Marianna Villano ◽  
Federico Aulenta ◽  
Costanza Ciucci ◽  
Tommaso Ferri ◽  
Antonio Giuliano ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Extracellular Electron Transfer ◽  
Reduction Of Co2
Sign in / Sign up

Export Citation Format

Share Document