Electrochemical carbon dioxide reduction with transition-metal based complexes.
Orestes Rivada-Wheelaghan a b
a Laboratoire d'Electrochimie Moléculaire, Université Paris Cité, 75013 Paris, France
b Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica Universidad de Sevilla, Avenida Américo Vespucio 49, 41092 Sevilla (Spain)
Materials for Sustainable Development Conference (MATSUS)
Proceedings of MATSUS23 & Sustainable Technology Forum València (STECH23) (MATSUS23)
#e-FuelSyn - Electrocatalysis for the Production of Fuels and Chemicals
València, Spain, 2023 March 6th - 10th
Organizers: Carla Casadevall Serrano and Julio Lloret Fillol
Invited Speaker, Orestes Rivada-Wheelaghan, presentation 360
Publication date: 22nd December 2022

Molecular electrocatalysts have received a renewed interest due to their capabilities towards sustainable and energy–efficient redox chemical transformations.1 Particularly, those involved in new strategies towards energy storage application.1a, 2 Along these lines, I will present our first means of molecular cooperativity under electrochemical reduction conditions targeting carbon dioxide reduction.3

First, I will provide direct experimental evidence on the correlation of remote interactions between a synthesized MnI-complex and different alkali cations with redox potential tuning. Additionally, the electrochemical behavior of the Mn-complex towards carbon dioxide will be discuss, including the effects of added alkali salts using cyclic voltammetry.3a

Later, I will present the formation, characterization and use of a dinuclear cobalt complex bearing a pyrazole-based ligand substituted with terpyridine groups at the 3 and 5 positions, for the electrocatalytic reduction carbon dioxide to carbon monoxide in the presence of Brönsted acids (94 % selectivity towards CO formation, at –1.35 V vs Saturated Calomel Electrode in DMF/TFE mixtures).3b Chemical, electrochemical and UV-vis spectro-electrochemical studies under inert atmosphere of this complex indicate pairwise reduction processes. And, infrared spectro-electrochemical studies under carbon dioxide and carbon monoxdie atmosphere are consistent with a reduced CO-containing dicobalt complex which results from the electroreduction of carbon dioxide. Additionally, our theoretical results indicate the cooperativity of the ligand platform during the reduction process, delocalizing the electron density at the ligand and reducing the overpotential of the reduction reaction.

References

(1) a) N. W. Kinzel, C. Werlé, W. Leitner, Angew. Chem. Int. Ed. 2021, 60, 11628–11686; b) N. Wolff, O. Rivada‐Wheelaghan, D. Tocqueville, ChemElectroChem 2021, 8, 4019–4027.

(2) a) T. R. Cook, D. K. Dogutan, S. Y. Reece, Y. Surendranath, T. S. Teets, D. G. Nocera, Chem. Rev. 2010, 110, 6474–6502.

(3) a) A. Srinivasan, J. Campos, N. Giraud, M. Robert, O. Rivada–Wheelaghan, Dalton Trans. 2020, 49, 16623–16626; b) A. Bohn, J. J. Moreno, P. Thuéry, M. Robert, O. Rivada-Wheelaghan, 2022, 10.1002/chem.202202361.

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