Proton relays in molecular electrocatalysis: how do they allow for reversible behavior ?

Vincent Artero^a

^aLaboratoire de Chimie et Biologie des Métaux, Université Grenoble Alpes, CNRS, CEA, Grenoble, France

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, Vincent Artero, presentation 087
DOI: https://doi.org/10.29363/nanoge.matsus.2023.087
Publication date: 22nd December 2022

Hydrogen is now confirmed as a key component of a CO₂-neutral economy, we need to transition towards. The production of large quantities of hydrogen now requires breakthroughs in finding new catalysts that are efficient, stable and cheap, i.e. based on abundant elements. Indeed fuel formation involves multi-electron multi-proton reactions that are inherently kinetically sluggish. Efficient catalysts can be found in living micro-organisms producing or metabolizing hydrogen thanks to hydrogenases. Catalysis in these enzymes only requires Earth-abundant metal centers, the reactivity of which is enhanced thanks to the presence of basic sites acting as proton relays [1] at their vicinity. Such active sites have been used as an inspiration to design new synthetic catalysts for H₂ evolution [2-4] and oxidation [5-6]. Specification, catalytic platforms with installed proton relays display bidirectional [7] and, in rare cases, reversible catalysis [5]. In this presentation we will show how a detailed molecular electrochemistry study can help understanding and quantifying the role of the protons relays related to these remarkable behaviors.

References:

[1] Saveant, J. M., Proton Relays in Molecular Catalysis of Electrochemical Reactions: Origin and Limitations of the Boosting Effect. Angew. Chem. Int. Ed. 2019, 58 (7), 2125-2128.

[2] Sun, D.; Harshan, A. K.; Pecaut, J.; Hammes-Schiffer, S.; Costentin, C.; Artero, V., Hydrogen Evolution Mediated by Cobalt Diimine-Dioxime Complexes: Insights into the Role of the Ligand Acid/Base Functionalities. Chemelectrochem 2021, 8 (14), 2671-2679.

[3] Queyriaux, N.; Sun, D.; Fize, J.; Pecaut, J.; Field, M. J.; Chavarot-Kerlidou, M.; Artero, V., Electrocatalytic Hydrogen Evolution with a Cobalt Complex Bearing Pendant Proton Relays: Acid Strength and Applied Potential Govern Mechanism and Stability. J. Am. Chem. Soc. 2019.

[4] Li, C.-B.; Bagnall, A. J.; Sun, D.; Rendon, J.; Koepf, M.; Gambarelli, S.; Mouesca, J.-M.; Chavarot-Kerlidou, M.; Artero, V., Electrocatalytic reduction of protons to dihydrogen by the cobalt tetraazamacrocyclic complex [Co(N4H)Cl2]+: mechanism and benchmarking of performances. Sustainable Energy & Fuels 2022, 6, 143-149.

[5] Wiedner, E. S.; Appel, A. M.; Raugei, S.; Shaw, W. J.; Bullock, R. M., Molecular Catalysts with Diphosphine Ligands Containing Pendant Amines. Chem. Rev. 2022.

[6] Schild, J.; Reuillard, B.; Morozan, A.; Chenevier, P.; Gravel, E.; Doris, E.; Artero, V., Approaching Industrially Relevant Current Densities for Hydrogen Oxidation with a Bioinspired Molecular Catalytic Material. J. Am. Chem. Soc. 2021, 143 (43), 18150-18158.

[7] Ahmed, M. E.; Nayek, A.; Krizan, A.; Coutard, N.; Morozan, A.; Dey, S. G.; Lomoth, R.; Hammarstrom, L.; Artero, V.; Dey, A., A Bidirectional Bioinspired [FeFe]-Hydrogenase Model. J. Am. Chem. Soc. 2022, 144 (8), 3614-3625.

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