2024/11/18 by Matthieu Haake, Bertrand Reuillard, Murielle Chavarot‐Kerlidou +2 · 1 voice · 3 citations
Energy · Engineering · #Advanced battery technologies research #Electrocatalysts for Energy Conversion #Metalloenzymes and iron-sulfur proteins
paper · doi:10.1002/anie.202413910
openalex publication_date 2024/11/18 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/22
Abstract The active sites of metalloenzymes involved in small molecules activation often contain pendant bases that act as proton relay promoting proton‐coupled electron‐transfer processes. Here we focus on hydrogenases and on the reactions they catalyze, i. e. the hydrogen evolution and oxidation reactions. After a short description of these enzymes, we review some of the various biomimetic and bioinspired molecular systems that contain proton relays. We then provide the formal electrochemical framework required to decipher the key role of such proton relay to enhance catalysis in a single direction and discuss the few systems active for H 2 evolution for which quantitative kinetic data are available. We finally highlight key parameters required to reach bidirectional catalysis (both hydrogen evolution and hydrogen oxidation catalyzed) and then transition to reversible catalysis (both reactions catalyzed in a narrow potential range) as well as illustrate these features on few systems from the literature.