Issue 33, 2024

Switchable molecular electrocatalysis

Abstract

We demonstrate a switchable electrocatalysis mechanism modulated by hydrogen bonding interactions in ligand geometries. By manipulating these geometries, specific electrochemical processes at a single catalytic site can be selectively and precisely activated or deactivated. The α geometry enhances dioxygen electroreduction (ORR) while inhibiting protium redox processes, with the opposite effect seen in the β geometry. Intramolecular hydrogen bonding in the α geometry boosts electron density at the catalytic center, facilitating a shift of ORR to a 4-electron pathway. Conversely, the β geometry promotes a 2-electron ORR and facilitates electrocatalytic hydrogen evolution through an extensive proton charge assembly; offering a paradigm shift to conventional electrocatalytic principles. The expectations that ligand geometry induced electron density modulations in the catalytic metal centre would have a comparable impact on both ORR and HER has been questioned due to the contrasting reactivity exhibited by α-geometry and β-geometry molecules. This further emphasizes the complex and intriguing nature of the roles played by ligands in molecular electrocatalysis.

Graphical abstract: Switchable molecular electrocatalysis

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Article information

Article type
Edge Article
Submitted
23 feb 2024
Accepted
04 jul 2024
First published
23 jul 2024
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 13262-13270

Switchable molecular electrocatalysis

S. Dutt, A. R. Kottaichamy, N. C. Dargily, S. Mukhopadhyay, B. Nayak, M. C. Devendrachari, C. P. Vinod, H. M. Nimbegondi Kotresh and M. Ottakam Thotiyl, Chem. Sci., 2024, 15, 13262 DOI: 10.1039/D4SC01284D

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