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How Metal Nuclearity Impacts Electrocatalytic H₂ Production in Thiocarbohydrazone-Based Complexes

Papadakis, Michael ; Barrozo, Alexandre ; Delmotte, Léa ; Straistari, Tatiana ; Shova, Sergiu ; Réglier, Marius ; Krewald, Vera ; Bertaina, Sylvain ; Hardré, Renaud ; Orio, Maylis (2023)
How Metal Nuclearity Impacts Electrocatalytic H₂ Production in Thiocarbohydrazone-Based Complexes.
In: Inorganics, 2023, 11 (4)
doi: 10.26083/tuprints-00023650
Article, Secondary publication, Publisher's Version

Abstract

Thiocarbohydrazone-based catalysts feature ligands that are potentially electrochemically active. From the synthesis point of view, these ligands can be easily tailored, opening multiple strategies for optimization, such as using different substituent groups or metal substitution. In this work, we show the possibility of a new strategy, involving the nuclearity of the system, meaning the number of metal centers. We report the synthesis and characterization of a trinuclear nickel-thiocarbohydrazone complex displaying an improved turnover rate compared with its mononuclear counterpart. We use DFT calculations to show that the mechanism involved is metal-centered, unlike the metal-assisted ligand-centered mechanism found in the mononuclear complex. Finally, we show that two possible mechanisms can be assigned to this catalyst, both involving an initial double reduction of the system.

Item Type: Article
Erschienen: 2023
Creators: Papadakis, Michael ; Barrozo, Alexandre ; Delmotte, Léa ; Straistari, Tatiana ; Shova, Sergiu ; Réglier, Marius ; Krewald, Vera ; Bertaina, Sylvain ; Hardré, Renaud ; Orio, Maylis
Type of entry: Secondary publication
Title: How Metal Nuclearity Impacts Electrocatalytic H₂ Production in Thiocarbohydrazone-Based Complexes
Language: English
Date: 2023
Place of Publication: Darmstadt
Year of primary publication: 2023
Publisher: MDPI
Journal or Publication Title: Inorganics
Volume of the journal: 11
Issue Number: 4
Collation: 19 Seiten
DOI: 10.26083/tuprints-00023650
URL / URN: https://tuprints.ulb.tu-darmstadt.de/23650
Corresponding Links:
Origin: Secondary publication DeepGreen
Abstract:

Thiocarbohydrazone-based catalysts feature ligands that are potentially electrochemically active. From the synthesis point of view, these ligands can be easily tailored, opening multiple strategies for optimization, such as using different substituent groups or metal substitution. In this work, we show the possibility of a new strategy, involving the nuclearity of the system, meaning the number of metal centers. We report the synthesis and characterization of a trinuclear nickel-thiocarbohydrazone complex displaying an improved turnover rate compared with its mononuclear counterpart. We use DFT calculations to show that the mechanism involved is metal-centered, unlike the metal-assisted ligand-centered mechanism found in the mononuclear complex. Finally, we show that two possible mechanisms can be assigned to this catalyst, both involving an initial double reduction of the system.

Uncontrolled Keywords: hydrogen evolution, bio-inspiration, electrocatalysis, quantum chemistry, reaction mechanism
Status: Publisher's Version
URN: urn:nbn:de:tuda-tuprints-236500
Additional Information:

This article belongs to the Special Issue Women’s Special Issue Series: Inorganics

Classification DDC: 500 Science and mathematics > 540 Chemistry
Divisions: 07 Department of Chemistry
07 Department of Chemistry > Theoretische Chemie (am 07.02.2024 umbenannt in Quantenchemie)
Date Deposited: 11 Apr 2023 11:35
Last Modified: 12 Apr 2023 05:02
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