Impactful Role of Cocatalysts on Molecular Electrocatalytic Hydrogen Production

Hydrogen evolution from a weak acid, acetic acid, occurs at extremely high rates for iron tetraphenylporphyrin in the presence tertiary amine as a cocatalyst. Kinetic analysis of H2 evolution for a range of amines with varying coordinative and acid–base properties reveals a dramatic rate enhancement...

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Bibliographic Details
Published in:ACS catalysis 2021-04, Vol.11 (8), p.4561-4567
Main Authors: Margarit, Charles G, Asimow, Naomi G, Thorarinsdottir, Agnes E, Costentin, Cyrille, Nocera, Daniel G
Format: Article
Language:English
Subjects:
Chemical Sciences
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Summary:Hydrogen evolution from a weak acid, acetic acid, occurs at extremely high rates for iron tetraphenylporphyrin in the presence tertiary amine as a cocatalyst. Kinetic analysis of H2 evolution for a range of amines with varying coordinative and acid–base properties reveals a dramatic rate enhancement derived from enhanced proton activity of a heteroconjugated adduct between acetic acid and the amine. Additionally, nonbulky tertiary amines (quinuclidine and diazabicyclooctane) result in a further increase in activity resulting from a trans effect for a TPPFe­(II)–H hydride intermediate. These findings reveal the design principle of a cocatalyst for creating more efficient molecular systems for hydrogen evolution electrocatalysis.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.1c00253