期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 19, 期 45, 页码 15166-15174出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201301860
关键词
bridging ligands; cobalt; density functional calculations; hydrogen evolution; proton coupled electron transfer
资金
- French National Research Agency (ANR) [NiFe-Cat ANR-10-BLAN-711, 11-LABX-003]
- DSV-ENERGY CEA Program
- FCH Joint Undertaking (ArtipHyction Project) [303435]
- FP7 CEA-Eurotalents COFUND Program
Cobalt(diimine-dioxime) complexes catalyze hydrogen evolution with low overpotentials and remarkable stability. In this study, DFT calculations were used to investigate their catalytic mechanism, to demonstrate that the initial active state was a Co-I complex and that H-2 was evolved in a heterolytic manner through the protonation of a Co(II)hydride intermediate. In addition, these catalysts were shown to adjust their electrocatalytic potential for hydrogen evolution to the pH value of the solution and such a property was assigned to the presence of a H+-exchange site on the oxime bridge. It was possible to establish that protonation of the bridge was directly involved in the H-2-evolution mechanism through proton-coupled electron-transfer steps. A consistent mechanistic scheme is proposed that fits the experimentally determined electrocatalytic and electrochemical potentials of cobalt(diimine-dioxime) complexes and reproduces the observed positive shift of the electrocatalytic potential with increasing acidity of the proton source.
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