Proceedings of nanoGe Fall Meeting 2018 (NFM18)
Publication date: 6th July 2018
The best known electrocatalyst for the production of hydrogen is platinum.[1] As this is a rare and precious metal, non-toxic and earth-abundant alternatives are needed. Amongst them are amorphous molybdenum sulphides (MoSx), which show excellent catalytic activities for proton reduction.[2] However, the mechanism of the hydrogen evolution reaction (HER) catalyzed by MoSx is still a subject of debate. Molecular molybdenum sulphido clusters like [Mo3S13]2− and [Mo2S12]2− can be considered as molecular structural models for the active sites of molybdenum sulfides and their study could thus contribute to solve this problem. Not much is known about the chemical properties and catalytic performance of these clusters so far.[3]
The molybdenum sulphido clusters [Mo3S13]2− and [Mo2S12]2− were prepared following literature procedures and were characterised by Raman spectroscopy, X-ray powder diffraction and mass spectrometry. [3,5] Additionally, the clusters were studied concerning their catalytical activities in electrochemical as well as chemical proton reduction set-ups.
In cyclovoltammetric and chronopotentiometric measurements, clusters immobilized on carbon electrodes showed high HER-activity in strongly (pH 0.3) and in weakly acidic solution (pH 4.5). In chronopotentiometric measures, immobilized [Mo3S13]2− showed better longterm stability than [Mo2S12]2− (Fig. 3). This result could be confirmed for homogeneous catalysis in the presence of EuII-DTPA at different pH values.
In chemical as well as in electrochemical set-ups [Mo3S13]2− and [Mo2S12]2− showed high catalytic HER-activities. Therefore the clusters have a high potential to act as molecular structural models for amorphous molybdenum sulphides building a bridge between homogeneous and heterogeneous catalysis. Thus further investigations by our group will follow, especially for the homogeneous system in solution where more detailed studies on the reaction mechanism are possible.
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