Controlling the spatial arrangement of molecular catalysts on electrodes is critical to developing an optimal electrocatalyst. Mo-S clusters have shown great promise in catalyzing hydrogen evolution for the generation of carbon-free fuel from water. Here, we report a synthetic approach to organize these molecular clusters into ordered dimers, cages, and chains through the use of organic linkers, as solved by single-crystal X-ray diffraction. We find the linkage through the coordination bond between thiolate and Mo3S7 leads to (1) a 40-fold enhancement in turnover frequency compared to the unlinked cluster, and (2) the periodic arrangement of clusters on the electrode with control over their distance, orientation, and density, thus enabling hydrogen evolution at high catalyst loading. The materials developed here outperform other Mo-S catalysts (both molecular and solid-state) and require only 89 mV of overpotential to achieve a current density of 10 mA cm-2.

Linking molybdenum-sulfur clusters for electrocatalytic hydrogen evolution

2019 Spring National Meeting

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