Transition metal cubane-like complexes, which naturally function as catalytic centers for hydrogen evolving enzymes, hold great promise as highly active, earth-abundant co-catalyst in artificial hydrogen photosynthesis systems. The performance of these structures in catalyzing photocatalytic hydrogen production depends heavily on their interface with solid-state semiconductor light absorbers, as well as their inherent stability under the reaction condition of hydrogen evolution reactions. Our recent results show that by integrating a chemical stable molecular [Mo3S4] cluster that mimic the cubane structure of natural catalytic center with semiconductor nanowire, the photo-production rate of hydrogen increase a significantly compared to bare nanowire surface. The hydrogen generated from the seminconductor-cubane composite increases linearly with time, indicating no degradation in catalytic activity. However, structural analysis of [Mo3S4] in the course of the reaction demonstrated structural evolution from molecular cubane into solid-state amorphous nanoparticles. The structure of the highly potent amorphous nanoparticles was studied with Surface Enhanced Raman Spectroscopy, Aberration Corrected High Resolution TEM and X-ray Adsorption Spectroscopy. Such measurements are crucial for identifying active catalytic species, understanding the reaction mechanism and developing more efficient and stable transition metal sulfide catalyst.

Biomimic molysulfide co-catalyst for hydrogen photosynthesis

248th National Meeting (2014)

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