Reasonable design of a catalyst of high efficiency and stability for water spliting represents a major challenge. Molecular catalysts can not only act as ideal structural models for detailed mechanism study on the molecular level, but also generate valuable molecular insight for further improvement of catalysts with both efficiency and robustness viabottom-up synthetic techniques.Here, we present our study by reviewing a water-soluble molecular K7[CoIIICoII(H2O)W11O39](1  )catalyst developed recently for solar energy conversion. To the best of our knowledge, the molecular Keggin polyoxometalate catalyst 1  is the first reported polyoxometalate containing cobalt with efficient hydrogen production activity under the visible light irradiation.Under the optimal photocatalytic condition (photoirradiation at ? = 420 nm, Eosin-Yas the photosensitizer, triethanolamine as the electron donor and Pt produced in situ photoreduction as co-catalyst),the turnover number (TON/based on catalyst) reached as high as 100; the initial quantum yield and the initial turnover frequency (TOF) at the first 10 minutes were 29% and 0.025 s-1, respectively.The hydrogen evolution average rate of 1   achieved 13395 �mol h-1g-1, as far as we are concerned, which is the highest among all the polyoxometalates photocatalytic systems reported so far. A possible mechanism of the hydrogen evolution reaction was proposed on the basis of steady-state fluorescence decay studies.Our study presents that the unique structural and electronic features of the studied molecular catalyst play the essential role in maintaining both catalytic stability and efficiency for hydrogen evolution.

Molecular Keggin polyoxometalate catalyst with high efficiency for visible-light driven hydrogen evolution

248th National Meeting (2014)

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