We describe two separate but linked efforts in conjunction developing robust, modular solar fuel production systems using polyoxometalates (POMs): making viable (fast, selective and very stable) water oxidation catalysts (WOCs) and carbon-free tunable photosensitizers (PSs).  We present new data and summarize literature data that indicate POM WOCs have one of three general fates: (1) they function as homogeneous catalysts; (2) they precipitate as salts, frequently with the PS cation; or (3) they serve as precursors to metal oxides which are the actual catalysts.  Which fate is operable depends on the elemental composition and structural class of POM as well as the solar fuel production conditions.  We describe a new catalyst containing a multi-cobalt active site stabilized by multi-dentate vanadium-containing POM ligands that turns over at >1000 s-1 which is by far the fastest reported thus far.  We also report POM based tunable metal-to-polyoxometalate chromophores of two types.

Polyoxometalates in solar fuel production

245th National Meeting (2013)

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