Solar Water Splitting by Semiconductor Nanocomposites and Hydrogen Storage with Quinoid Systems

Photocatalytic splitting of water was carried out in a two-phase system. The efficiencies of different types of nanocrystalline semiconductors were investigated and compared with commercialised TiO2 nanopowder. Generated hydrogen was chemically stored by use of a quinoid system, which seems to be useable for fuel cells. Solar light sensitive nanocomposites of CdSe/TiO2 and CdSxSey/TiO2 type were prepared and their good photocatalytic performance was demonstrated. In the visible range of 400 - 600 nm CdSxSey/TiO2 composites show comparable good results as in the UV range, which is very promising for their use as solar light water splitters. The concept of sensitising TiO2 with different kind of semiconductor nanoparticles, which is already known from quantum dot sensitised solar cells (QDSC), was demonstrated here for water splitting as well. Furthermore the kinetics of the storage reaction was investigated by UV-Vis spectroscopy and found to proceed via a consecutive reaction with an 1:1 charge transfer complex of quinone and hydroquinone as intermediate. The electron transfer process via a Fe2+/Fe3+ redox couple was investigated by UV-Vis spectroscopy as well as by a dye reaction on the TiO2 surface. A light microscopic view of the surface of larger aggregates of TiO2 nanoparticles indicated different areas of photocatalytic activity with photocatalysis preferentially at catalyst edges. The global electron transfer process could be traced by following the dye colour in real time.