Thermochemical solar hydrogen generation.

Solar direct, indirect and hybrid thermochemical processes are presented for the generation of hydrogen and compared to alternate solar hydrogen processes. A hybrid solar thermal/electrochemical process combines efficient photovoltaics and concentrated excess sub-bandgap heat into highly efficient elevated temperature solar electrolysis of water and generation of H2 fuel utilizing the thermodynamic temperature induced decrease of E(H2O) with increasing temperature. Theory and experiment is presented for this process using semiconductor bandgap restrictions and combining photodriven charge transfer, with excess sub-bandgap insolation to lower the water potential, and their combination into highly efficient solar generation of H2 is attainable. Fundamental water thermodynamics and solar photosensitizer constraints determine solar energy to hydrogen fuel conversion efficiencies in the 50% range over a wide range of insolation, temperature, pressure and photosensitizer bandgap conditions.