Hydrogen-Evolving Solar Cells

Abstract

Sunlight is directly converted to chemical energy in hydrogen-evolving photoelectrochemical cells with semiconductor electrodes. Their Gibbs free energy efficiency of solar-to-hydrogen conversion, 13.3 percent, exceeds the solar-to-fuel conversion efficiency of green plants and approaches the solar-to-electrical conversion efficiency of the best p-n junction cells. In hydrogen-evolving photoelectrodes, electron-hole pairs photogenerated in the semiconductor are separated at electrical microcontacts between the semiconductor and group VIII metal catalyst islands. Conversion is efficient when the island diameters are small relative to the wavelengths of sunlight exciting the semiconductor; when the island spacings are smaller than the diffusion length of electrons at the semiconductor surface; when the height of the potential energy barriers that separate the photogenerated electrons from holes at the semiconductor surface is raised by hydrogen alloying of the islands; when radiationless recombination of electron-hole pairs at the semiconductor-solution interface between the islands is suppressed by controlling the semiconductor surface chemistry; and when the semiconductor has an appropriate band gap (1.0 to 1.8 electron volts) for efficient solar conversion.