Efficient solar water-splitting using a nanocrystalline CoO photocatalyst

The generation of hydrogen from water using sunlight could potentially form the basis of a clean and renewable source of energy. Various water-splitting methods have been investigated previously(1-8), but the use of photocatalysts to split water into stoichiometric amounts of H-2 and O-2 (overall water splitting) without the use of external bias or sacrificial reagents is of particular interest because of its simplicity and potential low cost of operation(1-4). However, despite progress in the past decade, semiconductor water-splitting photocatalysts (such as (Ga1-x Zn-x)(N1-xOx)) do not exhibit good activity beyond 440 nm (refs 1,2,9) and water-splitting devices that can harvest visible light typically have a low solar-to-hydrogen efficiency of around 0.1%(6,7). Here we show that cobalt(II) oxide (CoO) nanoparticles can carry out overall water splitting with a solar-to-hydrogen efficiency of around 5%. The photocatalysts were synthesized from non-active CoO micropowders using two distinct methods (femtosecond laser ablation and mechanical ball milling), and the CoO nanoparticles that result can decompose pure water under visible-light irradiation without any co-catalysts or sacrificial reagents. Using electrochemical impedance spectroscopy, we show that the high photocatalytic activity of the nanoparticles arises from a significant shift in the position of the band edge of the material.