| An increasing global demand for energy, combined with an awareness of anthropogenic climate change, has recently fueled the search for abundant, carbon neutral energy sources. The sun offers an enormous amount of energy that is practically inexhaustible and well distributed across Earth. Thus, it is an ideal source for meeting our future energy needs in a carbon neutral fashion. This work focuses on using hematite and sunlight to oxidize water, which is the rate limiting step of splitting water into the energy dense fuel, hydrogen, and the byproduct, oxygen. Hematite is abundant, absorbs a large fraction of the solar spectrum and has an appropriately placed valence band for water oxidation. However, the often cited poor bulk properties, and slow charge transfer kinetics require large applied potentials to oxidize water. Atomic layer deposition (ALD) was utilized to deposit uniform thin films of hematite on transparent conductive substrates as model electrodes to better understand the nature of the limitations in the bulk and at the surface. Comparison of the oxidation of water to the oxidation of fast redox shuttles allowed for the separation of bulk and surface processes. A combination of electrochemical impedance spectroscopy, photoelectrochemical and electrochemical measurements were employed to determine the cause of the large required applied potential. It was found that photogenerated holes initially oxidize the electrode surface under water oxidation conditions, which is attributed to the first step in water oxidation. A critical number of these surface intermediates need to be generated in order for subsequent hole-transfer steps to proceed. At low applied potentials, these intermediates are subject to recombination from the large concentration of electrons in the conduction band due to low band bending. At higher applied potentials, high band bending eliminates surface recombination and the charge collection efficiency of the electrolyte reaches unity. A water oxidation mechanism is proposed to interpret these results. In addition, fundamental studies of hematite electrodes coated with the phosphate mediated cobalt oxide catalyst were performed. The catalyst was found to reduce the surface recombination mentioned above. However, oxidized cobalt oxide was still subject to electron recombination at low applied potentials. This recombination was reduced with the use of an alumina blocking layer, which resulted in a modified hematite electrode capable of oxidizing water with a near unity charge collection efficiency at low applied potentials. |
