Visible Light Driven Photoelectrodes Made of Earth Abundant Elements for Water Photoelectrolysis

With the aim of creating a clean and sustainable energy supply, the direct use of solar energy to produce chemical energy has been pursued for many years. Particularly, the photoelectrolysis of water to generate hydrogen by semiconductor photoelectrodes has attracted great attention because of its advantage of using only water and sunlight, both of which are widely distributed, as raw materials. The earth abundant and visible light absorbing materials are promising for this application for the advantages of easy access and high theoretical solar to hydrogen conversion efficiency. In this thesis, the cadmium sulfide based and copper oxide based photoelectrodes were fabricated and characterized to determine their potential for photoelectrolysis.;As one of the semiconductors with relatively narrow band gap, CdS (2.4eV) has a conduction band edge more negative than the water reduction potential level and a valence band edge more positive than the water oxidation potential level, enabling n-type CdS and p-type CdS as good candidates for photoanode and photocathode respectively. CdS thin film with thickness around 2mum was deposited onto Mo back contact on glass, which formed ohmic contact with CdS. The as-prepared CdS was intrinsic n-type due to the easy formation of sulfur vacancies and it was converted to p-type by the controlled thermal diffusion of copper atoms which substituted cadmium to produce acceptor state. The optimal Cu doping level for the interest of water photoelectrolysis was found to be at 5.4% concentration.;Cu2O with band gap of 2.0eV is another attracting competitor for the photoelectrode among the metal-oxide semiconductors. Both thin film and highly aligned nanowire arrays Cu2O were prepared by thermal oxidation of Cu film and Cu nanowires on Au substrates synthesized by electrodeposition. Cu2O was found to be p-type because of the copper vacancies. The photocurrent of the Cu2O nanowires photocathode was found to be twice that of the Cu2O film, and the bare Cu2O photocathode suffered from a significant photo-induced reductive decomposition. By modifying the surface of the Cu2O nanowires with protecting layers of CuO and TiO2, direct contact of Cu2O with the electrolyte was avoided, and the Cu2O/CuO/TiO2 coaxial nanocable structures were found to gain 74% higher photocurrent and 4.5 times higher stability.;Furthermore, the co-catalysts were also used to modify the photoelectrode surface to reduce the water splitting overpotentials by facilitating the transfer of the photo-induced carriers to the electrolyte. Cobalt based co-catalysts, both the Co2+ and Co3O4 thin film, enhanced the stability of the intrinsic n-CdS photoanode. The Pt modification of CdS:Cu, effectively eliminating the large transient photocurrent, enhanced the photocurrent and stability and positively shifted the onset potential of the cathodic photocurrent by 90 mV, and the hydrogen evolution from the p-type CdS:Cu/Pt photocathode was observed for the first time.;This thesis not only studied the water photoelectrolysis potentials of CdS and Cu2O, but also presented general methods to prevent photocorrosion and enhance photo-activity, which could be also applied to other visible light responsive and earth abundant materials to enlarge the range of material choice for solar water splitting.