Enhancing the photoelectrochemical water splitting characteristics of titanium and tungsten oxide based materials via doping and sensitization
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To better utilize solar energy for clean energy production, efforts are needed to overcome the natural diurnal variation and the diffuse nature of sunlight. Photoelectrochemical (PEC) hydrogen generation by water splitting is a promising approach to harvest solar energy. Hydrogen gas is a clean and high energy capacity fuel. However, the solar-to-hydrogen conversion efficiency is determined mainly by the properties of the materials employed as photoanodes. Improving the power-conversion efficiency of PEC water splitting requires the design of inexpensive and efficient photoanodes that have strong visible light absorption, fast charge separation, and lower charge recombination rate. In the present study, PEC characteristics of various semiconducting photoelectrodes such as TiO2, WO3 and CuWO4 were investigated. Due to the inherent wide gap, such metal oxides absorb only ultraviolet radiation. Since ultraviolet radiation only composes of 4% of the sun's spectrum, the wide band gap results in lower charge collection and efficiency. Thusto improve optical absorption and charge separation, it is necessary to modify the band gap with low band gap materials.The two approaches followed for modification of band gap are doping and sensitization. Here, TiO2 and WO3 based photoanodes were sensitized with ternary quatum dots, while doping was the primary method utilized to investigate the modification of the band gap of CuWO4.The first part of this dissertation reports the synthesis of ternary quantum dot - sensitized titania nanotube array photoelectrodes. Ternary quantum dots with varying band gaps and composition (MnCdSe, ZnCdSe and CdSSe) were tethered to the surface of TiO2 nanotubes using succcessive ionic layer adsorption and reaction (SILAR) technique. The stoichiometry of ternary quantum dots was estimated to beMn0.095Cd0.95Se, Zn0.16Cd0.84Se and CdS0.54Se0.46. The effect of varying number of sensitization cycles and annealing temperature on optical and photoelectrochemical properties of prepared photoanodes were studied. The absorption properties and surface morphology of the sensitized tubes was analyzed using UV-visible spectroscopy and scanning electron microscopy. The phase composition was determined using X-Ray diffraction and X-ray photoelectron spectroscopy techniques. Electrodes were also evaluated for their stability using inductively coupled plasma optical emission spectrometry. Results show that the sensitization of TiO2 nanotubes with MnCdSe (8.79 mA/cm2), ZnCdSe (12.70 mA/cm2) and CdSSe (15.58 mA/cm2) resulted in up to a 30 fold increase in photocurrent compared to unsensitized nanotubes (0.4 mA/cm2).In the second part, the application of WO3 as photoanode for water splitting was explored. The porous thin films of WO3 films were sensitized with ternary quantum dots (ZnCdSe) using the SILAR technique. The structural, surface morphological and optical properties of the sensitized WO3 thin films were studied. PEC characteristics of the sensitized films were found to be 120 fold increase (8.53 mA/cm2) in comparisonto that of unmodified WO3 films (0.07 mA/cm2).In the last part of this dissertation, CuWO4 was investigated as the potential photoanode material. The band gap of CuWO4 was estimated using density functional theory (DFT) calculations. The band structure was obtained using the first-principles plane wave self-consistent field (pwscf) method and the effect of nickel dopant on the band gap and optical properties of CuWO4 was evaluated. Theoretical calculations showed that doping led to a decrease in band gap. The validity of the theoretical approach was evaluated by experimentally synthesizing Ni-doped CuWO4 electrodes. Experimental results showed that the bandgap indeed decreases when CuWO4 was doped with Ni, and thus validated the DFT approach. Ternary quantum dots were found to increase the PEC activity of TiO2 and WO3 based photoelectrodes by 120 fold. In addition, a method of computing band gap of semiconductor using DFT modeling was developed and validated with experimental results.