Transtion metal oxides for solar water splitting devices.

摘要

Although the terrestrial flux of solar energy is enough to support human endeavors, storage of solar energy remains a significant challenge to large-scale implementation of solar energy production. One route to energy storage involves the capture and conversion of sunlight to chemical species such as molecular hydrogen and oxygen via water splitting devices. The oxygen evolution half-reaction particularly suffers from large kinetic overpotentials. Additionally, a photoactive material that exhibits stability in oxidizing conditions present during oxygen evolution represents a unique challenge for devices. These concerns can be potentially addressed with a metal oxide photoanode coupled with efficient water oxidation electrocatalysts. Despite decades of research, structure-composition to property relationships are still needed for the design of metal oxide oxygen evolution materials.;This dissertation investigates transition metal oxide materials for the oxygen evolution portion of water splitting devices. Chapter I introduces key challenges for solar driven water splitting. Chapter II elucidates the growth mechanism of tungsten oxide (WOX) nanowires (NWs), a proposed photoanode material for water splitting. Key findings include (1) a planar defect-driven pseudo-one-dimensional growth mechanism and (2) morphological control through the supersaturation of vapor precursors. Result 1 is significant as it illustrates that common vapor-phase syntheses of WOX NWs depend on the formation of planar defects through NWs, which necessitates reconsideration of WOX as a photoanode. Chapter III presents work towards (1) single crystal WOX synthesis and characterization and (2) WOX NW device fabrication. Chapter IV makes use of the key result that WOX NWs are defect rich and therefore conductive in order to utilize them as a catalyst scaffold for oxygen evolution in acidic media. Work towards utilizing NW scaffolds include key results such as stability under anodic potentials and strongly acidic conditions used for oxygen evolution. Chapter V includes work characterizing nickel oxide/oxyhydroxide oxygen evolution catalysts at near-neutral pH. Key findings include (1) previous reports of anodic conditioning resulting in greater catalytic activity are actually due to incidental incorporation of iron impurities from solution and (2) through intentional iron incorporation via electrochemical co-deposition, catalytic activity is increased ~50-fold over Fe-free catalysts. This dissertation contains previously published coauthored material.