Ionizing radiation induced catalysis on metal oxide particles. 1998 annual progress report

'High-level radioactive waste storage tanks within DOE sites contain significant amounts of organic components (solid and liquid phases) in the form of solvents, extractants, complexing agents, process chemicals, cleaning agents and a variety of miscellaneous compounds. These organics pose several safety and pretreatment concerns, particularly for the Hanford tank waste. Remediation technologies are needed that significantly reduce the amounts of problem organics without resulting in toxic or flammable gas emissions, and without requiring thermal treatments. These restrictions pose serious technological barriers for current organic destruction methods which utilize oxidation achieved by thermal or chemical activation. This project focuses on using ionizing radiation (a,b,g) to catalytically destroy organics over oxide materials through reduction/oxidation (redox) chemistry resulting from electron-hole (e{sup -}/h{sup +}) pair generation. Conceptually this process is an extension of visible and near-UV photocatalytic processes known to occur at the interfaces of narrow bandgap semiconductors in both solution and gas phases. In these processes, an electron is excited across the energy gap between the filled and empty states in the semiconductor. The excited electron does reductive chemistry and the hole (where the electron was excited from) does oxidative chemistry. The energy separation between the hole and the excited electron reflects the redox capability of the e{sup -}/h{sup +} pair, and is dictated by the energy of the absorbed photon and the bandgap of the material. The use of ionizing radiation overcomes optical transparency limitations associated with visible and near-UV illumination (g-rays penetrate much farther into a solution than UV/Vis light), and permits the use of wider bandgap materials (such as ZrO{sub 2}) which possess potentially greater redox capabilities than those with narrow bandgap materials. Experiments have been aimed at understanding the mechanism(s) of g-radiocatalysis and extending the body of knowledge about e{sup -}/h{sup +} pair chemistry of semiconducting metal oxide (MO) materials by examining the influence of surface structure, defects and dopants on the photocatalytic activity of narrow bandgap materials (TiO{sub 2}). An outcome of this proposed work will be a more thorough evaluation of the use of ionizing radiation in the catalytic remediation of organics (and other problem species) in high-level mixed waste.