第一原理モデリングによるPuO2ナノ粒子の形態に対する小分子吸着種の

The safe management of legacy civil plutonium stockpiles is among the most difficult challenges facing the nuclear industry. While geological disposal facilities (GDFs) are seen as the best solution, anticipating the evolution of waste forms over the lifetime of the GDF forms a critical part of the safety case. In the typical storage form of PuO2 powders, the chemical reactivity of Pu is determined by the exposed crystal facets and surface speciation, which are a complex function of temperature and the partial pressures of oxygen and small-molecule adsorbates. In this work, we use a first-principles modelling approach to develop a predictive thermodynamic model for the impact of the ubiquitous environmental contamininats H2O, CO2 and H2O2 on the equilibrium particle morphpology and surface speciation of stoichiometric and oxygen-deficient PuO2. We find that the presence of multiple adsorbates can lead to both synergistic and antagonistic interactions, with significant impacts on the energetically accessible nanoparticle morphologies and the exposure of the major {100}, {110} and {111} facets. Our model provides important reference data for the impact of environmental conditions on the surface chemistry of PuO2, and can be systematically improved to account for other variables including additional adsorbates, solvation, and surface coverage.