Impact of small-molecule adsorbates on the morphology of PuO₂nanoparticles from first-principles modelling

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 optimal 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 PuO2powders, 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 compounds H2O, CO2and H2O2on the equilibrium particle morphology 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 enhanced to account for other variables including additional adsorbates, solvation, and surface coverage.