The energetics of carbonated PuO2 surfaces affects nanoparticle morphology: a DFT+U study

Samuel Moxon, Adam R. Symington, Joshua Tse, James Dawson, Joseph Flitcroft, Stephen Charles Parker, David Cooke, Robert M. Harker, Marco Molinari

Research output: Contribution to journalArticlepeer-review

7 Citations (Scopus)


Radiolytic corrosion of actinide materials represent an issue for the long term storage and disposal of nuclear materials. Molecular species adsorbed at the surface of the actinides may impact the rate of radiolysis, and as the surfaces corrode, the soluble toxic and radioactive species leach into groundwater. It is therefore critical to characterise the surface composition of actinides. Here, we employ ab initio modelling to determine the surface composition of PuO 2 with respect to adsorbed CO 2. We found that CO 2 interacts strongly with the surface forming carbonate species. By mapping the energetics of this interaction, we then calculate the temperature of desorption, finding that surface morphology has a strong impact on the adsorption of CO 2, with the {100} being the most and the {111} the least affected by carbonation. Finally, we predict the effect of carbonation on the morphology of PuO 2 nanoparticles as a function of temperature and pressure, finding that truncated octahedral is the preferred morphology. This modelling strategy helps characterise surface compensition and nanoparticle morphology, and we discuss the implication for radiolytically driven dispersal of material into the environment.

Original languageEnglish
Pages (from-to)7728-7737
Number of pages10
JournalPhysical Chemistry Chemical Physics
Issue number15
Early online date11 Mar 2020
Publication statusPublished - 21 Apr 2020


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