Simulated temperature programmed desorption experiments for nanoceria powders

[Display omitted] •The article present explicit simulations of temperature-programmed desorption (TPD) experiments through a first-principles derived micro-kinetic model for nanopowders.•The simulations show that oxygen adsorption on ceria is strongly coordination-, and coverage dependent.•Metastable five-coordinated ridge Ce ions offer a plausible explanation for the broad spectra recorded in the TPD experiments and suggests a possible co-existence of Ce3+-ions and superoxide ions even in an oxidative environment.•Our simulations support the notation that small ceria nanoparticles display a supercharged oxygen storage capacity with a broad desorption peak. Density functional theory calculations (DFT), coupled with microkinetic modelling, have been used to simulate Temperature Programmed Desorption (TPD) experiments for calcined ceria nanopowders with the aim to gain insight into the chemistry governing their high redox activity. Our simulations consider two main nanoparticle models. One is a perfect ceria octahedron supercharged with adsorbed oxygen molecules turned into superoxide ions, as has previously been used to explain the enhanced oxygen storage capacity (OSC) in nanoceria. The other model is a variant where we have introduced oxygen vacancies under ridge Ce ions, thereby reducing their coordination numbers to five. The results from our microkinetic modelling suggest that including such five-coordinated Ce adsorption sites results in a TPD spectrum that better matches the experimental counterpart in terms of both peak position and width. In addition, this new structural model allows for the co-existence of Ce3+ ions, superoxide ions and O2 molecules, as seen in experiments in the literature.