Fluoride-capped nanoceria as a highly efficient oxidase-mimicking nanozyme: inhibiting product adsorption and increasing oxygen vacancies

Nanozymes aim to mimic enzyme activities using nanomaterials. Nanoceria (CeO2 nanoparticles) is an important model nanozyme for its rich redox chemistry. In particular, its oxidase-like activity allows oxidation reactions without the need of unstable and toxic H2O2. Fluoride can significantly improve its oxidase-like activity, and this work aims to understand the mechanism of fluoride-promoted catalysis. First, fluoride can adsorb on CeO2 tighter than other halides, but not as strong as phosphate as characterized by isothermal titration calorimetry (ITC). FT-IR spectroscopy indicates adsorption of fluoride likely via exchange with surface hydroxide groups. Fluoride capping inverses the surface charge of CeO2, facilitating desorption of the ABTS oxidation product, significantly increasing the turnover number. The Raman, EPR and XPS spectroscopy results demonstrate that the concentration of Ce3+ and the accompanying oxygen vacancy significantly increased upon adding F-, which can explain the enhanced catalytic activity. Finally, the electron transfer properties of fluoride-capped CeO2 were more efficient than that of the bare CeO2 as determined by a direct electrochemical measurement on a glass carbon electrode. This study has provided new insight into nanoceria, and can also further confirm the role of nanoceria as a model for engineering the surface of nanozymes.