In situ generation of H 2 O 2 using CaO 2 as peroxide storage depot for haloperoxidase mimicry with surface-tailored Bi-doped mesoporous CeO 2 nanozymes.

Designing the size, morphology and interfacial charge of catalyst particles at the nanometer scale can enhance their performance. We demonstrate this with nanoceria which is a functional mimic of haloperoxidases, a group of enzymes that halogenates organic substrates in the presence of hydrogen peroxide. These reactions in aqueous solution require the presence of H 2 O 2 . We demonstrate in situ generation of H 2 O 2 from a CaO 2 reservoir in polyether sulfone (PES) and poly(vinylidene fluoride) (PVDF) polymer beads, which circumvents the external addition of H 2 O 2 and expands the scope of applications for haloperoxidase reactions. The catalytic activity of nanoceria was enhanced significantly by Bi 3+ substitution. Bi-doped mesoporous ceria nanoparticles with tunable surface properties were prepared by changing the reaction time. Increasing reaction time increases the surface area S BET of the mesoporous Bi 0.2 Ce 0.8 O 1.9 nanoparticles and the Ce 3+ /Ce 4+ ratio, which is associated with the ζ -potential. In this way, the catalytic activity of nanoceria could be tuned in a straightforward manner. H 2 O 2 required for the reaction was released steadily over a long period of time from a CaO 2 storage depot incorporated in polyether sulfone (PES) and poly(vinylidene fluoride) (PVDF) beads together with Bi 0.2 Ce 0.8 O 1.9 particles, which may be used as precision fillers and templates for biological applications. The spheres are prepared as a dry powder with no surface functionalization or coatings. They are inert, chemically stable, and safe for handling. The feasibility of this approach was demonstrated using a haloperoxidase assay.