Defect-controlled halogenating properties of lanthanide-doped ceria nanozymes

Marine organisms combat bacterial colonization by biohalogenation of signaling compounds that interfere with bacterial communication. These reactions are catalyzed by haloperoxidase enzymes, whose activity can be emulated by nanoceria using milli- and micromolar concentrations of Br^- and H₂O₂. We show that the haloperoxidase-like activity of nanoceria can greatly be enhanced by Ln substitution in Ce_1-LnO_2-. Non-agglomerated nanosized Ce_1-LnO_2- (Ln = Pr, Tb, particle size < 10 nm) was prepared mechanochemically from CeCl₃ and Na₂CO₃ followed by short calcination. Lanthanide metals could be incorporated into the CeO₂ host without solubility limit, as shown for Tb. The distribution of the Ln³⁺ defect sites in the CeO₂ host structure was analyzed by electron spin resonance spectroscopy. Ce³⁺ and superoxide O₂^- species are present at surface sites. Their formation is promoted by increasing dopant concentration. Ce_1-LnO_2- was prepared in copious amounts by ball-milling. This energy-saving and residue-free method can be upscaled to industrial scale. The surface defect chemistry of Ce_1-LnO_2- was unravelled by vibrational spectroscopy. It is associated with the mechanochemical preparation and leads to enhanced catalytic activity. Although Ce_0.9Pr_0.1O_1.95 had a lower BET surface area than pure CeO₂, its catalytic activity, calibrated by oxidative bromination of phenol red, was much higher because the ζ-potential increased from 15 mV (for CeO₂) to 30 mV (for Ce_0.9Pr_0.1O_1.95). This facilitates adsorption of Br^- in aqueous conditions and explains the high catalytic activity of the Ln-substituted CeO₂. Ce_1-LnO_2- is an effective and "green" nanoparticle haloperoxidase mimic for antifouling applications, as no chemicals other than the ubiquitous Br^- and H₂O₂ (generated in daylight) are required, and only natural metabolites are released into the environment.