Ni-Mediated Pb-O Bond Activation in β-PbO2 for Efficient Ozone Electrosynthesis

Electrocatalytic ozone production (EOP) provides a sustainable route for advanced oxidation processes. Among various candidates, β-PbO 2 stands out as a proven ozone catalyst; however, its widespread implementation is severely hindered by sluggish kinetics and poor selectivity. Herein, we report a Ni-mediated electrocrystallization strategy that perturbs the local Pb–O environment within the β-PbO 2 framework without appreciable Ni incorporation into the final catalyst. Synchrotron x-ray absorption spectroscopy (XAS), combined with x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS), suggests the presence of lattice strain, electronic-state redistribution, and enhanced local structural disorder. These coupled geometric and electronic changes are consistent with enhanced lattice-oxygen participation during EOP. Consequently, the lattice oxygen-activated PbO 2 (O act -PbO 2 ) exhibits an O 3 yield of 425.6 mg h −1 g cat −1 (a 4.21-fold enhancement over pristine PbO 2 ) and a Faradaic efficiency of 14.73% at 2.5 V versus Ag/AgCl. Notably, an O 3 concentration of 12.30 mg L −1 is achieved within 5 min, and the electrode maintains stable operation for 300 h at 100 mA cm −2 . Furthermore, we establish a rapid and reliable analytical protocol for the quantification of electrogenerated O 3 . This work provides atomic-level insights into lattice oxygen activation and offers an effective strategy for the design of high-efficiency ozone electrosynthesis catalysts. Graphical A Ni-mediated electrocrystallization strategy is employed to regulate the local Pb–O framework without appreciable Ni incorporation. The resulting geometric and electronic modulations favor lattice-oxygen participation during ozone electrosynthesis, enabling an O 3 concentration of 12.30 mg L −1 and stable operation for 300 h.