Ni‐Mediated Pb‐O Bond Activation in β‐PbO 2 for Efficient Ozone Electrosynthesis

ABSTRACT 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.