Micro-area investigation on electrochemical performance improvement with Co and Mn doping in PbO₂ electrode materials

PbO₂-Co₃O₄-MnO₂ electrodes, used in the electrowinning industry and in the degradation of organic pollutants, have demonstrated an elevated performance through macroscopic electrochemical measurements. However, few reports have investigated localized electrochemical performance, which plays an indispensable role in determining the essential reasons for the improvement of the modified material. In this study, the causes of the increase in electrochemical reactivity are unveiled from a micro perspective through scanning electrochemical microscopy (SECM), X-ray diffraction (XRD), Raman microscopy (Raman), and X-ray photoelectronic energy spectroscopy (XPS). The results show that the increase of electrochemical reactivity of the modified electrodes results from two factors: transformation of the microstructure and change in the intrinsic physicochemical properties. Constant-height scanning maps indicate that the electrochemical reactivity of the modified electrodes is higher than that of the PbO₂ electrode on the whole and high-reactivity areas are orderly distributed, coinciding with the observations from SEM and XRD. Thus, one of the reasons for the improvement of the modified electrode performance is the refinement of the microscopic morphology. The other reason is the surge of the oxygen vacancy concentration on the surface of the coating, which is supported by XRD, Raman and XPS. This finding is detected by the probe approach curve (PAC), which can quantitatively characterize the electrochemical reactivity of a substrate. Heterogeneous charge transfer rate constants of the modified electrode are 4-5 times higher than that of the traditional PbO₂ electrode. This research offers some insight into the electrochemical reactivity of modified PbO₂ electrodes from a micro perspective.