Reaction selectivity-regulation via interfacial reconstruction for preventing hazardous slime generation: Driving mechanism of Pb-based anode with oxygen vacancy-rich MnO2

Limited selectivity in coexisted anodic reactions on lead-based anodes leads to severe lead-dissolution, anodic slime-generation and high energy-consumption. Herein, anodic reaction selectivity was regulated by phase-controlled MnO2 (MnO2-PC) on lead-based anodes which was prepared under a lower voltage and a higher Mn2+ concentration. Compared with alpha-MnO2 formed under normal conditions, composite phase of gamma-MnO2 and epsilon-MnO2 was obtained from MnO2-PC with specific crystal planes exposure and rich oxygen vacancy defects enabling higher oxygen evolution reaction selectivity (OER, overpotential reduced by similar to 99 mV). Meanwhile, reaction of lead corrosion and manganese oxidation, as the main reasons for generation of hazardous lead-containing slime, were synergistically suppressed by 86.8% and 91.7%, respectively. Density functional theory (DFT) calculations further clarified that the change in coordinative environment of Mn and O brought lower energy barrier of rate-determining step of OER and stronger electron delocalization ability of MnO2, beneficial for promoting the catalysis of OER. MnO2-PC also displayed excellent inhibition effects on the generation and accumulation of Mn3+, an important precursor of MnO2 slime, and changed the selectivity in the oxidative path of Mn2+. The long-term electrolysis tests proved the stable performance of Pb-Ag/MnO2-PC. This study provides an efficient, low-cost, high economic benefits and environmental-friendly strategy for designing target functional materials towards reaction selectivity regulation via phase-control and microstructure reconstruction.

Automated summary

Selective regulation of anodic reaction was achieved by phase-controlled MnO2 (MnO2-PC) on lead-based anodes, effectively addressing issues such as lead-dissolution, anodic slime-generation and high energy-consumption. MnO2-PC with specific crystal planes exposure and rich oxygen vacancy defects enabled higher oxygen evolution reaction selectivity, while synergistically suppressing lead corrosion and manganese oxidation. This study provides an efficient, low-cost, high economic benefits and environmental-friendly strategy for designing target functional materials towards reaction selectivity regulation via phase-control and microstructure reconstruction.