Dual-Modified C–Ce–Mn2O3 Heterostructured Anode Catalytic Layer with Ultrastable OER Performance in Concentrated H2SO4 for Sustainable Nonferrous Metal Electrodeposition
来源:ACS Publications
Mn2O3 emerges as a viable anode catalytic layer candidate for nonferrous metal electrodeposition, yet its industrial adoption is hindered by acid-triggered structural collapse and Mn3+ overoxidation. Here, we demonstrate a heterointerfacial engineering strategy that integrates carbon scaffolding with Ce-doped Mn2O3 (C–Ce–Mn2O3), achieving high stability in concentrated sulfuric acid (160 g·L–1) under aggressive polarization. The C–Ce–Mn2O3 anode sustained operation for 104.3 h at a current density of 1 A·cm–2 before reaching the operational failure threshold, whereas pristine Mn2O3 failed within 53.0 h under identical conditions, demonstrating 100.7% longer operational durability, corresponding to the 1095-day theoretical lifetime 2.07-fold over pristine Mn2O3. Density functional theory reveals that the injection of electrons from the Ce 4f orbital into toward Mn(III) optimizes the spin-down electronic state of Mn 3d and serves as an electron-sacrificing buffer zone for Mn(III), avoiding the overoxidation of Mn(III). The test results of Proto-LXRD indicate that carbon fiber can effectively reduce the internal stress of Mn2O3, increase the coating strength, and suppress the cracking and shell formation of the catalytic layer during electrochemical corrosion.