Cation defect engineering in LaCoO3 perovskite as the "Two birds one stone" strategy to enhanced Fenton-like reaction: Regulating Co spin state and optimizing electron transfer ability

The reactive oxygen species (ROS) triggered by peroxymonosulfate (PMS), primarily composed of radicals and nonradicals, can deeply and selectively remove pollutants in complex wastewater. However, the low efficiency of electron transfer and insufficient surface catalytic sites remain the main obstacles to the development of efficient and selective PMS activators. Herein, we constructed ABO(3) perovskite catalysts (LaCoO3) with adjustable La vacancies (V-La) densities through urea introduction. Experiment, characterization, and theoretical calculation jointly revealed that VLa could not only induce electron delocalization in Co site to enhance the Co 3d - O 2p covalency for accelerating ROS (sulfate radicals (SO4 center dot-), singlet oxygen (O-1(2)), and high valent cobalt (Co(IV) = O)) generation, but also trigger the transition of spin-polarization configuration to form Co3+ (t(2g)(5)e(g)(1)) with the intermediate spin state as new active sites for surface-bound PMS* complexes production. The nonradical-dominated and radical-assisted system containing multi-site achieved efficient PMS utilization (95.6 %), excellent decontamination activity (0.753 min(-1)), good mineralization ability (82.7 %), satisfactory acid-base resistance (working pH range 3-11), and environmental robustness for actual water treatment. This study reveals the role of cation vacancy engineering in achieving "Two birds one stone" for PMS activation at the atomic level, which will guide the rational design of Fenton-like catalysts.