Crystal Plane Regulation Promotes the Oriented Conversion of Radicals in Heterogeneous Persulfate Catalyzed Oxidation...

In heterogeneous persulfate-catalyzed oxidation systems, the mechanism underlying the crystal plane effects of the catalyst on the selective conversion of reactive oxygen species (ROS) remains ambiguous. In this study, nano-Co₃O₄ catalysts with varying crystallinity and exposure levels of (111) crystal planes are prepared via a hydrothermal method. Compared to low crystalline catalysts, high crystallinity catalysts predominantly expose (111) planes containing higher concentrations of Co²⁺ and oxygen vacancies (Ov), resulting in an increase degradation efficiency of p-nitrobenzaldehyde (4-NBA) from 74.5% to 100%. Radical quenching experiments and EPR characterization reveal that the degradation of 4-NBA occurs through a radical pathway, and quantification of radicals demonstrates that increasing exposure levels of (111) planes effectively promote radical yield (C_SO4•- increase from 18.2 to 172.8 µm and C_•OH increase from 1 to 58.9 µm). Furthermore, XPS and DFT calculations indicate that high crystallinity catalyst possesses more Ov active sites on (111) planes. The presence of Ov not only facilitates the adsorption of PMS molecules but also enhances electron transfer from Co²⁺ to PMS, leading to directed formation and efficient transformation of radicals. This study presents a novel strategy for promoting efficient radical formation in persulfate-activated systems.