The transformation among Mn^II, Mn^III and Mn^IV on the surface of the manganese oxides is a critical factor for peroxymonosulfate (PMS) activation. In this work, three kinds of Mn₃O₄ with different shapes (plate, cube and octahedra) were prepared to tune the surface Mn valence for ciprofloxacin (CIP) degradation, and the relationship between Mn^IV and PMS activation was established for the first time. The octahedral Mn₃O₄ (Mn₃O₄-O) owns high catalytic activity, Mn^IV is the primary active site on the surface of Mn₃O₄ for PMS activation to generate the active radicals, while the surface –OH groups play a key role in the formation of reactive intermediates. The quenching experiments and Electron paramagnetic resonance (EPR) results suggest that the SO₄‾• and •OH radicals are the main reactive radicals in the catalytic process. The PMS activation should mainly occur in the transformation from Mn^IV to Mn^III. This work is expected to elucidate the relationship between surface valence in manganese oxides and PMS activation by morphology-tuning.

锰氧化物表面上的Mn ^II，Mn ^III和Mn ^IV之间的转化是过氧化单硫酸盐（PMS）活化的关键因素。在这项工作中，制备了三种不同形状的Mn ₃ O ₄（板，立方和八面体）以调节表面环磷酰胺环丙沙星（CIP）降解的化合价，并且首次建立了Mn ^IV与PMS活化之间的关系。时间。八面体Mn ₃ O ₄（Mn ₃ O ₄ -O）具有高催化活性，Mn ^IV是Mn ₃ O ₄表面的主要活性位PMS活化生成活性自由基，而-OH表面在反应性中间体的形成中起关键作用。淬火实验和电子顺磁共振（EPR）的结果表明，SO ₄〜•和•OH基团在催化过程中的主要活性基团。PMS活化应主要发生在从Mn ^IV向Mn ^III的转变中。预期这项工作将通过形态学调节阐明锰氧化物的表面价与PMS活化之间的关系。