In this paper, we surprisingly found that the incorporation of unreducible metal oxides M_xO_y (M = Mg, Zn, Ca, Ba, Al) onto CuO hybrid magnetic nano ferric oxide (Cu@Fe₃O₄) may alter the reaction pathway in persulfate activation, and increase the reaction rate constant. The activation of peroxymonosulfate (PMS) by Cu@Fe₃O₄ led to a classic sulfate radical based oxidation process (SR-AOP) with an acetaminophen (ACE) degradation rate constant of 0.004 min⁻¹, while ¹O₂-dominated nonradical oxidation process was disclosed in CuM@Fe₃O₄ with wildly fluctuated reaction rate constants from 0.003 to 0.242 min⁻¹. Mechanism studies indicated that singlet oxygen (¹O₂) derived from the direct oxidation of superoxide anions radicals (O₂⁻) or the recombination of O₂⁻ was the main reactive oxygen species (ROS) in CuM@Fe₃O₄/PMS system. A series of characterization experiments (pH_pzc tests, XPS, H₂-TPR, et al.) and DFT calculation disclosed that the addition of an unreducible metal M yielded many positive effects: (1) the formation of surface oxygen vacancies (O_V) raised the zero point charge (pH_pzc) of CuM@Fe₃O₄, thus enhanced the adsorption and activation of PMS; (2) promoting the generation of a new Cu species (Cu³⁺) on the surface of CuM@Fe₃O₄, which then participated in the generation of ¹O₂. The different reducibility of Cu³⁺ led to differences in the catalytic properties of CuM@Fe₃O₄. In addition, the effects of various water matrix species and the results of reusability experiment, mineralization experiment, and ecotoxicity test exhibited that CuM@Fe₃O₄/PMS system possessed excellent practical application value.

在本文中，我们令人惊讶地发现不可还原的金属氧化物M _x O _y（M = Mg，Zn，Ca，Ba，Al）掺入CuO杂化磁性纳米三氧化二铁（Cu @ Fe ₃ O ₄）可能会改变反应过硫酸盐活化途径，并增加反应速率常数。Cu @ Fe ₃ O ₄对过氧一硫酸盐（PMS）的活化导致经典的基于硫酸根的氧化过程（SR-AOP），对乙酰氨基酚（ACE）降解速率常数为0.004 min ^-1，而¹ O ₂为主的非自由基CuM @ Fe ₃ O _4中公开了氧化过程反应速率常数从0.003到0.242 min ^-1剧烈波动。机制研究表明，单重态氧（¹ Ò ₂从超氧化物阴离子自由基的直接氧化（O衍生）₂ ^- ）或的O-重组₂ ^-是主要的活性氧物质（ROS）在CUM @的Fe ₃ ö ₄ / PMS系统。一系列表征实验（pH _pzc测试，XPS，H ₂ -TPR等）和DFT计算表明，添加不可还原金属M产生了许多积极作用：（1）表面氧空位（O _V）的形成）提高零点电荷（pH_PZC）的CUM @的Fe ₃ ö ₄，从而增强PMS的吸附和活化; （2）促进在CuM @ Fe ₃ O ₄表面生成新的Cu物种（Cu ³⁺），然后参与生成¹ O ₂。Cu ³⁺的不同还原性导致CuM @ Fe ₃ O ₄的催化性能不同。另外，各种水基质的影响以及可重复使用性试验，矿化试验和生态毒性试验的结果表明，CuM @ Fe ₃ O ₄/ PMS系统具有极好的实际应用价值。