Sulfate radical (SO₄^•–)-based heterogonous advanced oxidation processes (AOPs) show promising potential to degrade emerging contaminants, however, regulating the electron structure of a catalyst to promote its catalytic activity is challenging. Herein, a hybrid that consists of Co₃O_4-x nanocrystals decorated on urchin-like WO_2.72 (Co₃O_4-x/WO_2.72) with high-valence W and rich oxygen vacancies (OVs) used to modulate the electronic structure of Co-3d was prepared. The Co₃O_4-x/WO_2.72 that developed exhibited high catalytic activity, activating peroxymonosulfate (PMS), and degrading sulfamerazine (SMR). With the use of Co₃O_4-x/WO_2.72, 100% degradation of SMR was achieved within 2 min, at a pH of 7, with the reaction rate constant k₁ = 3.09 min^-1. Both characterizations and density functional theory (DFT) calculations confirmed the formation of OVs and the promotion of catalytic activity. The introduction of WO_2.72 greatly regulated the electronic structure of Co₃O_4-x. Specifically, the introduction of high-valence W enabled the Co-3d band centre to be closer to the Fermi level and enhanced e^– transfer ability, while the introduction of OVs-Co in Co₃O_4-x promoted the activity of electrons in the Co-3d orbital and the subsequent catalytic reaction. The reactive oxygen species (ROS) were identified as •OH, SO₄^•–, and singlet oxygen (¹O₂) by quenching experiments and electron spin resonance (EPR) analysis. The DFT calculation using the Fukui index indicated the reactive sites in SMR were available for an electrophilic attack, and three degradation pathways were proposed.

基于硫酸盐自由基 (SO ₄ ^•– ) 的异质高级氧化过程 (AOP) 显示出降解新兴污染物的巨大潜力，但是，调节催化剂的电子结构以提高其催化活性具有挑战性。在此，由装饰在海胆状 WO _2.72 (Co ₃ O _4-x /WO _{2.72 ) 上的 Co 3} O 4 _-x纳米晶体组成的杂化物具有高价 W 和富氧空位 (OV)，用于调制电子结构制备了 Co-3d。Co ₃ O _4-x /WO _2.72所开发的化合物表现出高催化活性，可激活过氧单硫酸盐 (PMS) 和降解磺胺甲基嘧啶 (SMR)。使用 Co ₃ O _4-x /WO _2.72时，在 pH 值为 7 的情况下，SMR 在 2 分钟内实现了 100% 的降解 ，反应速率常数k ₁ = 3.09  min ^-1。表征和密度泛函理论 (DFT) 计算都证实了 OV 的形成和催化活性的提升。_{WO 2.72}的引入大大调节了Co ₃ O _4-x的电子结构. 具体来说，高价W的引入使Co-3d能带中心更接近费米能级，增强了e-转移能力，而^Co ₃ O _4-x中OVs-Co的引入促进了电子在Co-3d轨道和随后的催化反应。通过猝灭实验和电子自旋共振 (EPR) 分析，将活性氧 (ROS) 鉴定为 •OH、SO ₄ ^•–和单线态氧 ( ¹ O _{2 )。}使用 Fukui 指数的 DFT 计算表明 SMR 中的反应位点可用于亲电攻击，并提出了三种降解途径。