A novel Co^II-Fenton-like heterogeneous catalyst, (H₃O)₂[Co^II(phen)(H₂O)₂]₂[Mo^VI₅O₁₅(PO₄)₂]·4H₂O (phen=1,10-phenanthroline, C₁₂N₂H₈) (1), is synthesized and utilized for photocatalytic degradation of organic dyes and antibiotic in a wide range of pH. The experimental results show that 1 acting as the Fenton-like catalyst with H₂O₂ exhibits remarkable activity at pH 3–9 under vis-light irradiation and is merited with excellent recyclability and reusability. A variety of analytical methods, including in-situ electron paramagnetic resonance (EPR) spectroscopy and density functional theory (DFT) calculations, are applied to study the mechanism on generation of ·OH and O₂^·− radicals for photocatalytic degradation. It suggests that, unlike the classical Fenton process involving the redox transformation of the central cations, the generation of ·OH and O₂^·− radicals is associated with the substitution of the coordinating water molecules at Co(II) by H₂O₂ and/or OEH⁻, followed by the light-driven O-O bond cleavage and dissociation The outcomes of this study are striking which overcome the obstacles in the classical Fe^II-Fenton process, including the slow redox transformation between Fe(II) and Fe(III) and the production of massive iron precipitates especially at elevated pH It opens up new avenues for the development of the high-performance Fenton(-like) catalysts for photocatalytic degradation over extended pH and provides new insight into the related process.

一种新型的Co ^II -Fenton型多相催化剂（H ₃ O）₂ [Co ^II（phen）（H ₂ O）₂ ] ₂ [Mo ^VI ₅ O ₁₅（PO ₄）₂ ]·4H ₂ O（phen = 1,10-菲咯啉C ₁₂ N ₂ H ₈）（1）被合成并用于在宽pH范围内光催化降解有机染料和抗生素。实验结果表明：1与H ₂ O _2共同作为Fenton状催化剂在可见光下在pH 3–9下显示出显着的活性，并具有出色的可回收性和可重复使用性。应用多种分析方法，包括原位电子顺磁共振（EPR）光谱和密度泛函理论（DFT）计算，来研究光催化降解·OH和O ₂ ^·-自由基的产生机理。这表明，不同于经典的Fenton过程涉及中心阳离子的氧化还原转化，·OH和O ₂ ^·-自由基的产生与Co（II）处配位水分子被H ₂ O ₂和H ₂ O取代有关。/或OEH ^-然后进行光驱动的OO键裂解和解离。本研究的结果令人瞩目，克服了经典的Fe ^II -Fenton过程中的障碍，包括Fe（II）和Fe（III）之间缓慢的氧化还原转化以及生产过程。大量的铁沉淀物，尤其是在pH升高的情况下。它为开发高性能的Fenton（样）催化剂开辟了新途径，该催化剂可在扩展的pH范围内进行光催化降解，并为相关过程提供了新见识。