Although several strategies have been developed to improve the efficiency of heterogeneous Fenton-like reactions, investigating the relationship among the electronic properties of the catalyst surface, the complex water matrix and catalytic activity remains challenges. Herein, the electron density of the active site Co(II) in Co Prussian blue analogs (Co-PBAs) is proved to be modulated by the anion source method. The elevated electron density of Co(II) and the higher metallicity of the catalyst lead to an increase in electron transport efficiency as revealed by X-ray photoelectron spectra (XPS), Fourier transform infrared spectroscopy (FT-IR), and density functional theory (DFT) calculations. Furthermore, the negative shift of the D-band center of Co(II) can effectively release intermediates to avoid catalyst poisoning. Bicarbonate has been demonstrated to activate peroxymonosulfate (PMS) by weakening the peroxide bond. Its activation mechanism involves free radical mechanism and non-radical mechanism: the first step is the generation of HCO₄^-, then it is further hydrolyzed to generate •OH and ¹O₂, and the other is HCO₄^- interact with Co(III) to form Co(IV)=O. In addition, the degradation pathways of target contaminants p-nitrophenol and toxicity verification of intermediate products have been investigated. This study provides guidance for the research of Fenton-like reactions.

尽管已经开发了几种策略来提高非均相类芬顿反应的效率，但研究催化剂表面的电子特性、复杂的水基质和催化活性之间的关系仍然是挑战。在此，证明了Co普鲁士蓝类似物（Co-PBA）中活性位点Co（II）的电子密度是通过阴离子源方法调制的。正如 X 射线光电子能谱 (XPS)、傅里叶变换红外光谱 (FT-IR) 和密度泛函理论所揭示的，Co(II) 的电子密度升高和催化剂金属丰度的提高导致电子传输效率的提高(DFT) 计算。此外，D的负移Co(II)的带中心可以有效释放中间体，避免催化剂中毒。碳酸氢盐已被证明通过削弱过氧化物键来激活过氧单硫酸盐 (PMS)。其活化机制包括自由基机制和非自由基机制：第一步是生成HCO ₄ ^-，然后进一步水解生成•OH和¹ O ₂，​​第二步是HCO ₄ ^-与Co(III ) 形成 Co(IV)=O。此外，还研究了目标污染物对硝基苯酚的降解途径和中间产物的毒性验证。该研究为类芬顿反应的研究提供了指导。