Electron structure modulation and bicarbonate surrounding enhance Fenton-like reactions performance of Co-Co PBA.

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.

Application of sulfate radicals-based advanced oxidation technology in degradation of trace organic contaminants (TrOCs): Recent advances and prospects.

The large amount of trace organic contaminants (TrOCs) in wastewater has caused serious impacts on human health. In the past few years, Sulfate radical (SO4•-) based advanced oxidation processes (SR-AOPs) are widely recognized for their high removal rates of recalcitrant TrOCs from water. Peroxymonosulfate (PMS) and persulfate (PS) are stable and non-toxic strong oxidizing oxidants and can act as excellent SO4•- precursors. Compared with hydroxyl radicals(·OH)-based methods, SR-AOPs have a series of advantages, such as long half-life and wide pH range, the oxidation capacity of SO4•- approaches or even exceeds that of ·OH under suitable conditions. In this review, we present the progress of activating PS/PMS to remove TrOCs by different methods. These methods include activation by transition metal, ultrasound, UV, etc. Possible activation mechanisms and influencing factors such as pH during the activation are discussed. Finally, future activation studies of PS/PMS are summarized and prospected. This review summarizes previous experiences and presents the current status of SR-AOPs application for TrOCs removal. Misconceptions in research are avoided and a research basis for the removal of TrOCs is provided.

Bicarbonate-enhanced iron-based Prussian blue analogs catalyze the Fenton-like degradation of p-nitrophenol.

P-nitrophenol (PNP), a widely used compound, is harmful to the environment and human health. In this study, four iron-based Prussian blue analogs (PBAs) were prepared by coprecipitation (Co-Fe PBA, Mn-Fe PBA, Cu-Fe PBA and Fe-Fe PBA). The Co-Fe PBA exhibited high peroxymonosulfate (PMS) activation performance for PNP degradation, removing over 90% of PNP in 60 min at an optimal pH of 7, temperature at 30 ℃, initial concentration of 20 mg/L, PBA dose of 0.2 g/L and PMS dose of 1 g/L. The physicochemical properties of the Co-Fe PBA were investigated by various characterization methods. The catalytic activity of PBA and the influence of various process parameters and water quality on the catalytic reaction were investigated to elucidate the mechanism of p-nitrophenol degradation by PBA-activated persulfate. Moreover, the mechanism of accelerated degradation of PNP under HCO3- conditions and the role of major reactive oxides were determined by EPR measurement methods and free radical trapping experiments. HCO3- was found to directly activate PMS to produce reactive oxygen species, and 1O2, ∙OH and SO4∙- were all greatly increased. This work presents a promising green heterogeneous catalyst for the degradation of emerging contaminants (ECs) in real wastewater with natural organic matter and coexisting anions by PMS activation.