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Generating High-valent Iron-oxo ≡FeIV =O Complexes in Neutral Microenvironments through Peroxymonosulfate Activation
Yan Bao1,2, Cheng Lian3, Kai Huang3
1Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, Institute of Fine Chemicals, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai, 200237, China.
Abstract:
The universal limit on the pH conditions is disturbing peroxymonosulfate (PMS)-triggered high-valent iron-oxo systems in environmental applications. Here, we propose for the first time the construction of a neutral microenvironment on the surface of Zn-Fe layered double hydroxide (ZnFe-LDH) by using the amphoteric properties of zinc hydroxide, which continuously generates ≡FeIV =O over a wide pH range of 3.0-11.0 in activating PMS. The ≡Zn(OH)2 moiety offers a neutral microenvironment at the phase interface, which mitigates the self-decomposition of ≡FeIV =O by protons and the hydrolysis reaction of iron by hydroxyl groups, which is supported by the Mossbauer spectra, density functional theory calculations and designed experiments. Consequently, ZnFe-LDH/PMS can satisfy the stability in long-term experiments, selectivity under conditions with high salinity or natural organic matter and efficient treatment of actual wastewater.
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