School of Environmental Science and Engineering, Huazhong University of Science and Technology (HUST), Wuhan, Hubei, 430074, PR China; Hubei Provincial Engineering Laboratory of Solid Waste Treatment, Disposal and Recycling, Huazhong University of Science and Technology (HUST), Wuhan, Hubei, 430074, PR China.
School of Environmental Science and Engineering, Huazhong University of Science and Technology (HUST), Wuhan, Hubei, 430074, PR China; Hubei Provincial Engineering Laboratory of Solid Waste Treatment, Disposal and Recycling, Huazhong University of Science and Technology (HUST), Wuhan, Hubei, 430074, PR China; Hubei Provincial Engineering Technology Research Center of Water Supply Safety and Pollution Control, Huazhong University of Science and Technology (HUST), Wuhan, Hubei, 430074, PR China; State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology (HUST), Wuhan, Hubei, 430074, PR China.
Environ Pollut. 2022 Nov 15;313:120097. doi: 10.1016/j.envpol.2022.120097. Epub 2022 Sep 8.
The narrow acid pH range and the nonselectivity of the dominant •OH limit the Fenton systems to remediate the organic wastewater. Inspired by the role of heme in physiological processes, we employed iron porphyrin as a novel homogeneous catalyst to address this issue. Multiple active species are identified during the activation of HO, including high-valent iron porphyrin ((por)Fe(IV)) species ((por)Fe(IV)-OH, (por)Fe(IV)=O) and oxygen-centered radicals (•OH, HO•/•O), as well as atomic hydrogen (*H) and carbon-centered radicals. With the cooperation of these active species, the degradation of pollutants could be resistant to the interference of concomitant ions and proceed over a wide pH range. This cooperative behavior is further verified by intermediates identified from bisphenol A degradation. Specifically, the presence of *H could facilitate the cleavage of the C-C bond and the addition of unsaturated or aromatic molecules. (Por)Fe(IV)=O could hydroxylate substrates with an oxygen rebound mechanism. Hydrogen atom abstraction of contaminants could be performed by (por)Fe(IV)-OH to form desaturated products by attacking oxygen-centered radicals. The ecotoxicity of bisphenol A could be significantly decreased through degradation. This study would provide a new approach to wastewater treatment and shed light on the interaction between metalloporphyrin and peroxide in an aqueous solution.
窄的酸性 pH 值范围和主导的 •OH 的非选择性限制了芬顿系统对有机废水的修复。受血红素在生理过程中作用的启发，我们采用铁卟啉作为一种新型均相催化剂来解决这个问题。在 HO 的激活过程中，鉴定出了多种活性物质，包括高价铁卟啉（(por)Fe(IV)）物种（(por)Fe(IV)-OH、(por)Fe(IV)=O）和氧中心自由基（•OH、HO•/•O）以及原子氢（*H）和碳中心自由基。这些活性物质的协同作用使污染物的降解能够抵抗共存离子的干扰，并在较宽的 pH 值范围内进行。这种协同作用通过从双酚 A 降解中鉴定出的中间体进一步得到验证。具体来说，*H 的存在可以促进 C-C 键的断裂和不饱和或芳香分子的加成。(por)Fe(IV)=O 可以通过氧回跳机制将底物羟基化。(por)Fe(IV)-OH 可以通过攻击氧中心自由基对污染物进行氢原子提取，形成不饱和产物。双酚 A 的生态毒性可以通过降解显著降低。这项研究为废水处理提供了一种新方法，并揭示了金属卟啉与过氧化物在水溶液中的相互作用。
