Zhang Ke, Huang Dongli, Zhang Ying, El Houda Bouroubi Nour, Chen Pan, Ganbold Naranchimeg, He Peng, Liu Junwu, Fang Yingchun, Gan Min, Zhu Jianyu, Yang Baojun
School of Minerals Processing and Bioengineering, Key Laboratory of Biohydrometallurgy of Ministry of Education, Central South University, Changsha, 410083, China.
Hunan Engineering Technology Research Center for Treatment and Recycling of Heavy Pollution Industrial Wastewater, China.
J Environ Manage. 2023 Jun 1;335:117540. doi: 10.1016/j.jenvman.2023.117540. Epub 2023 Feb 24.
Iron and manganese oxides/biochar composite materials (Fe/Mn-BC) are promising catalysts in the field of advanced oxidation. High purity chemical reagents are popular precursors for preparing Fe/Mn-BC, while the potential of low-cost natural minerals as precursors has been neglected. In this study, high-efficiency Fe/Mn-BC was synthesized by one-step pyrolysis method using hematite, phosphoromanganese, and bagasse. The synthesized Fe/Mn-BC removed 83.7% 2, 4-dichlorophenol (2, 4-DCP) within 30 min, about 8.8 and 10.6 times better than biochar (BC) and Fe/Mn complex, respectively. The removal of 2, 4-DCP in the Fe/Mn-BC + peroxydisulfate (PDS) system was influenced by catalyst dosage, PDS concentration, initial pH, organic acids, and chromium. Sulfate radical (SO) and hydroxyl radicals (•OH) generated by Fe/Mn-BC-activated PDS have similar contribution to the degradation of 2,4-DCP. A possible removal mechanism of 2, 4-DCP in the Fe/Mn-BC + PDS system was proposed based on Electron Spin Resonance spectroscopy, free radical quenching experiments, X-ray photoelectron spectroscopy, X-ray diffraction, and electrochemical measurement. Fe and Fe(II) in Fe/Mn-BC play significant role in catalytic degradation of 2, 4-DCP at the early stage of the reaction (within 0-5 min). Then, the interaction between Mn and BC or structural Mn and structural Fe gradually became dominant in the later stage. Similarly, the electron transfer promoted by biochar also played an important role in this catalysis. This discovery provided a new strategy for developing iron and manganese oxides/biochar composite materials to activate PDS for the elimination of refractory organic pollutants.
铁和锰的氧化物/生物炭复合材料(Fe/Mn-BC)是高级氧化领域中很有前景的催化剂。高纯度化学试剂是制备Fe/Mn-BC常用的前驱体,而低成本天然矿物作为前驱体的潜力却被忽视了。在本研究中,以赤铁矿、磷锰矿和甘蔗渣为原料,采用一步热解法合成了高效的Fe/Mn-BC。合成的Fe/Mn-BC在30分钟内去除了83.7%的2,4-二氯苯酚(2,4-DCP),分别比生物炭(BC)和Fe/Mn络合物好约8.8倍和10.6倍。Fe/Mn-BC + 过二硫酸盐(PDS)体系中2,4-DCP的去除受催化剂用量、PDS浓度、初始pH值、有机酸和铬的影响。Fe/Mn-BC活化PDS产生的硫酸根自由基(SO)和羟基自由基(•OH)对2,4-DCP的降解贡献相似。基于电子自旋共振光谱、自由基猝灭实验、X射线光电子能谱、X射线衍射和电化学测量,提出了Fe/Mn-BC + PDS体系中2,4-DCP可能的去除机制。Fe/Mn-BC中的Fe和Fe(II)在反应初期(0-5分钟内)对2,4-DCP的催化降解起重要作用。然后,Mn与BC之间或结构Mn与结构Fe之间的相互作用在后期逐渐占主导地位。同样,生物炭促进的电子转移在该催化过程中也起重要作用。这一发现为开发铁和锰的氧化物/生物炭复合材料以活化PDS去除难降解有机污染物提供了一种新策略。