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过硫酸盐活化花生壳生物炭耦合非晶态 Cu 掺杂 FeOOH 复合材料去除水溶液中四环素的研究进展。

Insights into removal of tetracycline by persulfate activation with peanut shell biochar coupled with amorphous Cu-doped FeOOH composite in aqueous solution.

机构信息

State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, 210023, China.

Nanjing Institute of Environmental Sciences, Ministry of Ecological Environment, Nanjing, 210042, China.

出版信息

Environ Sci Pollut Res Int. 2019 Jan;26(3):2820-2834. doi: 10.1007/s11356-018-3777-1. Epub 2018 Nov 28.

Abstract

Peanut shell biochar (BC) supported on Cu-doped FeOOH composite (Cu-FeOOH/BC) was synthesized using a facile and scalable method. The Cu-FeOOH/BC samples were characterized by Fourier transform infrared spectroscopy (FTIR), x-ray diffraction (XRD), scanning electron microscopy equipped with an energy-dispersive spectrometer (SEM-EDS), x-ray photoelectron spectroscopy (XPS), and Brunauer-Emmett-Teller (BET) techniques. Novel catalytic composites with different Cu/Fe molar ratios were compared systematically by activating persulfate (PS) for the tetracycline (TC) degradation. 0.5Cu-1FeOOH/BC (Cu/Fe molar ratio = 0.5:1) was confirmed as the optimum activation material and the removal of TC reached 98.0% after 120 min by combining with 20 mM PS at pH 7.0 and 25 °C. The influencing factors including catalyst loading, PS dosage, water matrix species, and pH on the performance system of 0.5Cu-1FeOOH/BC-PS were investigated, respectively. Reaction rate constants (K) on catalyst dosages (0.05, 0.10, 0.20, and 0.30 g L) were 0.0072, 0.0101, 0.0244, and 0.0144 min, and 0.0090, 0.0146, 0.0244, and 0.0178 min for the change of PS concentrations (5, 10, 20, and 30 mM), which indicated that increasing the concentrations of catalyst and PS appropriately improved TC degradation, but excessive dosages inhibited the reaction process of TC removal. The TC removal rate was inhibited by inorganic anions with the following order of HCO > Cl > HPO > SO > NO. Free radical quenching and capture experiments under different pH values revealed that sulfate radicals existed predominantly in acidic conditions and hydroxyl radicals in alkaline conditions. The catalyst showed an excellent recyclability and stability and the removal efficiency of TC still remained over 90% after five consecutive uses. To conclude, coupling of 0.5Cu-1FeOOH/BC and PS can be successfully applied as an effective and stable technique for the treatment of refractory organic pollutants in wastewater.

摘要

采用简便、可扩展的方法合成了花生壳生物炭负载的铜掺杂的 FeOOH 复合材料(Cu-FeOOH/BC)。通过傅里叶变换红外光谱(FTIR)、X 射线衍射(XRD)、带有能量色散光谱仪(SEM-EDS)的扫描电子显微镜、X 射线光电子能谱(XPS)和 Brunauer-Emmett-Teller(BET)技术对 Cu-FeOOH/BC 样品进行了表征。通过激活过硫酸盐(PS)对四环素(TC)进行降解,系统比较了具有不同 Cu/Fe 摩尔比的新型催化复合材料。在 pH 值为 7.0 和 25°C 时,结合 20 mM PS,0.5Cu-1FeOOH/BC(Cu/Fe 摩尔比=0.5:1)被确认为最佳活化材料,TC 的去除率达到 98.0%。考察了催化剂用量、PS 用量、水基质种类和 pH 值对 0.5Cu-1FeOOH/BC-PS 性能体系的影响。在催化剂用量(0.05、0.10、0.20 和 0.30 g/L)分别为 0.0072、0.0101、0.0244 和 0.0144 min,PS 浓度(5、10、20 和 30 mM)分别为 0.0090、0.0146、0.0244 和 0.0178 min 时,反应速率常数(K)表明适当增加催化剂和 PS 的浓度可以提高 TC 的降解,但是过量的剂量会抑制 TC 去除的反应过程。无机阴离子的抑制作用顺序为 HCO>Cl>HPO>SO>NO。不同 pH 值下的自由基猝灭和捕获实验表明,在酸性条件下主要存在硫酸根自由基,在碱性条件下主要存在羟基自由基。催化剂表现出优异的可回收性和稳定性,五次连续使用后 TC 的去除效率仍保持在 90%以上。总之,0.5Cu-1FeOOH/BC 和 PS 的耦合可以成功地应用于废水处理中难处理的有机污染物的有效和稳定技术。

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