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吡咯氮掺杂还原氧化石墨烯泡沫活化过二硫酸钠去除双酚A
左怡丹, 龙俊宏, 宋洁, 和丽金, 金华蕾, 夏丽红, 石苗, 罗利军, 戴建辉
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吡咯氮掺杂还原氧化石墨烯泡沫活化过二硫酸钠去除双酚A
Removal of bisphenol A by pyrrole nitrogen doped reduced graphene oxide foam for peroxodisulfate activation
以吡咯为氮源,通过水热-冷冻干燥法制备易回收的氮掺杂还原氧化石墨烯泡沫(nitrogen doped reduced graphene oxide foam,N-RGF),并用于活化过二硫酸盐(peroxodisulfate,PDS)去除双酚A(bisphenol A,BPA)。利用扫描电子显微镜、X射线衍射、光电子能谱、傅里叶变换红外光谱、BET比表面积和热重分析等技术对材料的结构进行表征和分析,探究溶解性有机质和无机离子对材料性能的影响。结果表明,以吡咯为氮源制备的N-RGF材料具有孔道较小且分布均匀(2~3.5 μm)、比表面积大(90.029 m2/g)、孔体积大(0.541 7 cm3/g)、石墨相氮含量高(4.3%)和弹性好等优点。N-RGF活化PDS降解BPA的动力学速率常数(0.008 35 min-1)是RGF(0.001 42 min-1)的5.88倍,且水中溶解性有机质和无机离子对N-RGF活化PDS降解BPA基本没有影响。活性物种捕获实验和电子顺磁共振检测结果显示单线态氧(1O2)是N-RGF活化PDS降解BPA的主要活性物种。SPE-UHPLC-MS(solid phase extraction combined with ultra-high-performance liquid chromatography-mass spectrometry)中间体检测结果显示有10个中间体,提出了可能的降解途径,且通过MCF-7细胞活力测试发现降解过程产物的雌激素活性基本消除。
The nitrogen doped reduced graphene oxide foam (N-RGF) with excellent recyclability was prepared by hydrothermal method followed freeze drying treatment using pyrrole as nitrogen source, and was applied to activate peroxodisulfate (PDS) to remove bisphenol A (BPA). The structures of as-prepared samples were investigated by SEM, XRD, XPS, FT-IR, BET and TG techniques. The effects of dissolved organic matter (DOM) and inorganic ions on the removal of BPA by N-RGF were explored. The results showed that the N-RGF prepared using pyrrole as nitrogen source has a 3-dimensional foam structure with relatively uniform pores (2~3.5 μm), large specific surface area (90.029 m2/g) and pore volume (0.541 7 cm3/g), high graphitic nitrogen content (4.3%). Moreover, N-RGF has strong elasticity, which is beneficial for the stability and recyclability. The degradation kinetic rate constant of BPA over N-RGF (0.008 35 min-1) was 5.88 times than that of RGF (0.001 42 min-1). The DOM and inorganic ions showed little inhibiting effect on the catalytic performance of N-RGF. The reactive species capture experiment and electron paramagnetic resonance (EPR) showed that singlet oxygen (1O2) is the main active species for BPA degradation. Ten intermediates were identified by solid phase extraction combined with ultra-high-performance liquid chromatography-mass spectrometry (SPE-UHPLC-MS), and possible degradation pathways were proposed. Moreover, the estrogenic activity of treated solution was excluded by the MCF-7 estrogen activity test.
双酚A / 吡咯 / 石墨相氮 / 还原氧化石墨烯泡沫 / 过二硫酸盐活化 {{custom_keyword}} /
bisphenol A / pyrrole / graphitic nitrogen / reduced graphene oxide foam / peroxodisulfate activation {{custom_keyword}} /
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图1 N-RGF的SEM图图2 GO和N-RGF的XRD图图3 N-RGF和GO的FT-IR谱图图4 N-RGF的XPS全谱图(a)及C 1s(b)、O 1s(c)、N 1s(d)分峰拟合图图5 N-RGF的N2吸附脱附等温线及孔径分布图6 N-RGF热重分析图7 不同氮掺杂量(a)、水热反应时间(b)和水热反应温度(c)制备的N-RGF活化PDS去除BPA的性能曲线图8 不同pH值(a)和PDS质量浓度(b)对N-RGF活化PDS去除BPA的影响图9 RGF/PDS、N-RGF/PDS和PDS体系降解BPA的性能比较(a)及相应的伪一级动力学拟合曲线(b)图10 活性物种捕获实验(a)及DMPO(b)和TEMP(c)的EPR图谱图11 N-RGF活化PDS去除BPA机理图图12 N-RGF活化PDS降解BPA的可能途径图13 N-RGF活化PDS降解BPA过程中的产物对MCF-7细胞活力的影响图14 HA、FA、Cl-、 HCO 3 -对 N-RGF活化PDS降解BPA的影响图15 N-RGF活化PDS降解BPA的重复使用实验/
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