Preparation of nano core-shell PS-CHO@RGO composite microspheres by in-situ polymerization as a potassium hydrogen persulfate catalytic activator for methylene blue degradation
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摘要: 还原氧化石墨烯(RGO)具有比表面积大、电子传输效率高、吸附速率快等优点，在处理油污、重金属离子、有机染料等领域均有应用，但由于自团聚而造成的分散性差等问题限制了其进一步应用。采用原位聚合法制备纳米核-壳型聚苯乙烯醛基微球(PS-CHO)@RGO复合微球。利用TEM、Raman、XRD、XPS及绝缘电阻测试仪对PS-CHO@RGO复合微球的形貌及理化性能进行表征。以亚甲基蓝(MB)为目标污染物，探究了PS-CHO@RGO复合微球在少量过硫酸氢钾(PMPS)存在下的氧化活性，并提出了降解机制。结果表明，RGO片层均匀包覆于PS-CHO微球表面，有效改善了分散性。制备所得PS-CHO@RGO复合微球的渗透阈值低，导电网络完善。降解实验中，PS-CHO@RGO复合微球可以激发PMPS生成硫酸根自由基(SO4−•)，MB的氧化降解率显著提高，60 min内可达98%以上。PS-CHO@RGO复合微球同时表现出良好的稳定性，通过高速离心的方式实现循环利用。Abstract: The reduced graphene oxide (RGO) has been widely used in the treatment of oil, heavy metal ions, organic dyes and other fields due to the large specific surface area, high electron transport efficiency and fast adsorption rate. However, the poor dispersion caused by agglomeration limited the further research. In-situ polymerization was used to prepare nano core-shell polystyrene aldehyde microspheres (PS-CHO)@RGO composite microspheres. The morphology and physicochemical properties of the PS-CHO@RGO composite microspheres were characterized by TEM, Raman, XRD, XPS and insulation resistance tester. The methylene blue (MB) was selected as the target pollutant, the oxidation activity of PS-CHO@RGO composite microspheres in the presence of potassium hydrogen persulfate (PMPS) was investigated, and the degradation mechanism was proposed. The results indicate that RGO layer is uniformly coated on the surface of PS-CHO microspheres, which effectively improved the dispersion. The prepared PS-CHO@RGO composite microspheres are described as low penetration threshold and perfect conductive network. In the degradation experiment, PS-CHO@RGO composite microspheres can stimulate PMPS to generate sulfate radicals (SO4−•), over 98% of MB is catalytically degraded within 60 minutes. Meanwhile, the PS-CHO@RGO composite microspheres also show good stability and can be recycled by high-speed centrifugation.
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Key words:
- composite microspheres /
- reduced graphene oxide (RGO) /
- core-shell type /
- methylene blue /
- catalytic /
- degradation
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图 1 聚苯乙烯醛基微球@还原氧化石墨烯(PS-CHO@RGO)复合微球合成示意图及样品照片
Figure 1. Preparation schematic diagram of polystyrene aldehyde microspheres@reduced graphene oxide (PS-CHO@RGO) composite microspheres and photograph of preparated samples
PVP—Polyvinylpyrrolidone
图 2 PS-CHO微球(a)、氧化石墨烯(GO) (b)和PS-CHO@RGO复合微球(c)的TEM图像
Figure 2. TEM images of PS-CHO microspheres (a), graphene oxide (GO) (b) and PS-CHO@RGO composite microspheres (c)
图 3 PS-CHO微球、GO和PS-CHO@RGO复合微球的拉曼图谱
Figure 3. Raman spectra of PS-CHO microspheres, GO and PS-CHO@RGO composite microspheres
图 4 PS-CHO微球、石墨粉(GP)、GO和PS-CHO@RGO复合微球的XRD图谱
Figure 4. XRD patterns of PS-CHO microspheres, graphite powder (GP), GO and PS-CHO@RGO composite microspheres
图 5 GP、GO和PS-CHO@RGO复合微球的C1s XPS图谱
Figure 5. C1s XPS spectra of GP, GO and PS-CHO@RGO composite microspheres
图 6 不同RGO体积分数的PS-CHO@RGO复合微球的电导率
Figure 6. Conductivity of PS-CHO@RGO composite microspheres with different volume fraction of RGO
图 7 PS-CHO@RGO复合微球的催化活性: (a)不同浓度亚甲基蓝(MB)的吸光度; (b)吸光度与浓度线性方程;(c)不同反应条件下MB浓度的变化曲线; (d)循环催化曲线
Figure 7. Catalytic activities of PS-CHO@RGO composite microspheres: (a) Absorbance of different concentrations of methylene blue (MB); (b) Linear equation of absorbance and concentration of MB; (c) Concentration rate curves of MB under different reaction conditions; (d) Cyclic catalysis plots
PMPS—Potassium hydrogen persulfate
图 8 PS-CHO@RGO复合微球催化降解MB的机制
Figure 8. Catalytic degradation mechanism of MB by PS-CHO@RGO composite microspheres
表 1 GP、GO和PS-CHO@RGO复合微球的化学元素含量
Table 1. Chemical element contents of GP, GO and PS-CHO@RGO composite microspheres
Sample C/at% O/at% C/O ratio GP 98.05 1.03 93.38 GO 60.23 39.67 1.51 PS-CHO@RGO 90.34 9.66 9.35 
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