Polydopamine-halloysite nanotubes modified stainless steel mesh and its oil-water separation performance
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摘要: 工业含油废水的大量产生和漏油事故的频发，促使高效处理含油废水成为全球性问题。通过浸渍法将聚多巴胺(Polydopamine，PDA)和埃洛石纳米管(Halloysite nanotubes，HNTs)原位沉积在不锈钢网上，制备了超亲水/水下超疏油滤网(PDA-HNTs/SSM)并用于油水分离。利用SEM、EDS、FTIR、XRD、XPS和接触角仪表征了改性不锈钢网的表面形貌、化学组成和润湿性。结果表明，通过调整PDA与HNTs的浸渍周期可控制材料的润湿性和表面微/纳复合结构，10个浸渍周期得到的PDA-HNTs/SSM的超亲水性/水下超疏油性能最优，水下二氯甲烷接触角大于157°，滑动角小于5°。分别采用二甲苯、环己烷、正己烷、石油醚和二氯甲烷进行油水分离测试，PDA-HNTs/SSM的分离效率均大于99%，经50次循环使用后其分离效率在95.5%以上，且在浓度为1 mol/L的HCl、NaOH和NaCl溶液中静置7天或经砂纸摩擦10 m后，仍保持稳定的水下超疏油性和良好的油水分离能力。Abstract: The massive generation of industrial oily wastewater and the frequent occurrence of oil spills have caused efficient treatment of oily wastewater to emerge as a global challenge. A superhydrophilic/ underwater superoleophobic stainless mesh (PDA-HNTs/SSM) was conveniently fabricated by in-situ immersion of polydopamine (PDA) and halloysite nanotubes (HNTs) and used for oil-water spearation. The surface morphology, chemical composition and wettability of the modified SSM were analyzed by SEM, EDS, FTIR, XRD, XPS and contact Angle instrument. The results showed that the wettability and surface micro-nano hierarchical structure of PDA-HNTs/SSM can be controlled by immersion times of PDA-HNTs. PDA-HNTs/SSM obtained by immersion for 10 times had the best wetting performance, the contact angle underwater of dichloromethane was 157°, and the sliding Angle is less than 5°. Dimetylbenzene, cyclohexane, n-hexane, petroleum ether and dichloromethane were used for oil-water separation test. The separation efficiency of PDA-HNTs/SSM was more than 99%, and still maintained above 95.5% after 50 cycles. Moreover, after standing in 1 mol/L HCl, NaOH and NaCl solution for 7 days or rubbing with sandpaper for 10 m, PDA-HNTs/SSM still maintained stable underwater superhydrophobility and good oil-water separation ability.
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图 1 超亲水/水下超疏油滤网(PDA-HNTs/SSM)的制备
Figure 1. Fabrication of the superhydrophilic/underwater superoleophobic stainless mesh (PDA-HNTs/SSM)
DA—Dopamine
图 2 浸渍次数对PDA-HNTs/SSM水下油接触角与滚动角的影响
Figure 2. Effect of soakage times on oil contact angle and sliding angle of PDA-HNTs/SSM
图 3 SSM的水接触角 (a)、水滴在PDA/SSM (b) 与PDA-HNTs/SSM (c) 表面的润湿过程、水下油滴在PDA/SSM (d) 和PDA-HNTs/SSM (e) 表面的表现
Figure 3. Water contact angle of SSM (a), water droplet wetting process on PDA/SSM (b) and PDA-HNTs/SSM (c), underwater oil droplet contact of PDA/SSM (d) and PDA-HNTs/SSM (e)
图 4 PDA-HNTs/SSM的五种油水下油接触角和滚动角
Figure 4. Contact angle and sliding angle of PDA-HNTs/SSM with five kinds of oil
图 5 不同PDA与HNTs浸渍次数下材料的SEM图像
Figure 5. SEM images under different soakage times of PDA and HNTs
图 6 PDA/SSM、HNTs和PDA-HNTs/SSM的FTIR图谱 (a) 和XRD图谱 (b)
Figure 6. FTIR spectra (a) and XRD patterns (b) of PDA/SSM, HNTs and PDA-HNTs/SSM
图 8 SSM、PDA/SSM和PDA-HNTs/SSM的XPS图谱 (a) 和C1s (b) 图谱，PDA/SSM和PDA-HNTs/SSM的N1s (c)、O1s (d) 能谱
Figure 8. XPS spectra (a) and C1s spectra (b) of SSM, PDA/SSM and PDA-HNTs/SSM; N1s (c) and O1s (d) spectra of PDA/SSM and PDA-HNTs/SSM
图 9 PDA-HNTs/SSM的油水循环分离效率(插图为SEM图像) (a)、循环后耐油入侵表现 (b)、摩擦对油接触角与分离效率的影响(插图为SEM图像) (c) 和苛刻环境下的油接触角与分离效率 (d)
Figure 9. Oil-water circulation separation efficiency (Inset is SEM images) (a), the performance of oil invasion resistance after circulation (b), the effect of friction on the oil contact angle and separation efficiency (Inset is SEM images) (c) and the oil contact angle and separation efficiency in harsh environments of PDA-HNTs/SSM (d)
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