Fe3O4/PDMS modified collagen sponge and its oil-water separation performance
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摘要: 为发展一种原料丰富、绿色环保、易于在复杂环境中操控使用、循环使用性好的多功能油水分离用海绵材料,采用浸渍法对胶原海绵进行聚二甲基硅氧烷(PDMS)/四氧化三铁(Fe3O4)纳米颗粒复合改性,制备了超疏水胶原基复合海绵(Fe3O4/PDMS-COL),表征了改性后化学结构与微观结构的变化,研究了油水分离性能。通过接触角测量可知:当胶原(COL)浓度为10 mg/mL、PDMS浓度为15vol%时,复合海绵的水接触角为150.3°。FTIR、XPS、XRD及TG测试结果表明Fe3O4/PDMS与胶原海绵成功发生复合,FE-SEM观察结果表明Fe3O4纳米粒子的加入可有效构造表面粗糙结构。海绵可吸附多种不同类型的油相如苯、正己烷、乙酸乙酯、真空泵油、花生油等,其中对乙酸乙酯的吸附量达47 g/g,且对不同油相的分离效率在99%以上。以苯为吸附物,连续循环使用20次后,海绵的接触角与磁性均未发生明显下降。海绵还可有效分离水包油乳液。在外加磁场作用下实施多种场景下的油水分离实验,Fe3O4/PDMS-COL表现出良好的磁操控性。此外,海绵还具有较好的阻燃性能。利用近红外光热响应性,Fe3O4/PDMS-COL还具备了吸附分离复杂环境中固体状油脂/水体系的潜力。Abstract: In order to develop a multi-functional oil-water separation sponge that is rich in raw materials, environmentally friendly, easy to operate in complex environment, and of good reusability, superhydrophobic collagen-based composite sponge (Fe3O4/PDMS-COL) was prepared by impregnating collagen sponge with polydimethylsiloxane (PDMS)/ferroferric oxide nanoparticles (Fe3O4). The changes of chemical structure and microstructure after modification were characterized, and the oil-water separation performance was studied. According to the measurement of contact angle, when the concentration of collagen (COL) is 10 mg/mL and the concentration of PDMS is 15vol%, the water contact angle of the composite sponge reaches 150.3°. The results from FTIR, XPS, XRD and TG show that Fe3O4/PDMS compounds with collagen sponge successfully. FE-SEM observation shows that the addition of Fe3O4 nanoparticles construct rough surface structures effectively. Fe3O4/PDMS-COL can adsorb a variety of oil phases, including benzene, n-hexane, ethyl acetate, vacuum pump oil, peanut oil, among which the adsorption capacity (47 g/g) toward ethyl acetate is the highest, meanwhile the separation efficiency towards various oil phases reaches no less than 99%. After recycling for 20 times for absorbing benzene, both of the contact angle and magnetism of the sponge do not reduce significantly. Moreover, Fe3O4/PDMS-COL has a desirable emulsion separation ability and can effectively separate oil-in-water emulsion. Oil-water separation experiments were carried out in various scenarios under the action of external magnetic field, demonstrating the favourable magnetic responsiveness and manipulation. In addition, Fe3O4/PDMS-COL exhibits a good flame retardant performance. Furthermore, Fe3O4/PDMS-COL possesses an excellent separation capacity toward solid oil/water system in a complex environment, due to its near infrared photothermal effect.
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Key words:
- collagen /
- sponge /
- water pollutants /
- polydimethylsiloxane /
- magnetic field effects-control /
- photothermal conversion
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图 4 Fe3O4/PDMS-COL海绵的磁性表现 (a)、对不同液滴的疏水表现 (b)、海绵内部的疏水表现 (c) 及在极端条件(冷冻、加热)下的疏水表现 (d)
Figure 4. Magnetic performance (a), hydrophobic performance toward different droplets (b), hydrophobic performance of the interior (c) and hydrophobic performance under different conditions (freezing, heating) (d) of Fe3O4/PDMS-COL sponge
图 6 Fe3O4/PDMS-COL海绵在重力作用下的油水分离实验 ((a1)~(a3))、外部驱动作用下的抽滤实验 ((b1)~(b3)) 和外部驱动作用下的连续性油水分离实验 ((c1)~(c3))
Figure 6. Oil-water separation experiment under gravity ((a1)-(a3)), filtration experiment under external drive ((b1)-(b3)) and continuous oil-water separation experiment under external drive ((c1)-(c3)) of Fe3O4/PDMS-COL sponge
图 7 Fe3O4/PDMS-COL海绵对不同油相的吸附容量 (a)、对不同油相的分离效率 (b)、苯每次循环利用后的水接触角 (c) 和20次循环利用后的磁性图 (d)
Figure 7. Absorption capacity toward different oils (a), adsorption efficiency toward different oils (b), water contact angle after each recycling from benzene (c) and magnetic diagram after 20 cycles of recycling (d)
图 9 ((a1)~(a3)) Fe3O4/PDMS-COL海绵在弯管内的油水分离实验;((b1)~(b5)) 在U形管中水层下方重油的去除情况(该管中包含三相液体,分别为:正己烷(上层,透明,轻油)、水(中层,蓝色)和三氯甲烷(下层,红色,重油))
Figure 9. ((a1)-(a3)) Oil-water separation experiment of Fe3O4/PDMS-COL sponge on curved track; ((b1)-(b5)) Removal of heavy oil under the water layer in the U-shaped tube (The tube contains three-phase liquids, namely n-hexane (upper layer, transparent, light oil) , water (middle layer, blue) and chloroform (lower layer, red, heavy oil))
表 1 不同聚二甲基硅氧烷(PDMS)与胶原浓度下海绵的接触角
Table 1. Contact angles of sponges at different concentrations of polydimethylsiloxane (PDMS) and collagen
PDMS
concentration/
vol%Contact
angle/(°)Collagen
concentration/
(mg·mL−1)Contact
angle/(°)5 114.7±0.2 3 109.0±0.3 10 120.1±0.5 6 114.6±0.5 15 150.3±0.6 10 150.3±0.5 20 149.0±0.3 15 140.3±0.4 30 150.5±0.3 20 125.7±0.7 -
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