Fe<sub>3</sub>O<sub>4</sub>/聚二甲基硅氧烷改性胶原海绵及其油水分离性能

郭晨晨; 张云龙; 王瑜; 丁翠翠; 黄六莲; 陈礼辉; 张敏

doi:10.13801/j.cnki.fhclxb.20220506.001

Fe₃O₄/聚二甲基硅氧烷改性胶原海绵及其油水分离性能

doi: 10.13801/j.cnki.fhclxb.20220506.001

1.
福建农林大学　材料工程学院，福州 350108
2.
福建工程学院　生态环境与城市建设学院，福州 350118

基金项目: 国家自然科学基金 (22178056；22078060)

详细信息

通讯作者:
张敏，博士，副教授，硕士生导师，研究方向为生物质高值转化与功能化　E-mail: mzhang@fafu.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2022-02-28
- 修回日期: 2022-04-16
- 录用日期: 2022-04-23
- 网络出版日期: 2022-05-07
- 刊出日期: 2022-08-22

Fe₃O₄/PDMS modified collagen sponge and its oil-water separation performance

1.
College of Material Engineering, Fujian Agriculture and Forestry University, Fuzhou 350108, China
2.
College of Ecological Environment and Urban Construction, Fujian University of Technology, Fuzhou 350118, China

摘要

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。
- 胶原 /
- 海绵 /
- 水污染物 /
- 聚二甲基硅氧烷 /
- 磁场效应-控制 /
- 光热转换
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.
- collagen /
- sponge /
- water pollutants /
- polydimethylsiloxane /
- magnetic field effects-control /
- photothermal conversion

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图 1 胶原(COL)和PDMS浓度对海绵水接触角的影响

Figure 1. Effects of collagen (COL) and PDMS concentrations on water contact angle of sponges

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图 2 未改性胶原海绵、Fe₃O₄粉体、Fe₃O₄-COL海绵和Fe₃O₄/PDMS-COL复合海绵的FTIR图谱 (a)、XPS图谱 (b)、XRD图谱 (c) 及TG曲线 (d)

Figure 2. FTIR spectra (a), XPS spectrum (b), XRD patterns (c) and TG curves (d) of unmodified collagen sponge, Fe₃O₄ powder, Fe₃O₄-COL sponge and Fe₃O₄/PDMS-COL composite sponge

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图 3 Fe₃O₄/PDMS-COL海绵的FE-SEM图((a) 500倍放大倍率; (a1) 10000倍放大倍率; (a2) 20000倍放大倍率)与EDS图(b)

Figure 3. FE-SEM images ((a) 500 times magnification; (a1) 10000 times magnification; (a2) 20000 times magnification) and EDS images (d) of Fe₃O₄/PDMS-COL sponge

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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

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图 5 Fe₃O₄/PDMS-COL海绵分离轻油/水混合物 (a) 和重油/水混合物 (b)

Figure 5. Separation of light oil/water mixture (a) and heavy oil/water mixture (b) by Fe₃O₄/PDMS-COL sponge

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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

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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)

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图 8 水包油(O/W)型乳液分离实验 (a) 和乳液分离前后的光学显微镜图像 (b)

Figure 8. Oil in water (O/W) emulsion separation experiment (a) and optical microscope images before and after emulsion separation (b)

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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))

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图 10 Fe₃O₄/PDMS-COL海绵的阻燃效果 ((a), (b))、燃烧后海绵的外观状态 (c) 及疏水性 (d)

Figure 10. Flame retardant effect of Fe₃O₄/PDMS-COL sponge ((a), (b)), appearance status (c) and hydrophobicity (d) of Fe₃O₄/PDMS-COL sponge after combustion

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图 11 近红外光热效应下Fe₃O₄/PDMS-COL海绵的固体油脂/水分离情况

Figure 11. Separation of solid oil/water by Fe₃O₄/PDMS-COL sponge under near infrared photothermal effect

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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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