超浸润性可逆切换的超双疏复合海绵材料的制备及油水分离应用

何影格; 陈媛媛; 刘维仪; 张延宗

doi:10.13801/j.cnki.fhclxb.20200709.001

超浸润性可逆切换的超双疏复合海绵材料的制备及油水分离应用

doi: 10.13801/j.cnki.fhclxb.20200709.001

何影格^1,,
陈媛媛^1,,
刘维仪^1,,
张延宗^{1, 2, ,}

1.
四川农业大学　环境学院，成都 611130
2.
四川省农村环境技术保护工程技术中心，成都 611130

基金项目: 四川省重大科技专项课题(2019YFS0520)，四川省科技计划重点研发项目(2017SZ0039)

详细信息

通讯作者:
张延宗，博士，教授，博士生导师，研究方向为环境材料　 E-mail：yzzhang@sicau.edu.cn

中图分类号: TB332
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出版历程
- 收稿日期: 2020-05-08
- 录用日期: 2020-06-24
- 网络出版日期: 2020-07-09
- 刊出日期: 2021-03-15

Preparation of superamphiphobic composite sponge material with super-wetting reversible switching and application in oil-water separation

HE Yingge^1
,,
CHEN Yuanyuan^1
,,
LIU Weiyi^1
,,
ZHANG Yanzong^{1, 2
, ,}

1.
College of Environment, Sichuan Agricultural University, Chengdu 611130, China
2.
Agricultural Environmental Engineering Center of Sichuan Province, Chengdu 611130, China

摘要

摘要: 通过简单的溶胶-凝胶法制备了全氟癸基三甲氧基硅烷(PFDMS)-正癸酸(DA)-TiO₂溶液，经浸泡后得到PFDMS-DA-TiO₂超双疏海绵。PFDMS-DA-TiO₂超双疏海绵在质量分数为25wt%~28wt%的氨气诱导下，表面浸润性由超双疏切换为超亲水-空气中超疏油。利用FTIR和SEM对改性前后PFDMS-DA-TiO₂海绵表面进行表征，分析其化学组成和表面形貌，研究了DA的体积比对PFDMS-DA-TiO₂超双疏海绵表面浸润性可逆切换效果的影响，并对其耐盐性、耐磨性及油水分离性能进行了测试。结果表明：DA的最佳体积比为5.8%，其油水分离效率与通量分别可达99.6%、4775 L/(m²·h)。PFDMS-DA-TiO₂超双疏海绵经磨损实验及在质量分数为3.5wt%的NaCl溶液中浸泡12 h后，均保持优异的超双疏性能，表现出较高的耐磨性和耐盐性。经氨气诱导，其表面浸润性在超双疏与超亲水-空气中超疏油之间可逆切换20次后，两种润湿性能仍能各自保持稳定，可用于实际工业中高效可控地分离油水混合物。
- 聚氨酯海绵 /
- 超亲水-空气中超疏油 /
- 超双疏 /
- 氨气诱导 /
- 油水分离
Abstract: The perfluorodecyltrimethoxysilane (PFDMS)-n-decanoic acid (DA)-TiO₂ solution was prepared by a simple sol-gel method, and immersed to obtain the PFDMS-DA-TiO₂ superamphiphobic sponge. Under the induction of ammonia gas with a mass fraction of 25wt%–28wt%, the surface wettability of the PFDMS-DA-TiO₂ sponge is switched from superamphiphobic to superhydrophilic and superoleophobic in air. The surface of the PFDMS-DA-TiO₂ sponge before and after modification was characterized by FTIR and SEM, and its chemical composition and surface morphology were analyzed. The effect of the volume ratio of DA on the reversible switching effect of the PFDMS-DA-TiO₂ superhydrophilic sponge surface infiltration was studied, and its salt tolerance, friction resistance and oil-water separation performance were tested. The results show that the optimal volume ratio of DA is 5.8%. At this time, the oil-water separation efficiency and flux can reach 99.6% and 4775 L/(m²·h), respectively. After the PFDMS-DA-TiO₂ superhydrophilic sponge was subjected to an abrasion test and immersed in 3.5wt% NaCl solution for 12 h, they all exhibit excellent superamphiphobic performance and sponges show high abrasion resistance and salt tolerance. After 20 times of reversibly switching of surface wettability between superamphiphobic and superhydrophobic-superhydrophilic in air induced by ammonia, the two wetting properties can still maintain their own stability, which can be used to effectively separate oil-water mixtures in practical industries.
- polyurethane sponge /
- superhydrophilic and superoleophobic in air /
- superamphiphobic /
- ammonia-induced /
- oil-water separation

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图 1 原始海绵和全氟癸基三甲氧基硅烷(PFDMS)-正癸酸(DA)-TiO₂海绵的SEM图像

Figure 1. SEM images of original sponge and perfluorodecyltrimethoxysilane (PFDMS)-n-decanoic acid (DA)-TiO₂ sponge

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图 2 PFDMS、PFDMS-DA-TiO₂海绵表面粉末和钛酸丁酯的FTIR图谱

Figure 2. FTIR spectra of PFDMS, PFDMS-DA-TiO₂ sponge surface powder and butyl titanate

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图 3 PFDMS-DA-TiO₂海绵表面浸润性的可逆切换

Figure 3. Reversible switching of surface wettability of PFDMS-DA-TiO₂ sponge

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图 4 氨气诱导前后PFDMS-DA-TiO₂海绵表面粉末的FTIR

Figure 4. FTIR spectra of PFDMS-DA-TiO₂ modified sponge surface powder before and after ammonia induction

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图 5 PFDMS-DA-TiO₂海绵表面浸润性可逆切换次数

Figure 5. Surface wettability reversible switching times of PFDMS-DA-TiO₂ sponge

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图 6 不同DA体积比的PFDMS-DA-TiO₂海绵表面浸润性切换程度: (a)水的接触角、滚动角及疏水性能转变; (b)油的接触角和滚动角变化

Figure 6. Degree of PFDMS-DA-TiO₂ sponge surface wettability switching at different volume ratios of DA: (a) Water contact angle, rolling angle and hydrophobic property conversion; (b) Oil contact angle and rolling angle change

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图 7 PFDMS-DA-TiO₂海绵的性能: (a) 3.5wt% NaCl溶液浸泡时间对PFDMS-DA-TiO₂海绵表面超双疏性能的影响; (b)不同磨损距离对PFDMS-DA-TiO₂海绵表面超双疏性能的影响

Figure 7. Performance of PFDMS-DA-TiO₂ sponge: (a) Effect of immersion time of 3.5wt% NaCl solution on superamphiphobic performance of PFDMS-DA-TiO₂ sponge surface; (b) Effect of different wear distances on superamphiphobic performance of PFDMS-DA-TiO₂ sponge surface

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图 8 柴油-水分离过程

Figure 8. Separation process of diesel-water

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图 9 油的净化: (a)~(c)柴油的净化; (d)~(f)三氯甲烷的净化

Figure 9. Purification of oil: (a)–(c) Purification of diesel oil; (d)–(f) Purification of chlorofor

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参考文献(30)

[1]	XU Q, XU H, CHEN J R, et al. Graphene and grapheme oxide: Advanced membranes for gas separation and water purification[J]. Inorganic Chemistry Frontiers,2015,46(30):417-424.
[2]	GAO J F, XIN S, HUANG X W, et al. Facile preparation of polymer microspheres and fibers with a hollow core and porous shell for oil adsorption and oil/water separation[J]. Applied Surface Science,2018,439:394-404. doi: 10.1016/j.apsusc.2018.01.013
[3]	张锦山, 董季玲, 武伟, 等. 特殊浸润性油水分离材料研究进展[J]. 功能材料, 2019, 12(50):12041-12050. ZHANG J S, DONG J L, WU W, et al. Research progress on special infiltrating oil-water separation materials[J]. Journal of Function Material,2019,12(50):12041-12050(in Chinese).
[4]	WANG B, LIANG W X, GUO Z G, et al. Biomimetic super-lyophobic and super-lyophilic materials applied for oil/water separation: A new strategy beyond nature[J]. Chemical Society Reviews,2015,44(1):336-361. doi: 10.1039/C4CS00220B
[5]	DAI Y H, CHEN D Y, LI N J, et al. Self-healing and superwettablenanofibrous membranes for efficient separation of oil-in-water emulsions[J]. Journal of Materials Chemistry A,2019,54(4):3648-3660.
[6]	WU C, HUANG X Y, WU X F, et al. Mechanically flexible and multifunctional polymer-based graphene foams for elastic conductors and oil-water separators[J]. Advanced Materials,2013,25(39):5658-5662. doi: 10.1002/adma.201302406
[7]	MIRSHAHGHASSEMI S, LEAD J R. Oil recovery from water under environmentally relevant conditions using magnetic nanoparticles[J]. Environmental Science & Technology,2015,49(19):729-736.
[8]	王鹏伟, 刘明杰, 江雷. 仿生多尺度超浸润界面材料[J]. 物理学报, 2016, 65(18):56-78. WANG P W, LIU M J, JIANG L. Bioinspiredmultiscale interfacial materials with superwettability[J]. Acta Physica Sinica,2016,65(18):56-78(in Chinese).
[9]	KRISHNAN S, WANG N, OBER C K, et al. Comparison of the fouling release properties of hydrophobic fluorinated hydrophilic PEGylated block copolymer surfaces: Attachment strength of the diatom navicula and the green alga ulva[J]. Biomacromolecules,2006,7(5):1449-1462. doi: 10.1021/bm0509826
[10]	李文涛, 雍佳乐, 杨青, 等. 基于特殊浸润性材料的油水分离[J]. 物理化学学报, 2018, 34(5):456-475. doi: 10.3866/PKU.WHXB201709211 LI W T, YONG J L, YANG Q, et al. Oil-water separation based on the materials with special wettability[J]. Acta Physico-Chimica Sinica,2018,34(5):456-475(in Chinese). doi: 10.3866/PKU.WHXB201709211
[11]	XUE Z X, DAO Y Z, LIU N, et al. Special wettable materials for oil/water separation[J]. Journal of Materials Chemistry A,2014,2(8):2445-2460. doi: 10.1039/C3TA13397D
[12]	屈孟男, 马利利, 何金梅, 等. 特异润湿型油水分离材料的研究进展[J]. 材料导报, 2017, 31(10):152-161. QU M N, MA L L, HE J M, et al. Research progress of specific wetting oil-water separation materials[J]. Materials Review,2017,31(10):152-161(in Chinese).
[13]	YANG J, ZHANG Z Z, XU X H, et al. Superhydrophilic-superoleophobic coatings[J]. Journal of Materials Chemistry,2012,22(7):2834-2837.
[14]	杨明全. 超亲油材料在油水分离中的应用研究[D]. 大庆: 东北石油大学, 2017. YANG M Q. Research on the application of superoleophilic materials for oil/water separation[D]. Daqing: Northeast Petroleum University, 2017(in Chinese).
[15]	曾新娟, 王丽, 皮丕辉, 等. 特殊润湿性油水分离材料的开发与研究[J]. 化学进展, 2018, 30(1):73-86. doi: 10.7536/PC170828 ZENG X J, WANG L, PI P H, et al. Development and research of special wettable oil-water separation materials[J]. Progress in Chemistry,2018,30(1):73-86(in Chinese). doi: 10.7536/PC170828
[16]	PAN Q M, WANG M, WANG H B. Separating small amount of water and hydrophobic solvents by novel superhydrophobic copper meshes[J]. Applied Surface Science,2008,254:6002-6006. doi: 10.1016/j.apsusc.2008.03.034
[17]	WENZEL R N. Resistance of solid surfaces to wetting by water[J]. Industrial and Engineering Chemistry,1936,28(8):988-994.
[18]	DASSIE A, BOXTER S. Wettability of porous surfaces[J]. Transactions of the Faraday Society,1994,40(40):546-551.
[19]	李芝华, 沈玉婷. 一种氟硅烷改性聚丁二烯型聚氨酯水声透声材料及其制备方法: 中国, 109912966[P]. 2019-06-21. LI Z H, SHEN Y T. The invention relates to a fluorosilane modified polybutadiene type polyurethane underwater acoustic translucent material and a preparation method thereof: China, 109912966[P]. 2019-06-21(in Chinese)
[20]	徐林, 任煜, 张红阳, 等. 碱减量-氟硅烷处理涤纶织物的拒水拒油性[J]. 印染, 2017, 43(18):1-4. XU L, REN Y, ZHANG H Y, er al. Water and oil-repellency of polyester fabrics after alkali deweighting-fluoroalkylsilanes treatment[J]. Dyeing and Finishing,2017,43(18):1-4(in Chinese).
[21]	ZHOU H M, CHEN R R, LIU Q, et al. Fabrication of ZnO/epoxy resin superhydrophobic coating on AZ31 magnesium alloy[J]. Chemical Engineering Journal,2019,368:261-272. doi: 10.1016/j.cej.2019.02.032
[22]	李云涛, 晏华, 汪宏涛, 等. 正癸酸-月桂酸-硬脂酸三元低共熔体系/膨胀石墨复合相变材料的制备与表征[J]. 材料导报, 2017, 31(2):94-99. LI Y T, YAN H, WANG H T, et al. Preparation and characterization of decanoic acid-lauric acid-stearic acid temary eutectic mixture/expanded graphene composite phase change material with a low eutectic temperature[J]. Materials Review,2017,31(2):94-99(in Chinese).
[23]	YOU Y, ZHANG S Y, WAN L, et al. Preparation of continuous TiO₂ fibers by sol-gel method and its photocatalytic degradation on formaldehyde[J]. Applied Surface Science,2012,258(8):3469-3474. doi: 10.1016/j.apsusc.2011.11.099
[24]	YANG J, LI D, WANG X, et al. Rapid synthesis of nanocrystalline TiO₂/SnO₂ binary oxides and their photoinduced decomposition of methyl orange[J]. Journal of Solid State Chemistry,2002,165(1):193-198. doi: 10.1006/jssc.2001.9526
[25]	胡佩卓, 刘莲, 王海静, 等. 磷钼酸铵/聚丙烯酸复合凝胶吸附剂的合成及对铯的分离[J]. 核化学与放射化学, 2019, 41(4):362-369. HU P Z, LIU L, WANG H J, et al. Synthesis of ammonium phosphomolybdate/polyacrylic acid composite gel adsorbent and separation of cesium[J]. Journal of Nuclear and Radiochemistry,2019,41(4):362-369(in Chinese).
[26]	王春会, 李树材. 纳米TiO₂/阴离子水性聚氨酯粘合剂的研究[J]. 中国粘合剂, 2006, 15(3):1-3. WANG C H, LI S C. Study on nano-TiO₂/anionic aqueous polyurethane adhesive[J]. China Adhesives,2006,15(3):1-3(in Chinese).
[27]	刘婉颖, 邱宇洪, 刘颖, 等. 纳米TiO₂对D16T铝合金微弧氧化膜耐磨性的影响及机理[J]. 表面技术, 2019, 28(10):180-189. LIU W Y, QIU Y H, LIU Y, et al. Effect and mechanism of nano-TiO₂ on wear resistance of micro-arc oxidation film on D16T aluminium alloy[J]. Surface Technology,2019,28(10):180-189(in Chinese).
[28]	LIU S H, HAN G, SHU M H, et al. Monodispersed inorganic/organic hybrid spherical colloids: Versatile synthesis and their gas-triggered reversibly switchable wettability[J]. Journal of Materials Chemical,2010,20(44):10001-10009. doi: 10.1039/c0jm02101f
[29]	XU Z G, ZHAO Y, WANG H X, et al. A superamphiphobic coating with an ammonia-triggered transition to superhydrophilic and superoleophobic for oil-water separation[J]. Angewandte Chemie International Edition,2015,54(15):4527-4530.
[30]	LI F R, WANG Z R, HUANG S C, et al. Flexible, durable, and unconditioned superoleophobic/superhydrophilic surfaces for controllable transport and oil-water separation[J]. Advanced Funcational Materials,2018,28(20):1706867. doi: 10.1002/adfm.201706867