Superhydrophobic porous foams constructed based on the high internal phase emulsion template method

doi:10.16085/j.issn.1000-6613.2023-1542

Abstract

Abstract:

The discharge of industrial oily wastewater and the occurrence of marine oil spills have led to serious damage to the aquatic environment. In order to achieve efficient and cost-effective oil/water separation, a superhydrophobic porous foam was successfully fabricated in this study applying the high internal phase emulsion template method. The physical and chemical structures of the materials were characterized by SEM, MIP, FTIR and XPS, and the wettability of the materials was also tested. These materials exhibited superhydrophobic-super oleophilic properties, evidenced by a high water contact angle of 146.8°, an impressively low water rolling angle of merely 6° and an almost negligible oil contact angle. The hydrophobicity of the material can be easily tailored by adjusting the monomer ratios. Remarkably, this material demonstrated exceptional oil-absorption capabilities with oil-absorption rates ranging from 30.17g/g to 76.65g/g across various oils and organic reagents. Furthermore, the material addressed surface oil spills and underwater heavy oil release, maintaining a consistent oil recovery efficiency of 90% throughout 10 cycles. Further research was conducted on the adsorption process of the material on oil products, and the results showed a closer adherence to the pseudo-first-order adsorption kinetic model (R²>0.99) for diesel and ethanol. Consequently, the material presented as a superhydrophobic-super oleophilic porous substance, exhibiting elevated oil adsorption ratio, remarkable oil recovery efficiency and commendable reusability. Its potential applications in the realm of oil-water separation were abundant.

Key words: high internal phase emulsion template method, superhydrophobic, porous material, oil recovery, oil/water separation

摘要：

工业含油废水的排放和海洋溢油事故的发生导致水体区域环境遭到了严重破坏，为了实现高效且低成本的油水分离，本研究利用高内相乳液模板法构筑了一种超疏水多孔泡沫。利用扫描电子显微镜、压泵仪、傅里叶变换红外光谱、X射线光电子能谱对材料的物理、化学结构进行了表征，测试了材料的润湿性：水接触角达146.8°，水滚动角为6°，油接触角几乎为0°，显示出超疏水-超亲油特性，且材料的润湿性可通过调整单体之间的配比进行调控。材料对不同类型的油或有机试剂，吸收倍率在30.17~76.65g/g，显示出优异的吸油能力。材料能有效清理水面浮油和水下重油，并可循环利用，经历10次吸附-脱附实验后，油品的回收效率依然维持在90%左右。进一步研究了材料对油品的吸附过程，结果表明，其对柴油和乙醇的吸附过程更符合伪一阶吸附动力学模型（R²>0.99）。综上表明，该材料是一种吸油倍率高、油回收效率良好且可重复利用的超疏水-超亲油多孔材料，在油水分离领域具有广阔的应用前景。

关键词: 高内相乳液模板法, 超疏水, 多孔材料, 油品回收, 油水分离

CLC Number:

O632.7

WEN Zhipeng, KE Siyin, YANG Huilin, LI Yong, YU Chuanming, LIAO Mingneng. Superhydrophobic porous foams constructed based on the high internal phase emulsion template method[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5633-5641.

温志鹏, 柯思因, 杨惠林, 李泳, 余传明, 廖铭能. 基于高内相乳液模板法构筑的超疏水多孔泡沫[J]. 化工进展, 2024, 43(10): 5633-5641.

Figures/Tables 10

样品编号	TFEMA/g	DVB/g	超纯水/mL
1	0.10	0.40	10
2	0.20	0.30	10
3	0.25	0.25	10
4	0.30	0.20	10
5	0.30	0.20	15
6	0.30	0.20	20

文献	材料	吸附油品	吸油倍率/g·g^-1
Wang等^[33]	木质气凝胶	乙醇	13
Wang等^[33]	木质气凝胶	乙酸乙酯	15
Khosravi等^[34]	疏水海绵	四氯化碳	58
Gu等^[35]	纳米粒子	柴油	3.63
Wang等^[36]	碳海绵	四氯化碳	43
本文	超疏水多孔泡沫（样品6）	乙醇	30.17
		乙酸乙酯	41.96
		四氯化碳	76.65
		柴油	33.03

模型名称	表达式	油品类型	参数
模型名称	表达式	油品类型	R²	斜率	截距
伪一阶吸附动力学模型	$l n q e - q t = l n q e - K 1 t$	乙醇	0.9921	-0.03324	3.264
伪一阶吸附动力学模型	$l n q e - q t = l n q e - K 1 t$	柴油	0.9945	-0.02874	3.050
伪二阶吸附动力学模型	$t q t = 1 K 2 × q e 2 + t q e$	乙醇	0.9664	0.01570	0.2804
伪二阶吸附动力学模型	$t q t = 1 K 2 × q e 2 + t q e$	柴油	0.9793	0.2405	0.4369
Elovich吸附动力学模型	$q t = K 3 l n t + B$	乙醇	0.9816	6.322	2.053
Elovich吸附动力学模型	$q t = K 3 l n t + B$	柴油	0.9695	5.704	-0.7562
Weber-Morris吸附动力学模型	$q t = K 4 × t 12 + C$	乙醇	0.9514	2.510	7.120
Weber-Morris吸附动力学模型	$q t = K 4 × t 12 + C$	柴油	0.9717	2.002	4.768

模型名称	表达式	油品类型	参数
模型名称	表达式	油品类型	R²	斜率	截距
伪一阶吸附动力学模型	$l n q e - q t = l n q e - K 1 t$	乙醇	0.9921	-0.03324	3.264
伪一阶吸附动力学模型	$l n q e - q t = l n q e - K 1 t$	柴油	0.9945	-0.02874	3.050
伪二阶吸附动力学模型	$t q t = 1 K 2 × q e 2 + t q e$	乙醇	0.9664	0.01570	0.2804
伪二阶吸附动力学模型	$t q t = 1 K 2 × q e 2 + t q e$	柴油	0.9793	0.2405	0.4369
Elovich吸附动力学模型	$q t = K 3 l n t + B$	乙醇	0.9816	6.322	2.053
Elovich吸附动力学模型	$q t = K 3 l n t + B$	柴油	0.9695	5.704	-0.7562
Weber-Morris吸附动力学模型	$q t = K 4 × t 12 + C$	乙醇	0.9514	2.510	7.120
Weber-Morris吸附动力学模型	$q t = K 4 × t 12 + C$	柴油	0.9717	2.002	4.768

References 44

1	DAI Lei, CHENG Ting, WANG Yan, et al. A self-assembling guar gum hydrogel for efficient oil/water separation in harsh environments[J]. Separation and Purification Technology, 2019, 225: 129-135.
2	ASIF Zunaira, CHEN Zhi, AN Chunjiang, et al. Environmental impacts and challenges associated with oil spills on shorelines[J]. Journal of Marine Science and Engineering, 2022, 10(6): 762.
3	HU Jiang, ZHU Jundong, GE Shengzhuo, et al. Biocompatible, hydrophobic and resilience graphene/chitosan composite aerogel for efficient oil-water separation[J]. Surface and Coatings Technology, 2020, 385: 125361.
4	LIU Zitian, MA Wensong, LIN Ligang, et al. Mussel- and nacre-inspired dual-bionic alginate-based hydrogel coating with multi-matrix applicability, high separation stability and antifouling performance for oil/water separation[J]. International Journal of Biological Macromolecules, 2023, 246: 125686.
5	YOUNG Thomas. An essay on the cohesion of fluids[J]. Philosophical Transactions of the Royal Society of London, 1805, 95: 65-87.
6	CASSIE A B D, BAXTER S. Wettability of porous surfaces[J]. Transactions of the Faraday Society, 1944, 40(0): 546-551.
7	YU Chuanming, LIN Wenyu, JIANG Jine, et al. Preparation of a porous superhydrophobic foam from waste plastic and its application for oil spill cleanup[J]. RSC Advances, 2019, 9(65): 37759-37767.
8	ZHAO Caimei, CHEN Lei, YU Chuanming, et al. Fabrication of hydrophobic NiFe₂O₄@poly(DVB-LMA) sponge via a pickering emulsion template method for oil/water separation[J]. Soft Matter, 2021, 17(8): 2327-2339.
9	YANG Xiaocang, YIN Zhengqiao, ZHANG Xiaoyu, et al. Fabrication of emulsion-templated macroporous poly(ε‍-caprolactone) towards highly effective and sustainable oil/water separation[J]. Polymer, 2020, 204: 122852.
10	TU Shuhua, CHEN Min, WU Limin. Robust porous organosilica monoliths via a surfactant-free high internal phase emulsion process for efficient oil-water separation[J]. Journal of Colloid and Interface Science, 2020, 566: 338-346.
11	WANG Fan, MA Rongrong, TIAN Yaoqi. Fabrication of superhydrophobic/oleophilic starch cryogel via a simple sol-gel immersion process for removing oil from water[J]. Industrial Crops and Products, 2022, 184: 115010.
12	LIU Meng, TAN Xinyu, LI Xinyi, et al. Transparent superhydrophobic EVA/SiO₂/PTFE/KH-570 coating with good mechanical robustness, chemical stability, self-cleaning effect and anti-icing property fabricated by facile dipping method[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 658: 130624.
13	TIAN Jie, BAO Jiaxin, LI Lianhui, et al. Facile fabrication of superhydrophobic coatings with superior corrosion resistance on LA103Z alloy by one-step electrochemical synthesis[J]. Surface and Coatings Technology, 2023, 452: 129090.
14	SHAO Chuang, JIANG Mingliang, ZHANG Jingpeng, et al. Construction of a superhydrophobic wood surface coating by layer-by-layer assembly: Self-adhesive properties of polydopamine[J]. Applied Surface Science, 2023, 609: 155259.
15	ZHENG Jiawei, YANG Jinchuan, CAO Wen, et al. Fabrication of transparent wear-resistant superhydrophobic SiO₂ film via phase separation and chemical vapor deposition methods[J]. Ceramics International, 2022, 48(21): 32143-32151.
16	TANG Wei, JIAN Yulan, SHAO Mingjun, et al. A novel two-step strategy to construct multifunctional superhydrophobic wood by liquid-vapor phase deposition of methyltrimethoxysilane for improving moisture resistance, anti-corrosion and mechanical strength[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2023, 666: 131314.
17	LIU Jun, GUO Hong, SUN Zhiye, et al. Preparation of photothermal membrane for vacuum membrane distillation with excellent anti-fouling ability through surface spraying[J]. Journal of Membrane Science, 2021, 634: 119434.
18	KABALNOV Alexey. Ostwald ripening and related phenomena[J]. Journal of Dispersion Science and Technology, 2001, 22(1): 1-12.
19	PIORKOWSKI Daniel T, MCCLEMENTS David Julian. Beverage emulsions: Recent developments in formulation, production, and applications[J]. Food Hydrocolloids, 2014, 42: 5-41.
20	PARK Sun Hee, HONG Chi Rac, CHOI Seung Jun. Prevention of Ostwald ripening in orange oil emulsions: Impact of surfactant type and Ostwald ripening inhibitor type[J]. LWT, 2020, 134: 110180.
21	CARRANZA Arturo, PÉREZ-GARCÍA María G, SONG Kunlin, et al. Deep-eutectic solvents as MWCNT delivery vehicles in the synthesis of functional poly(HIPE) nanocomposites for applications as selective sorbents[J]. ACS Applied Materials & Interfaces, 2016, 8(45): 31295-31303.
22	马艳明. 甲基丙烯酸三氟乙酯改性聚合物的合成、表征及性能研究[D]. 济南: 济南大学, 2013.
	MA Yanming. Fluoropolymer based on trifluoroethyl methacrylate (TFEMA): Synthesis, characterization and properties[D]. Jinan: University of Jinan, 2013.
23	HOON Kim Kyung, HOON Cho Jong, Hwang Jin UNG, et al. A key strategy to form a LiF-based SEI layer for a lithium-ion battery anode with enhanced cycling stability by introducing a semi-ionic CF bond[J]. Journal of Industrial and Engineering Chemistry, 2021, 99: 48-54.
24	KHALAF Mai M, EL-LATEEF Hany M ABD, Van-Duong DAO, et al. Electrocatalysis of methanol oxidation in alkaline electrolytes over novel amorphous Fe/Ni biphosphate material prepared by different techniques[J]. Nanomaterials, 2022, 12(19): 3429.
25	LEE Chunwoo, YAMAGUCHI Satoshi, IMAZATO Satoshi. Quantitative evaluation of the degradation amount of the silane coupling layer of CAD/CAM resin composites by water absorption[J]. Journal of Prosthodontic Research, 2023, 67(1): 55-61.
26	Tae-Gyu WOO, PARK Il-Song, JUNG Kwang-Hee, et al. Effect of N₂ plasma treatment on the adhesion of Cu/Ni thin film to polyimide[J]. Metals and Materials International, 2011, 17(5): 789-795.
27	HE Chao, ZHAO Jun, YANG Yanhui, et al. Multiscale characteristics dynamics of hydrochar from hydrothermal conversion of sewage sludge under sub- and near-critical water[J]. Bioresource Technology, 2016, 211: 486-493.
28	DE A DIAS Frederico G, VEIGA Amanda G, GOMES Antônio Pedro A DA C P, et al. Using XPS and FTIR spectroscopies to investigate polyamide 11 degradation on aging flexible risers[J]. Polymer Degradation and Stability, 2022, 195: 109787.
29	KEHRER Matthias, DUCHOSLAV Jiri, HINTERREITER Andreas, et al. XPS investigation on the reactivity of surface imine groups with TFAA[J]. Plasma Processes and Polymers, 2019, 16(4): 1800160.
30	TAO Chengan, WANG Jianfang, QIN Shiqiao, et al. Fabrication of pH-sensitive graphene oxide-drug supramolecular hydrogels as controlled release systems[J]. Journal of Materials Chemistry, 2012, 22(47): 24856-24861.
31	ZOU Yanqi, ZHOU Xiaoyu, XIE Liuhong, et al. Vertically-ordered mesoporous silica films grown on boron nitride-graphene composite modified electrodes for rapid and sensitive detection of carbendazim in real samples[J]. Frontiers in Chemistry, 2022, 10: 939510.
32	SUN Lidong, PENG Cong, KONG Lingchen, et al. Interface-structure-modulated CuF₂/CF _x composites for high-performance lithium primary batteries[J]. Energy & Environmental Materials, 2023, 6(2): e12323.
33	WANG Kaili, LIU Xiaorong, TAN Yi, et al. Two-dimensional membrane and three-dimensional bulk aerogel materials via top-down wood nanotechnology for multibehavioral and reusable oil/water separation[J]. Chemical Engineering Journal, 2019, 371: 769-780.
34	KHOSRAVI Maryam, AZIZIAN Saeid. Synthesis of a novel highly oleophilic and highly hydrophobic sponge for rapid oil spill cleanup[J]. ACS Applied Materials & Interfaces, 2015, 7(45): 25326-25333.
35	GU Junjun, JIANG Wei, WANG Fenghe, et al. Facile removal of oils from water surfaces through highly hydrophobic and magnetic polymer nanocomposites[J]. Applied Surface Science, 2014, 301: 492-499.
36	WANG Ni, DENG Ziwei. Synthesis of magnetic, durable and superhydrophobic carbon sponges for oil/water separation[J]. Materials Research Bulletin, 2019, 115: 19-26.
37	YU Chuanming, JIANG Jin'e, LIU Yeyuan, et al. Facile fabrication of compressible, magnetic and superhydrophobic poly(DVB-MMA) sponge for high-efficiency oil-water separation[J]. Journal of Materials Science, 2021, 56(4): 3111-3126.
38	MUSTAPHA S, SHUAIB D T, NDAMITSO M M, et al. Adsorption isotherm, kinetic and thermodynamic studies for the removal of Pb(‍Ⅱ), Cd(‍Ⅱ‍), Zn(‍Ⅱ) and Cu(‍Ⅱ) ions from aqueous solutions using Albizia lebbeck pods[J]. Applied Water Science, 2019, 9(6): 142.
39	AMER Mohammad W, AHMAD Rafat A, AWWAD Akl M. Biosorption of Cu(‍Ⅱ), Ni(‍Ⅱ), Zn(‍Ⅱ) and Pb(‍Ⅱ) ions from aqueous solution by Sophora japonica pods powder[J]. International Journal of Industrial Chemistry, 2015, 6(1): 67-75.
40	PATEL Himanshu. Elution profile of cationic and anionic adsorbate from exhausted adsorbent using solvent desorption[J]. Scientific Reports, 2022, 12(1): 1665.
41	ADEWOYE T L, OGUNLEYE O O, ABDULKAREEM A S, et al. Optimization of the adsorption of total organic carbon from produced water using functionalized multi-walled carbon nanotubes[J]. Heliyon, 2021, 7(1): e05866.
42	WEN Zhipeng, YANG Huilin, Mingzhe LYU, et al. A compressible porous superhydrophobic material constructed by a multi-template high internal phase emulsion method for oil-water separation[J]. RSC Advances, 2023, 13(37): 25920-25929.
43	RAO V Trinadha, SUNEEL V, ALEX M J, et al. Assessment of MV Wakashio oil spill off Mauritius, Indian Ocean through satellite imagery: A case study[J]. Journal of Earth System Science, 2022, 131(1): 21.
44	WHITE Helen K, HSING Pen-Yuan, CHO Walter, et al. Impact of the Deepwater Horizon oil spill on a deep-water coral community in the Gulf of Mexico[J]. Proceedings of the National Academy of Sciences of the United States of America, 2012, 109(50): 20303-20308.

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