巯基化Zr-MOFs/聚酯无纺布复合材料制备及应用

doi:10.16085/j.issn.1000-6613.2021-0451

化工进展 ›› 2022, Vol. 41 ›› Issue (2): 854-861.DOI: 10.16085/j.issn.1000-6613.2021-0451

巯基化Zr-MOFs/聚酯无纺布复合材料制备及应用

陈运涛¹^,²^,³^,⁴(), 董晓旭⁵, 王洋⁴^,⁶, 王健男¹, 崔美⁵, 黄仁亮⁵()

^1.中交天津港湾工程研究院有限公司，天津 300222
^2.港口岩土工程技术交通运输行业重点实验室，天津 300222
^3.天津市港口岩土工程技术重点实验室，天津 300222
^4.中交第一航务工程局有限公司，天津 300222
^5.天津大学海洋科学与技术学院，天津 300072
^6.中交河海工程有限公司，天津 300222

收稿日期:2021-03-07 修回日期:2021-04-17 出版日期:2022-02-05 发布日期:2022-02-23
通讯作者: 黄仁亮
作者简介:陈运涛（1980—），男，高级工程师，研究方向为软土地基加固及污染治理。E-mail：chenyuntao@163.com。
基金资助:
国家自然科学基金(21976132)

Preparation and application of mercapto-functionalized Zr-MOFs/polyester fabric composite

CHEN Yuntao¹^,²^,³^,⁴(), DONG Xiaoxu⁵, WANG Yang⁴^,⁶, WANG Jiannan¹, CUI Mei⁵, HUANG Renliang⁵()

^1.CCCC Tianjin Port Engineering Institute Co. , Ltd. , Tianjin 300222, China
^2.Key Laboratory of Port Geotechnical Engineering of the Ministry of Communication, Tianjin 300222, China
^3.Key Laboratory of Port Geotechnical Engineering of Tianjin, Tianjin 300222, China
^4.First Harbor Engineering Co. , Ltd. of CCCC, Tianjin 300222, China
^5.School of Marine Science and Technology, Tianjin University, Tianjin 300072, China
^6.Hehai Engineering Co. , Ltd. of CCCC, Tianjin 300222, China

Received:2021-03-07 Revised:2021-04-17 Online:2022-02-05 Published:2022-02-23
Contact: HUANG Renliang

摘要/Abstract

摘要：

重金属和有机溶剂是水体中常见的污染物，十分有必要开发能够吸附重金属并同时分离有机溶剂的多功能复合材料。本论文以聚酯无纺布（NWF）为基底，经聚二甲基硅氧烷（PDMS）表面改性，进而采用原位生长方式将巯基化锆基金属有机骨架化合物（Zr-MOFs，简称PCN-222）负载在无纺布表面，制备了一种疏水的PDMS/PCN-222@NWF复合材料。在低表面能PDMS改性和原位生长PCN-222晶体所形成的粗糙表面共同作用下，其水接触角为141.7°。油水分离测试结果显示其分离效率最高可达98.6%，并且经过5次循环使用后，分离效率仍然可达94%以上。此外，由于无纺布表面负载有巯基化PCN-222颗粒，PDMS/PCN-222@NWF复合物可同时吸附水中的Hg²⁺，最高吸附量达294.4mg/g。

关键词: 重金属, 吸附, 分离, 金属有机骨架化合物, 疏水

Abstract:

Heavy metal ions and organic solvents are common pollutants in water. It is important to develop multifunctional composites to simultaneously remove heavy metal ions and separate organic solvents from water. In this study, a hydrophobic composite (PDMS/PCN-222@NWF) was successfully prepared via surface modification of PDMS and in situ growth of the mercapto functionalized Zr-MOFs (PCN-222) on the surface of the polyester non-woven fabric (NWF). The as-prepared composite had a water contact angle (WCA) of 141.7°, which was probably attributed to both the rough surface derived from in situ growth of PCN-222 crystals and the low surface energy due to coating of hydrophobic PDMS. The PDMS/PCN-222@NWF composite can effectively separate oil-water mixture with a maximum separation efficiency about 98.6%, and the separation efficiency can still reach above 94% after 5 cycles of reuse. In addition, the PDMS/PCN-222@NWF composite can also selectively remove Hg²⁺ ions from water with a maximum adsorption capacity of 294.4mg/g due to the coating of mercapto functionalized PCN-222 crystals on the surface of non-woven fabric.

Key words: heavy metal ions, adsorption, separation, metal-organic frameworks, hydrophobicity

中图分类号:

TQ028.8

陈运涛, 董晓旭, 王洋, 王健男, 崔美, 黄仁亮. 巯基化Zr-MOFs/聚酯无纺布复合材料制备及应用[J]. 化工进展, 2022, 41(2): 854-861.

CHEN Yuntao, DONG Xiaoxu, WANG Yang, WANG Jiannan, CUI Mei, HUANG Renliang. Preparation and application of mercapto-functionalized Zr-MOFs/polyester fabric composite[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 854-861.

图/表 15

图1 PDMS/PCN-222@NWF复合物制备的示意图

图2 原始无纺布及改性无纺布扫描电镜图

图3 无纺布（NWF）和PDMS/PCN-222@NWF的XPS图

图4 PDMS/PCN-222@NWF复合材料C、N、O、Si、Zr和S元素的EDS图

表1 PDMS/PCN-222@NWF中各元素相对含量汇总

元素	相对含量/%
C	61.8
O	21.9
N	0.1
Si	8.4
S	3.1
Zr	4.7

图5 PDMS/PCN-222@NWF复合物表面生长的巯基化PCN-222晶体PXRD图谱

图6 原始无纺布及改性无纺布的水接触角

图7 疏水PDMS/PCN-222@NWF复合物分离水-氯仿混合溶液

表2 PDMS/PCN-222@NWF复合物对不同油水体系的分离效率

编号	油-水混合物	分离效率/%
1	正己烷-水	98.6
2	二氯甲烷-水	96.6

图8 二氯甲烷-水混合物的循环分离效率

图9 NWF、PDMS@NWF和PDMS/PCN-222@NWF复合物对Hg2+的吸附量

图10 不同pH对PDMS/PCN-222@NWF吸附Hg2+的影响（离子浓度为20mg/L）

图11 PDMS/PCN-222@NWF对Hg2+的吸附时间历程[10mg PDMS/PCN-222@NWF，20mL Hg2+溶液（20mg/L），

pH=6，25℃]

表3 Hg2+吸附的拟二级动力学模型参数

q_e（实验值）

/mg·g^-1

R²

图12 水与正己烷体积比对Hg2+吸附量的影响

参考文献 25

1	SONG S, YANG H, SU C P, et al. Ultrasonic-microwave assisted synthesis of stable reduced graphene oxide modified melamine foam with superhydrophobicity and high oil adsorption capacities[J]. Chemical Engineering Journal, 2016, 306: 504-511.
2	李竞草, 吴冬霞, 常丽萍, 等. 疏水性金属-有机骨架材料的研究进展[J]. 化工进展, 2020, 39(1): 224-232.
	LI J C, WU D X, CHANG L P, et al. Research progress of hydrophobic metal-organic framework materials[J]. Chemical Industry and Engineering Progress, 2020, 39(1): 224-232.
3	XU Z Q, WANG J W, LI H J, et al. Coating sponge with multifunctional and porous metal-organic framework for oil spill remediation[J]. Chemical Engineering Journal, 2019, 370: 1181-1187.
4	ZHANG Y, ZHANG N, ZHOU S, et al. Facile preparation of ZIF-67 coated melamine sponge for efficient oil/water separation[J]. Industrial & Engineering Chemistry Research, 2019, 58(37): 17380-17388.
5	KOBIELSKA P A, HOWARTH A J, FARHA O K, et al. Metal-organic frameworks for heavy metal removal from water[J]. Coordination Chemical Reviews, 2018, 358: 92-107.
6	WANG K, GU J, YIN N. Efficient removal of Pb(Ⅱ) and Cd(Ⅱ) using NH₂-functionalized Zr-MOFs via rapid microwave-promoted synthesis[J]. Industrial & Engineering Chemistry Research, 2017, 56(7): 1880-1887.
7	WANG B, LYU X, FENG D, et al. Highly stable Zr(Ⅳ)-based metal-organic frameworks for the detection and removal of antibiotics and organic explosives in water[J]. Journal of the American Chemical Society, 2016, 138(19): 6204-6216.
8	WANG B, WANG P, XIE L, et al. A stable zirconium based metal-organic framework for specific recognition of representative polychlorinated dibenzo-p-dioxin molecules[J]. Nature Communications, 2019, 10: 3861.
9	XIE L, LIU X, HE T, et al. Metal-organic frameworks for the capture of trace aromatic volatile organic compounds[J]. Chem., 2018, 4(8): 1911-1927.
10	LI J, YU J, LU W, et al. Porous materials with pre-designed single-molecule traps for CO₂ selective adsorption[J]. Nature Communications, 2013, 4: 1538.
11	CHUNG C H, LIU W C, HONG J L. Superhydrophobic melamine sponge modified by cross-linked urea network as recyclable oil absorbent materials[J]. Industrial & Engineering Chemistry Research, 2018, 57(25): 8449-8459.
12	KIM D, KIM D W, BUYUKCAKIR O, et al. Highly hydrophobic ZIF-8/carbon nitride foam with hierarchical porosity for oil capture and chemical fixation of CO₂[J]. Advanced Functional Matererials, 2017, 27(23): 8.
13	LEI Z W, DENG Y H, WANG C Y. Multiphase surface growth of hydrophobic ZIF-8 on melamine sponge for excellent oil/water separation and effective catalysis in a Knoevenagel reaction[J]. Journal of Materials Chemistry A, 2018, 6(7): 3258-3263.
14	DONG X X, CUI M, HUANG R L, et al. Polydopamine-assisted surface coating of MIL-53 and dodecanethiol on a melamine sponge for oil-water separation[J]. Langmuir, 2020, 36: 1212-1220.
15	CHAKRABORTY A, BHATTACHARYYA S, HAZRA A, et al. Post-synthetic metalation in an anionic MOF for efficient catalytic activity and removal of heavy metal ions from aqueous solution[J]. Chemical Communications, 2016, 52(13): 2831-2834.
16	ALQADAMI A A, KHAN M A, SIDDIQUI M R, et al. Development of citric anhydride anchored mesoporous MOF through post synthesis modification to sequester potentially toxic lead(Ⅱ) from water[J]. Microporous and Mesoporous Materials, 2018, 261: 198-206.
17	FU L K, WANG S X, LIN G, et al. Post-functionalization of UiO-66-NH₂ by 2,5-dimercapto-1,3,4-thiadiazole for the high efficient removal of Hg(Ⅱ) in water[J]. Journal of Hazardous Materials, 2019, 368: 42-51.
18	LIN D W, LIU X, HUANG R L, et al. One-pot synthesis of mercapto functionalized Zr-MOFs for the enhanced removal of Hg²⁺ ions from water[J]. Chemical Communications, 2019, 55: 6775-6778.
19	CAO C Y, GE M Z, HUANG J Y, et al. Robust fluorine-free superhydrophobic PDMS-ormosil@fabrics for highly effective self-cleaning and efficient oil-water separation[J]. Journal of Materials Chemistry A, 2016, 4: 12179-12187.
20	ZHU T X, LI S H, HUANG J Y, et al. Rational design of multi-layered superhydrophobic coating on cotton fabrics for UV shielding, self-cleaning and oil-water separation[J]. Materials Design, 2017, 134: 342-351.
21	ZHANG G Y, ZHUANG Y H, SHAN D, et al. Zirconium-based porphyrinic metal-organic framework (PCN-222): enhanced photoelectrochemical response and its application for label-free phosphoprotein detection[J]. Analytical Chemistry, 2016, 88: 11207-11212.
22	ZHANG Y Z, WANG X Y, WANG C H, et al. Facile preparation of flexible and stable superhydrophobic non-woven fabric for efficient oily wastewater treatment[J]. Surface and Coatings Technology, 2019, 357: 526-534.
23	马杨, 王佳铭, 贺高红, 等. 微孔膜法油水分离-表面性质及微观结构的研究进展[J]. 化工进展, 2020, 39(6): 2145-2155.
	MA Y, WANG J M, HE G H, et al. Micro-porous membrane technology for oil-water separation: progress in surface properties and microscopic structures[J]. Chemical Industry and Engineering Progress, 2020, 39(6): 2145-2155.
24	刘晓真, 张泰, 肖长发. 疏水亲油分离膜的润湿性研究进展[J]. 化工进展, 2020, 39(11): 4516-4528
	LIU X Z, ZHANG T, XIAO C F. Research progress on wettability of hydrophobic-oleophylic membranes in oil-water separation[J]. Chemical Industry and Engineering Progress, 2020, 39(11): 4516-4528.
25	曹思静, 潘子鹤, 杜志平, 等. 超亲水/水下超疏油膜的制备及油水分离性能[J]. 化工进展, 2018, 37(10): 3744-3750.
	CAO S J, PAN Z H, DU Z P, et al. Fabrication of superhydrophilic/underwater superoleophobic mesh for oil-water separation[J]. Chemical Industry and Engineering Progress, 2018, 37(10): 3744-3750.

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巯基化Zr-MOFs/聚酯无纺布复合材料制备及应用

Preparation and application of mercapto-functionalized Zr-MOFs/polyester fabric composite

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