柔性可水洗的Zr-MOFs复合纳米纤维薄膜的制备和性能表征

doi:10.6023/A21080402

摘要/Abstract

柔性高吸附性材料在废水废气处理、防护服制造、有毒有害物质监测等诸多领域中发挥着关键的作用. 本工作采用水相合成的方法, 以三氟乙酸(trifluoroacetic acid, TFA)为结构导向剂, 以水为溶剂, 在静电纺纳米纤维上原位生长了金属有机框架材料NO₂-UiO-66, 制备了NO₂-UiO-66@PAN(聚丙烯腈)柔性纳米纤维膜材料. 并研究了不同配比的三氟乙酸/去离子水、不同的金属盐与有机配体比例以及水热生长时间对NO₂-UiO-66形貌和负载效果的影响. 最佳TFA添加含量为φ_TFA=30%, 金属盐与配体物质的量比为1∶1.5, 水热生长时间为4 h. 采用扫描电子显微镜(scanning electron microscope, SEM)、X射线衍射(X-ray diffraction, XRD)、傅里叶红外光谱(Fourier transform infrared spectroscopy, FT-IR)、热重(thermogravimetry, TG)分析及氮气吸附-脱附测试对NO₂-UiO-66@PAN纳米纤维膜结构进行了表征. 结果表明, NO₂-UiO-66均匀地负载在了纳米纤维上, 负载量可达33.28%, 比表面积为504.16 m²/g、孔体积为0.241 cm³/g. 并且在经过高温(320 ℃)、弯折和水、酸、碱洗涤后仍能保持结构的稳定性. 通过以上表征分析, 发现将NO₂-UiO-66负载在纳米纤维上能够得到物理和化学稳定性质优异的膜材料, 在有毒有害等恶劣条件下有很大的应用潜力.

关键词: 静电纺丝, 纳米纤维, 金属有机框架, NO₂-UiO-66, 水相合成

Flexible high adsorption materials play a key role in many fields such as wastewater and exhaust gas treatment, protective clothing manufacturing, toxic and harmful substance monitoring. In situ growth of NO₂-UiO-66 on electrostatic spun nanofiber was obtained by aqueous synthesis using trifluoroacetic acid as regulator, and water as solvent. The effects of different ratio of trifluoroacetic acid (TFA)/deionized water, different metal salt and ligand proportions and hydrothermal growth time on NO₂-UiO-66 morphology and load effects were studied. The add content of TFA was φ_TFA=30%, the molar ratio of metal salt and the ligand was 1∶1.5, and the hydrothermal growth time was maintained at 4 h, which proved to be the optimal synthetic conditions. The specific synthesis procedure of the NO₂-UiO-66@polyacrylonitrile composite nanofiber membrane (NO₂-UiO-66@PAN NM) was as follows: First, 10% (w) of PAN spinning liquid was woven into nanofiber membrane using the electrospinning method. Second, a solvent having a TFA content of 30% was prepared in a sealed glass bottle, followed by addition of metal salt (ZrCl₄) and organic ligand (2-nitroterephthalic acid, NO₂-H₂BDC). Finally, the PAN nanofiber was immersed in the precursor mixture, and after 30 min of ultrasonic treatment, it was placed in an oven at 100 ℃ for 4 h to obtain the NO₂-UiO-66@PAN NM. The structure of NO₂-UiO-66@PAN NM was characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry (TG) and nitrogen adsorption-desorption test. The characterization results showed that the NO₂-UiO-66 were uniformly loaded on nanofibers. The load could reach 33.28%, the Brunner-Emmet-Teller measurements (BET) surface area was 504.16 m²/g, and the pore volume was 0.241 cm³/g. Further, the NO₂-UiO-66@PAN nanofiber membrane still remained in the stability of the structure after being treated with high temperature (320 ℃), bending and washing with water, acid and alkali. Through the above characterization analysis, it was found that the NO₂-UiO-66 loaded on the nanofibers, which enabled the membrane material excellent in physical and chemical stable properties, and has a large application potential under harsh conditions such as toxic and harmful.

Key words: electrospinning, nanofiber, metal-organic framework, NO₂-UiO-66, aqueous synthesis

引用此文

郝肖柯, 翟振宇, 孙亚昕, 李从举. 柔性可水洗的Zr-MOFs复合纳米纤维薄膜的制备和性能表征[J]. 化学学报, 2022, 80(1): 49-55.

Xiaoke Hao, Zhenyu Zhai, Yaxin Sun, Congju Li. Preparation and Performance Characterization of Flexible and Washable Zr-MOFs Composite Nanofiber Membrane[J]. Acta Chimica Sinica, 2022, 80(1): 49-55.

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图/表 9

图1. 使用不同含量TFA合成的NO2-UiO-66@PAN NM XRD图像

Figure 1. XRD patterns of NO2-UiO-66@PAN NM synthesized using different contents of TFA

图2. 使用不同含量TFA合成的NO2-UiO-66@PAN NM SEM图像: (a) 10%, (b) 20%, (c) 30%, (d) 40%和(e) 50%

Figure 2. SEM images of NO2-UiO-66@PAN NM synthesized using different contents of TFA: (a) 10%, (b) 20%, (c) 30%, (d) 40% and (e) 50%

图3. 添加不同物质的量比的金属盐和配体合成的NO2-UiO-66@PAN NM SEM图像: (a) 1∶1, (b) 1∶1.5和(c) 1∶2

Figure 3. SEM images of NO2-UiO-66@PAN NM by adding different molar ratios of metal salts and ligands: (a) 1∶1, (b) 1∶1.5 and (c) 1∶2

图4. 不同水热时间合成的NO2-UiO-66@PAN NM SEM图像: (a) 1 h, (b) 2 h和(c) 4 h

Figure 4. SEM images of NO2-UiO-66@PAN NM synthesized by different hydrothermal growth time: (a) 1 h, (b) 2 h and (c) 4 h

图5. PAN NM和NO2-UiO-66@PAN NM的FT-IR谱图

Figure 5. FT-IR spectra of PAN NM and NO2-UiO-66@PAN NM

图6. PAN NM和NO2-UiO-66@PAN NM的TG曲线

Figure 6. Thermogravimetry curves of PAN NM and NO2-UiO-66@PAN NM

图7. NO2-UiO-66@PAN NM的N2吸附-脱附曲线及孔径分布

Figure 7. N2 adsorption-desorption curve and pore size distribution of NO2-UiO-66@PAN NM

图8. (a)纯PAN NM; NO2-UiO-66@PAN NM: (b)尺寸, (c)质量, 柔性测试: (d)弯曲, (e)对折, (f)缠绕

Figure 8. (a) Pure PAN NM; NO2-UiO-66@PAN NM: (b) size, (c) quality and flexible experiment: (d) bending, (e) fold, (f) twine

图9. NO2-UiO-66@PAN NM经过水、酸和碱洗涤后的XRD图像

Figure 9. XRD patterns of NO2-UiO-66@PAN NM after washing by water, acid and alkali

参考文献 39

[1]	Hao, X. K.; Zhang, X. L.; Zhai, Z. Y.; Li, C. J. Fine Chem. 2021, 38, 249 ; (in Chinese)
	( 郝肖柯, 张秀玲, 翟振宇, 李从举, 精细化工 2021, 38, 249.)
[2]	Hu, M. L.; Masoomi, M. Y.; Morsali, A. Coord. Chem. Rev. 2019, 387, 415. doi: 10.1016/j.ccr.2019.02.021
[3]	Georgiadis, A. G.; Charisiou, N.; Yentekakis, I. V.; Goula, M. A. Materials 2020, 13, 3640. doi: 10.3390/ma13163640
[4]	Lyu, L. X.; Zhao, Y. L.; Wei, Y. Y.; Wang, H. H. Acta Chim. Sinica 2021, 79, 869 ; (in Chinese) doi: 10.6023/A21030099
	( 吕露茜, 赵娅俐, 魏嫣莹, 王海辉, 化学学报 2021, 79, 869.)
[5]	Zeng, J. Y.; Wang, X. S.; Zhang, X. Z.; Zhuo, R. X. Acta Chim. Sinica 2019, 77, 1156 ; (in Chinese) doi: 10.6023/A19070259
	( 曾锦跃, 王小双, 张先正, 卓仁禧, 化学学报 2019, 77, 1156.)
[6]	Lazaro, I. A.; Wells, C. J. R.; Forgan, R. S. Angew. Chem. Int. Ed. 2020, 59, 5211. doi: 10.1002/anie.v59.13
[7]	He, P. C.; Zhou, J.; Zhou, A. W.; Dou, Y. B.; Li, J. R. Chem. J. Chin. Univ. 2019, 40, 855 ; (in Chinese)
	( 何鹏琛, 周健, 周阿武, 豆义波, 李建荣, 高等学校化学学报, 2019, 40, 855.)
[8]	Wang, D. K.; Li, Z. H. Res. Chem. Intermediat. 2017, 43, 5169. doi: 10.1007/s11164-017-3042-0
[9]	Wang, Y.; Li, B. T.; Zhang, B. C.; Tian, S. Y.; Yang, X.; Ye, H.; Xia, Z. J.; Zheng, G. X. J. Electroanal. Chem. 2020, 878, 114576. doi: 10.1016/j.jelechem.2020.114576
[10]	Hu, R.; Zhang, X.; Chi, K. N.; Yang, T.; Yang, Y. H. ACS Appl. Mater. Inter. 2020, 12, 30770. doi: 10.1021/acsami.0c06291
[11]	Sule, R.; Mishra, A. K. Environ. Sci. Pollut. R. 2020, 27, 16004. doi: 10.1007/s11356-020-08299-x
[12]	Wang, X. F.; Song, X. Z.; Sun, K. M.; Cheng, L.; Ma, W. Polyhedron 2018, 152, 155. doi: 10.1016/j.poly.2018.06.037
[13]	Cui, Y. J.; Li, B.; He, H. J.; Zhou, W.; Chen, B. L.; Qian, G. D. Acc. Chem. Res. 2016, 49, 483. doi: 10.1021/acs.accounts.5b00530
[14]	Jiao, L.; Seow, J. Y. R.; Skinner, W. S.; Wang, Z. U.; Jiang, H. L. Mater. Today 2019, 27, 43. doi: 10.1016/j.mattod.2018.10.038
[15]	Falcaro, P.; Ricco, R.; Yazdi, A.; Imaz, I.; Furukawa, S.; Maspoch, D.; Ameloot, R.; Evans, J. D.; Doonan, C. J. Coord. Chem. Rev. 2016, 307, 237. doi: 10.1016/j.ccr.2015.08.002
[16]	Zhang, H. B.; Nai, J. W.; Yu, L.; Lou, X. W. Joule 2017, 1, 77. doi: 10.1016/j.joule.2017.08.008
[17]	Liu, X. L. Front. Chem. Sci. Eng. 2020, 14, 216. doi: 10.1007/s11705-019-1857-5
[18]	Ahmad, K.; Nazir, M. A.; Qureshi, A. K.; Hussain, E.; Najam, T.; Javed, M. S.; Shah, S. S. A.; Tufail, M. K.; Hussain, S.; Khan, N. A.; Shah, H. U. R.; Ashfaq, M. Mat. Sci. Eng. B-Adv. 2020, 262, 114766.
[19]	Rada, Z. H.; Abid, H. R.; Sun, H. Q.; Shang, J.; Li, J. Y.; He, Y. D.; Liu, S. M.; Wang, S. B. Prog. Nat. Sci. 2018, 28, 160. doi: 10.1016/j.pnsc.2018.01.016
[20]	Luu, C. L.; Nguyen, T. T. V.; Nguyen, T.; Hoang, T. C. 2015, 6, 025004.
[21]	Stassen, I.; Dou, J. H.; Hendon, C.; Dinca, M. ACS Central Sci. 2019, 5, 1425. doi: 10.1021/acscentsci.9b00482
[22]	Taima-Mancera, I.; Rocio-Bautista, P.; Pasan, J.; Ayala, J. H.; Ruiz-Perez, C.; Afonso, A. M.; Lago, A. B.; Pino, V. Molecules 2018, 23, 2869. doi: 10.3390/molecules23112869
[23]	Zhang, L. Y.; Chen, H.; Bai, X. J.; Wang, S.; Li, L. L.; Shao, L.; He, W. X.; Li, Y. N.; Wang, T. Q.; Zhang, X. M.; Chen, J. Y.; Fu, Y. Chem. Commun. 2019, 55, 8293. doi: 10.1039/C9CC02614B
[24]	Hong, Y.; Liu, C. Y.; Cao, X. C.; Chen, Y.; Chen, C.; Chen, Y.; Pan, Z. J. Polymers 2018, 10, 1386. doi: 10.3390/polym10121386
[25]	Wahiduzzaman; Khan, M. R.; Harp, S.; Neumann, J.. J. Mater. Eng. Perform. 2016, 25, 1276. doi: 10.1007/s11665-016-1966-y
[26]	Wang, S. B.; Lin, Y.; Yang, J.; Shi, L.; Yang, G.; Zhuang, X. P.; Li, Z. H. Int. J. Hydrogen Energ. 2021, 46, 19106. doi: 10.1016/j.ijhydene.2021.03.033
[27]	Zhai, Z. Y.; Zhang, X. L.; Wang, J. N.; Li, H. Y.; Sun, Y. X.; Hao, X. K.; Qin, Y.; Niu, B.; Li, C. J. Chem. Eng. J. 2021, 428, 131720. doi: 10.1016/j.cej.2021.131720
[28]	Lu, A. X.; Ploskonka, A. M.; Tovar, T. M.; Peterson, G. W.; DeCoste, J. B. Ind. Eng. Chem. Res. 2017, 56, 14502. doi: 10.1021/acs.iecr.7b04202
[29]	Ma, K. K.; Islamoglu, T.; Chen, Z. J.; Li, P.; Wasson, M. C.; Chen, Y. W.; Wang, Y. F.; Peterson, G. W.; Xin, J. H.; Farha, O. K. J. Am. Chem. Soc. 2019, 141, 15626. doi: 10.1021/jacs.9b07301
[30]	Diring, S.; Furukawa, S.; Takashima, Y.; Tsuruoka, T.; Kitagawa, S. Chem. Mater. 2010, 22, 4531. doi: 10.1021/cm101778g
[31]	Surya, S. G.; Bhanoth, S.; Majhi, S. M.; More, Y. D.; Teja, V. M.; Chappanda, K. N. CrystEngComm 2019, 21, 7303. doi: 10.1039/C9CE01323G
[32]	Zhang, Y. Q.; Chu, Q.; Shi, Y.; Gao, J. S.; Xiong, W.; Huang, L.; Ding, Y. Acta Chim. Sinica 2021, 79, 361 ( in Chinese); doi: 10.6023/A20100478
	( 张雅祺, 楚奇, 石勇, 高金索, 熊巍, 黄磊, 丁越, 化学学报 2021, 79, 361.)
[33]	Shamsabadi, A. S.; Ranjbar, M.; Tavanai, H.; Farnood, A. Mater. Res. Express. 2019, 6, 055051. doi: 10.1088/2053-1591/ab0709
[34]	Zhang, X. F.; Wang, Z. G.; Feng, Y.; Zhong, Y. X.; Liao, J. Q.; Wang, Y. Q.; Yao, J. F. Fuel 2018, 234, 256. doi: 10.1016/j.fuel.2018.07.035
[35]	Ma, Y. L.; Liu, R. X.; Meng, S. Y.; Niu, L. T.; Yang, Z. W.; Lei, Z. Q. Acta Chim. Sinica 2019, 77, 153 ; (in Chinese) doi: 10.6023/A18090372
	( 马亚丽, 刘茹雪, 孟双艳, 牛力同, 杨志旺, 雷自强, 化学学报 2019, 77, 153.)
[36]	Choi, J.; Yoo, K. S.; Kim, D.; Kim, J.; Othman, M. R. ACS Appl. Nano Mater. 2021, 4, 4895. doi: 10.1021/acsanm.1c00444
[37]	Woo, H. C.; Yoo, D. K.; Jhung, S. H. ACS Appl. Mater. Inter. 2020, 12, 28885. doi: 10.1021/acsami.0c07123
[38]	Li, H.; Chu, H. J.; Ma, X. L.; Wang, G. R.; Liu, F. S.; Guo, M.; Lu, W. P.; Zhou, S. J.; Yu, M. Z. Chem. Eng. J. 2021, 408, 127277. doi: 10.1016/j.cej.2020.127277
[39]	Piscopo, C. G.; Polyzoidis, A.; Schwarzer, M.; Loebbecke, S. Micropor. Mesopor. Mat. 2015, 208, 30. doi: 10.1016/j.micromeso.2015.01.032