一种新型磺酸修饰的共价有机框架用于二氧化碳吸收和染料吸附

doi:10.6023/A21100454

摘要/Abstract

环境污染是地球现今的重要问题之一, 而其中就包括水污染与温室效应. 共价有机框架(covalent organic frameworks, COFs)作为一种新兴的晶态多孔聚合物, 因其优异的吸附性能, 在污染治理领域具有广阔的应用前景. 本工作报道了一种基于β-酮胺单体通过迈克尔加成-消除反应合成的磺酸型微孔COF (JUC-603). 该COF不仅能有效分离水中染料, 而且具有显著的二氧化碳吸收能力. 本研究为环境修复中的染料分离和二氧化碳吸收领域提供了一种具有潜力的材料.

关键词: 多孔材料, 共价有机框架, 染料吸附, 二氧化碳吸收, 迈克尔加成-消除反应

Environmental pollution is one of the most severe problems facing the earth today, including water pollution and the greenhouse effect caused by the indiscriminate discharge of organic dyes and abundant carbon dioxide emissions (CO₂), respectively. Therefore, removing dyes from water and eliminating CO₂ in the atmosphere is an urgent issue that needs to be solved. Among them, with low cost and high adsorption efficiency, porous materials have become one of the most common materials to adsorb organic dyes and uptake CO₂. Covalent organic frameworks (COFs), as a burgeoning class of crystalline porous polymers, present a promising application potential in many areas, such as gas adsorption and separation, heterogeneous catalysis, semiconductors and sensors due to their regular pores, modifiable frameworks, extensive specific areas and excellent stability. Especially the introduction of the functional groups to the skeleton of COFs provides abundant active sites to adsorb specific dyes and uptake gases. Inspired by this, we report a microporous COF (JUC-603, JUC=Jilin University China) decorated with sulfonic acid group. This COF was successfully synthesized through β-ketoenamine based Michael addition-elimination reaction of 1,3,5-tris(3-dimethylamino-1-oxoprop-2-en-yl)benzene (TDOEB) and p-phenylenediamine (PPDA). A series of characterizations proved that JUC-603 had high crystallinity, opening microporous pore and excellent stability. Nitrogen adsorption-desorption isotherm revealed a high Brunauer-Emmett-Teller (BET) surface area (774 m²/g) and large pore size (1.6 nm). Moreover, we studied the adsorption of JUC-603 on dyes from aqueous solutions by ultraviolet- visible spectrophotometry and the uptake capacity through CO₂ adsorption-desorption. These results showed that JUC-603 could selectively adsorb cationic dyes such as crystal violet and methylene blue as well as uptake CO₂ effectively (52 cm³/g at 273 K and 0.1 MPa). The ideal performance was attributed to the modulation of active sulfonic acid sites on the framework of JUC-603. This research thus indicates that the COF as a promising functionalized porous material has great potential in environmental remediation.

Key words: porous material, covalent organic frameworks, dye adsorption, CO₂ uptake, Michael addition-elimination reaction

引用此文

王自陶, 刘耀祖, 王钰杰, 方千荣. 一种新型磺酸修饰的共价有机框架用于二氧化碳吸收和染料吸附[J]. 化学学报, 2022, 80(1): 37-43.

Zitao Wang, Yaozu Liu, Yujie Wang, Qianrong Fang. A New Covalent Organic Framework Modified with Sulfonic Acid for CO₂ Uptake and Selective Dye Adsorption[J]. Acta Chimica Sinica, 2022, 80(1): 37-43.

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图/表 9

图式1. 3-PD和JUC-603的合成

Scheme 1. Syntheses of 3-PD and JUC-603

图1. 3-PD的PXRD (a)和孔道结构图(b); JUC-603的PXRD (c)和孔道结构图(d)

Figure 1. (a) PXRD patterns and (b) structural representations of 3-PD; (c) PXRD patterns and (d) structural representations of JUC-603

图2. 3-PD的红外谱图(a), 固态13C NMR光谱(c)和热重曲线(e); JUC-603的红外谱图(b), 固态13C NMR光谱(d)和热重曲线(f)

Figure 2. (a) FT-IR spectra, (c) solid-state 13C NMR spectrum and (e) TGA curve of 3-PD; (b) FT-IR spectra, (d) solid-state 13C NMR spectrum and (f) TGA curve of JUC-603

图3. JUC-603在各种有机溶剂和1.0 mol/L盐酸水溶液中处理24 h后的PXRD

Figure 3. PXRD patterns of JUC-603 after the treatment in a variety of organic solvents and acid (1.0 mol/L HCl) aqueous solution for 24 h

图4. 3-PD (a)和JUC-603 (b)的吸附-脱附曲线; 利用NLDFT推导出的3-PD (c)和JUC-603 (d)的孔径分布示意图

Figure 4. N2 adsorption-desorption isotherms of (a) 3-PD and (b) JUC-603; the pore-size distribution of (c) 3-PD and (d) JUC-603 estimated by nonlocal density functional theory (NLDFT)

COFs	CO₂吸收能力/(cm³•g^-1)
COF-1	51
COF-5	31
COF-103	38
TDCOF-5	47
DmaTph	37
RT-COF-1	44
3-PD	45
JUC-603	51.7

表1. 几种常见COFs的CO2吸收能力

Table 1. The CO2 uptake ability of several common COFs

图5. 3-PD分别在298 K (a)和273 K (b)的CO2吸收值; JUC-603在298 K (c)和273 K (d)的CO2吸收值

Figure 5. CO2 uptakes for 3-PD at (a) 298 K and (b) 273 K as well as JUC-603 at (c) 298 K and (d) 273 K

图6. 结晶紫(a)和亚甲基蓝(b)的标准紫外曲线; 投入JUC-603 (c)和3-PD (d)结晶紫水溶液的紫外-可见吸收光谱图; 投入JUC-603 (e)和3-PD (f)亚甲基蓝水溶液的紫外-可见吸收光谱图; 3-PD和JUC-603对橙黄G (g)和荧光素Na (h)水溶液2 h吸附能力的比较

Figure 6. The standard UV-Vis curves of crystal violet (a) and methylene blue trihydrate (b); UV-Vis absorption spectra of crystal violet aqueous solution in the presence of (c) JUC-603 and (d) 3-PD; UV-Vis absorption spectra of methylene blue trihydrate aqueous solution in the presence of (e) JUC-603 and (f) 3-PD; comparison of (g) acid orange 10 and (h) fluorescein sodium adsorption between 3-PD and JUC-603 after 2 h

图7. JUC-603在吸附不同染料后的PXRD

Figure 7. PXRD patterns of JUC-603 after adsorbing different dyes

参考文献 21

[22]	Demessence, A.; Alessandro, D. M.; Foo, L.; Long, J. R. J. Am. Chem. Soc. 2009, 131, 8784. doi: 10.1021/ja903411w
[23]	Lu, W.; Yuan, D.; Sculley, J.; Zhao, D.; Krishna, R.; Zhou, H. J. Am. Chem. Soc. 2011, 133, 18126. doi: 10.1021/ja2087773
[24]	Rao, M. R.; Fang, Y.; Feyter, S. D.; Perepichka, D. F. J. Am. Chem. Soc. 2017, 139, 2421. doi: 10.1021/jacs.6b12005
[25]	Liu, Y.; Wang, Y.; Li, H.; Guan, X.; Zhu, L.; Xue, M.; Yan, Y.; Valtchev, V.; Qiu, S.; Fang, Q. Chem. Sci. 2019, 10, 10815. doi: 10.1039/C9SC03725J
[26]	Materials Studio, Ver. 7.0, Accelrys Inc., San Diego, CA.
[1]	Nugent, P.; Belmabkhout, Y.; Burd, S. D.; Cairns, A. J.; Luebke, R.; Forrest, F.; Pham, T.; Ma, S.; Space, B.; Wojtas, L.; Eddaoudi, M.; Zaworotko, M. J. Nature 2013, 495, 80. doi: 10.1038/nature11893
[2]	Pachauri, R. K.; Reisinger, A. IPCC Fifth Assessment Report, 2014.
[3]	Côté, A. P.; Benin, A. I.; Ockwig, N. W.; O′Keeffe, M.; Matzger, A. J.; Yaghi, O. M. Science 2005, 310, 1166. doi: 10.1126/science.1120411
[4]	Colson, J. W.; Woll, A. R.; Mukherjee, A.; Levendorf, M. P.; Spitler, E. L.; Shields, V. B.; Spencer, M. G.; Park, J.; Dichtel, W. R. Science 2011, 332, 228. doi: 10.1126/science.1202747
[5]	Feng, X.; Ding, X. S.; Jiang, D. L. Chem. Soc. Rev. 2012, 41, 6010. doi: 10.1039/c2cs35157a
[6]	Ding, S.; Wang, W. Chem. Soc. Rev. 2013, 42, 548. doi: 10.1039/C2CS35072F
[7]	Guan, X.; Chen, F.; Fang, Q.; Qiu, S. Chem. Soc. Rev. 2020, 49, 1357. doi: 10.1039/C9CS00911F
[8]	Kuhn, P.; Antonietti, M.; Thomas, A. Angew. Chem. Int. Ed. 2008, 47, 3450. doi: 10.1002/(ISSN)1521-3773
[9]	Wang, S.; Wang, Q.; Shao, P.; Han, Y.; Gao, X.; Ma, L.; Yuan, S.; Ma, X.; Zhou, J.; Feng, X.; Wang, B. J. Am. Chem. Soc. 2017, 139, 4258. doi: 10.1021/jacs.7b02648
[10]	Wang, X.; Han, X.; Zhang, J.; Wu, X.; Liu, Y.; Cui, Y. J. Am. Chem. Soc. 2016, 138, 12332. doi: 10.1021/jacs.6b07714
[11]	Sun, Q.; Aguila, B.; Perman, J.; Nguyen, N.; Ma, S. Q. J. Am. Chem. Soc. 2016, 138, 15790. doi: 10.1021/jacs.6b10629
[12]	Chandra, S.; Kandambeth, T. S.; BabaRao, R.; Marathe, M. Y.; Kunjir, S. M.; Banerjee, R. J. Am. Chem. Soc. 2014, 136, 6570. doi: 10.1021/ja502212v
[13]	Liang, R.; Cui, F.; Ru-Han, A.; Qi, Q.; Zhao, X. CCS Chem. 2020, 2, 139. doi: 10.31635/ccschem.020.201900094
[14]	Wang, H.; Zeng, Z.; Xu, P.; Li, L.; Zeng, G.; Xiao, R.; Tang, Z.; Huang, D.; Tang, L.; Lai, C.; Jiang, D.; Liu, Y.; Yi, H.; Qin, L.; Ye, S.; Ren, X.; Tang, W. Chem. Soc. Rev. 2019, 48, 488. doi: 10.1039/C8CS00376A
[15]	Wang, Z.; Li, H.; Yan, S.; Fang, Q. Acta Chim. Sinica 2020, 78, 63 ; (in Chinese) doi: 10.6023/A19110397
	( 王志涛, 李辉, 颜士臣, 方千荣, 化学学报 2020, 78, 63.)
[16]	Chang, J.; Xu, G.; Li, H.; Fang, Q. Chem. J. Chinese Univ. 2020, 41, 1609 ; (in Chinese)
	( 常建红, 徐国杰, 李辉, 方千荣, 高等学校化学学报, 2020, 41, 1609.)
[17]	Fang, J.; Zhao, W.; Zhang, M.; Fang, Q. Acta Chim. Sinica 2021, 79 186 ; (in Chinese) doi: 10.6023/A20100471
	( 方婧, 赵文娟, 张明浩, 方千荣, 化学学报 2021, 79, 186.)
[18]	Liu, J.; Zhang, M.; Wang, N.; Wang, C.; Ma, L. Acta Chim. Sinica 2020, 78, 311 ; (in Chinese) doi: 10.6023/A19120426
	( 刘建国, 张明月, 王楠, 王晨光, 马隆龙, 化学学报 2020, 78, 311.)
[19]	Peng, Z.; Ding, H.; Chen, R.; Gao, C.; Wang, C. Acta Chim. Sinica 2019, 77, 681 ; (in Chinese) doi: 10.6023/A19040118
	( 彭正康, 丁慧敏, 陈如凡, 高超, 汪成, 化学学报 2019, 77, 681.)
[20]	Wang, T.; Zhao, L.; Wang, K.; Bai, Y.; Feng, F. Acta Chim. Sinica 2021, 79, 600 ; (in Chinese) doi: 10.6023/A20120578
	( 王涛, 赵璐, 王科伟, 白云峰, 冯峰, 化学学报 2021, 79, 600.)
[21]	Luo, Y.; Li, B.; Wang, W.; Wu, K.; Tan, B. Adv. Mater. 2021, 24, 5703. doi: 10.1002/adma.v24.42