3D打印Eu-MOFs水凝胶对丙酮和4-硝基苯胺(PNA)识别性能的研究

doi:10.6023/A25020047

摘要/Abstract

通过高分辨率数字光处理3D打印技术原位合成了Eu-BTC MOFs(金属有机骨架化合物, MOF)水凝胶, 用于小分子丙酮和4-硝基苯胺(PNA)的检测识别. 首先通过3D打印的方式得到了一种含有配体均苯三甲酸(H₃BTC)的三维(3D)水凝胶前驱体, 接着在其基础上原位合成Eu-BTC MOFs水凝胶. 然后利用该水凝胶对甲醇、乙醇等小分子进行荧光检测, 结果发现其能够选择性识别丙酮和PNA, 其检测限分别为2.43 μL和1.74 μmol/L. 最后, 通过X射线粉末衍射、紫外可见光谱、红外和X射线光电子能谱等表征探究了其传感机制: 水凝胶与被检测分子之间的相互作用是导致荧光猝灭的根本原因. 通过该方法得到的Eu-MOFs水凝胶可以有效避免粉末MOF材料在应用中存在易聚集、难回收、保质期短和应用成本高等问题, 因此其在光学传感新领域具有非常大的潜力, 而且为MOF材料的宏观应用提供了一种开创性的方法.

关键词: 3D打印, 水凝胶, 原位合成, 丙酮, 4-硝基苯胺, 识别

In this work, a stretch Eu-BTC MOFs hydrogel was synthesized in situ by high-resolution digital light processing (DLP) 3D printing technology for the detection and recognition of small molecule acetone and 4-nitroaniline (PNA). First, mix acrylamide (AAm), terephthalic acid (H₃BTC) and polyethylene glycol diacrylate (PEGDA) at room temperature, then add 2,4,6-trimethylbenzoyl diphenyloxyphosphate (TPO) and methyl orange (MO), heat them to 60 ℃ in a dark environment and stir them evenly, then add acrylic acid (AA) and ammonia, stir them evenly to obtain hydrogel precursor solution, print and solidify them layer by layer from bottom to top through a high-resolution DLP printer (405 nm ultraviolet light source) to obtain a 3D solid precursor model, wash the printed sample with ethanol, and remove the residual precursor solution from the surface. Finally, the UV cured hydrogel structure was immersed in the mixed solution of Eu(NO₃)₃•6H₂O water/dimethylacetamide (DMA) (mass ratio 1:3) for 24 h, where the concentration of Eu^3＋ was 1.0 mol/L, allowing Eu^3＋ to fully diffuse into the hydrogel matrix, and then Eu-BTC MOFs hydrogel was synthesized in situ. Then Fourier transform infrared spectroscopy (FT-IR), X-ray Powder diffraction, Elemental analysis and other characterizations were used to determine its structure and fluorescence performance, and Eu MOFs hydrogel was used to carry out fluorescence recognition tests on organic molecules such as methanol, ethanol, nitrobenzene, etc. The results showed that it could selectively recognize acetone and PNA, and the detection limits of acetone and PNA were 2.43 μL and 1.74 μmol/L, respectively. The results show that the interaction between the hydrogel and the detected molecule is the root cause of fluorescence quenching. The Eu MOFs hydrogel obtained by this method can effectively avoid the problems of easy aggregation, difficult recovery, short shelf life and high application cost of powdered MOF materials in sensor applications. This material not only demonstrates its potential in the new field of optical sensing, but also provides a simple strategy for optimizing the macroscopic applications of MOF materials.

Key words: 3D printing, hydrogel, in situ synthesis, acetone, p-nitrobenzene, recognition

引用此文

朱永朝, 陈姿仪, 周俊, 梁文杰, 徐海. 3D打印Eu-MOFs水凝胶对丙酮和4-硝基苯胺(PNA)识别性能的研究[J]. 化学学报, 2025, 83(8): 887-894.

Yongchao Zhu, Ziyi Chen, Jun Zhou, Wenjie Liang, Hai Xu. Recognition Performance of 3D Printed Eu-MOFs Hydrogel for Acetone and 4-Nitroaniline (PNA)[J]. Acta Chimica Sinica, 2025, 83(8): 887-894.

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图/表 6

图1. (a) Eu-MOFs水凝胶的EDS图谱; (b) Eu-MOFs水凝胶和单晶Eu-MOFs粉体的XRD图谱; (c) Eu-MOFs水凝胶和单晶Eu-MOFs粉体的FT-IR; (d) Eu-MOFs水凝胶的稳态荧光发射光谱(PL), 插图为材料在365 nm紫外灯照射时的光学照片; (e) Eu-MOFs水凝胶的固体紫外-可见光谱图

Figure 1. (a) EDS mapping of Eu-MOFs hydrogel; (b) XRD pattern of Eu-MOFs hydrogel and single crystal Eu-MOFs powder; (c) FT-IR spectra of Eu-MOFs hydrogel and single crystal Eu-MOFs powder; (d) Photoluminescence (PL) spectra of Eu-MOFs hydrogel, the insert is the optical photograph of Eu-MOFs hydrogel under the UV light with a wavelength of 365 nm; (e) UV-vis spectra of Eu-MOFs hydrogel

图2. (a) Eu-MOFs水凝胶在不同溶剂添加前(深绿色)和添加后(浅黄色)的荧光强度对比; (b) Eu-MOFs水凝胶在体积分数5%其他溶剂与体积分数95%丙酮混合前和混合后(浅黄色)的荧光强度对比; (c) Eu-MOFs水凝胶荧光强度随丙酮体积变化的光谱图(体积单位: μL); (d)通过Stern-Volmer方程得到添加丙酮的体积与水凝胶荧光强度变化相对值的线性关系; (e)添加丙酮后, Eu-MOFs水凝胶荧光强度的时间响应; (f) 5个循环过程中, Eu-MOFs水凝胶荧光强度的变化, 其中I0为初始荧光强度, I为循环过程中荧光强度检测值

Figure 2. (a) Comparison of fluorescence intensity of Eu-MOFs hydrogel before (dark green) and after (light yellow) addition of different solvents; (b) Comparison of fluorescence intensity of Eu-MOFs hydrogel before (dark green) and after (light yellow) mixing 5% (volume fraction) other solvents with 95% (volume fraction) acetone; (c) Spectrogram of fluorescence intensity of Eu-MOFs hydrogel as a function of acetone volume (volume unit: μL); (d) The linear relationship between the volume of the added acetone and the relative value of the fluorescence intensity change of the hydrogel was obtained by the Stern-Volmer equation; (e) Time response of fluorescence intensity of Eu-MOFs hydrogel after acetone addition; (f) The change of fluorescence intensity of Eu-MOFs hydrogel during five cycles, where I0 is the initial fluorescence intensity, and I is the detection value of fluorescence intensity during the cycle.

MOF	灵敏度/检出限	可逆性	Ref.
[Eu₅(DBA)₃]_n	LOD: 1.24 μmol/L	—	[40]
[Me₂NH₂]₂[(Eu)₂(ofdp)₂(DMF)(H₂O)]•7H₂O•DMF	LOD: 7.4% (volume fraction)	—	[41]
MOF-808-Tb	浓度低于8600 μmol/L, 荧光强度降低到近50%	是	[42]
[Cd(dcba)(DMA)]•DMA	K_sv: 8.4×10⁴ L•mol^－1	是	[43]
DhaTab-COF-EuIL	LOD: 1.0% (volume fraction)	—	[44]
Eu/Tb@Bi-MOF	—	—	[45]
Eu-BPDA	丙酮浓度0.028% (volume fraction)时, 荧光强度降低50%	是	[46]
3D-printed Eu-MOFs	LOD: 2.43 μL	是	本工作

表1. 不同MOFs传感器对丙酮的传感性能比较

Table 1. Comparison of acetone sensing performance of different sensors of MOFs

图3. (a) Eu-MOFs水凝胶添加丙酮前后的X射线衍射图谱; (b) Eu-MOFs水凝胶添加丙酮前后的红外图谱; (c)丙酮添加前后Eu-MOFs水凝胶的XPS光谱和精细谱.

Figure 3. (a) X-ray diffraction patterns of Eu MOFs hydrogel before and after adding acetone; (b) FT-IR spectra of Eu MOFs hydrogel before and after adding acetone; (c) XPS survey spectra and high-resolution spectra of Eu MOFs hydrogel before and after acetone addition

图4. (a) Eu-MOFs水凝胶对不同有机小分子的荧光响应, 每个有机小分子的浓度为0.15 mmol•L－1. 绿色条表示不存在PNA时的荧光强度, 红色条表示存在PNA时的荧光强度; (b)不同PNA浓度下, Eu-MOFs水凝胶的荧光强度(浓度单位: mmol•L－1); (c)通过Stern-Volmer方程得到不同浓度的PNA与水凝胶荧光强度变化相对值的线性关系

Figure 4. (a) Fluorescence response of Eu-MOFs hydrogel to different organic small molecules, and the concentration of each organic small molecule is 0.15 mmol•L－1. The green bar represents the fluorescence intensity in the absence of PNA, while the red bar represents the fluorescence intensity in the presence of PNA; (b) spectrogram of fluorescence intensity of Eu-MOFs hydrogel changing with PNA concentration (concentration unit: mmol•L－1); (c) the linear relationship between PNA of different concentrations and the relative value of fluorescence intensity of hydrogel was obtained by Stern-Volmer equation

图5. (a) Eu-MOFs水凝胶添加丙酮前后的X射线衍射图谱; (b)有机小分子的吸收光谱与Eu-MOFs水凝胶的发射光谱; (c)不含有PNA和(d)含有PNA的Eu-MOFs水凝胶的时间衰减曲线

Figure 5. (a) X-ray diffraction patterns of Eu MOFs hydrogel before and after adding acetone; (b) absorption spectra of small organic molecules and emission spectra of Eu-MOF hydrogels; (c) time-resolved decay curve of Eu MOFs hydrogels with PNA and (d) without PNA

参考文献 49

[1]	Gao, P.; Mukherjee, S.; Zahid Hussain, M.; Ye, S.; Wang, X.; Li, W.; Cao, R. Chem. Eng. J. 2024, 492, 152377.
[2]	Wang, F.-X.; Zhang, Z.-C.; Wang, C.-C.; Yi, X.-H.; Yi, S. Sep. Purif. Technol. 2024, 337, 126409.
[3]	Song, K.; Pan, Y.-T.; Zhang, J.; Song, P.; He, J.; Wang, D.-Y.; Yang, R. Chem. Eng. J. 2023, 468, 143653.
[4]	Khan, M. M.; Rahman, A.; Matussin, S. N. Nanomaterials 2022, 12, 2820.
[5]	He, H.; Li, R.; Yang, Z.; Chai, L.; Jin, L.; Alhassan, S. I.; Ren, L.; Wang, H.; Huang, L. Catal. Today 2021, 375, 10.
[6]	Dhakshinamoorthy, A.; Asiri, A. M.; García, H. Angew. Chem., Int. Ed. 2016, 55, 5414.
[7]	Baig, U.; Waheed, A.; Jillani, S. M. S. Chem Asian J. 2023, 19, e202300619.
[8]	Lin, G.; Zeng, B.; Li, J.; Wang, Z.; Wang, S.; Hu, T.; Zhang, L. Chem. Eng. J. 2023, 460, 141710.
[9]	Guo, X.; Wang, L.; Wang, L.; Huang, Q.; Bu, L.; Wang, Q. Front. Chem. 2023, 11, 1116524.
[10]	Mohammed Ameen, S. S.; Omer, K. M. ACS Appl. Mater. Interfaces 2024, 16, 31895.
[11]	Zhang, S.; Xiao, J.; Zhong, G.; Xu, T.; Zhang, X. Analyst 2024, 149, 1381.
[12]	Sule, R.; Mishra, A. K.; Nkambule, T. T. Int. J. Energy Res. 2021, 45, 12481.
[13]	Suganthi, S.; Ahmad, K.; Oh, T. H. Molecules 2024, 29, 5373.
[14]	Mhettar, P.; Kale, N.; Pantwalawalkar, J.; Nangare, S.; Jadhav, N. ADMET DMPK 2023, 12, 27.
[15]	Jin, J.; Xue, J.; Liu, Y.; Yang, G.; Wang, Y.-Y. Dalton Trans. 2021, 50, 1950.
[16]	Han, C. Q.; Liu, X. Y. Angew. Chem., Int. Ed. 2024, 64, e202416286.
[17]	Li, B.; Zhao, D.; Wang, F.; Zhang, X.; Li, W.; Fan, L. Dalton Trans. 2021, 50, 14967.
[18]	Jie, B.; Lin, H.; Zhai, Y.; Ye, J.; Zhang, D.; Xie, Y.; Zhang, X. Chem. Eng. J. 2023, 454, 139931.
[19]	Liang, D. P.; Feng, L. Y.; Lu, X. Y.; Peng, D. B.; Zhang, T. W. Technol. Dev. Chem. Ind. 2024, 53, 1 (in Chinese).
	(梁冬萍, 冯莉源, 陆昕妍, 彭定柏, 张桐玮, 化工技术与开发, 2024, 53, 1.)
[20]	Sun, T.; Gao, Y.; Du, Y.; Zhou, L.; Chen, X. Front. Chem. 2021, 8, 624592.
[21]	Zhao, S.-N.; Wang, G.; Poelman, D.; Voort, P. Materials 2018, 11, 572.
[22]	Dong, C.-L.; Li, M.-F.; Yang, T.; Feng, L.; Ai, Y.-W.; Ning, Z.-L.; Liu, M.-J.; Lai, X.; Gao, D.-J. Rare Metals 2020, 40, 505.
[23]	Feng, L.; Dong, C.; Li, M.; Li, L.; Jiang, X.; Gao, R.; Wang, R.; Zhang, L.; Ning, Z.; Gao, D.; Bi, J. J. Hazard. Mater. 2020, 388, 121816.
[24]	Liu, Q.; Hu, X.; Dong, X.; Liu, P.; Zhang, N.; Gao, Z.; Wang, W.; Li, H.; Wang, S.; Liu, X.; Tang, Y. Food Chem. 2024, 454, 139756.
[25]	Gao, Y.; Li, M.; Yu, R.; Zhou, Z. H.; Gao, Y.; Jiang, R. L.; Zhang, J. X. Chin. Rare Earths 2024, 45, 80 (in Chinese).
	(高源, 李猛, 于睿, 周子涵, 高禹, 蒋荣立, 张吉雄, 稀土, 2024, 45, 80.)
[26]	Wei, J. X.; Wang, H.; Gu, Q. Y. Chin. J. Inorg. Anal. Chem. 2023, 13, 790 (in Chinese).
	(魏佳欣, 王浩, 谷庆阳, 中国无机分析化学, 2023, 13, 790.)
[27]	Liu, W. S.; Chen, X. Y.; Zhi, W. K.; Wang, X. Q.; Wang, F. Mater. Rep. 2023, 37, 21030231-1 (in Chinese).
	(刘维赛, 陈晓怡, 智文科, 王旭泉, 王飞, 材料导报, 2023, 37, 21030231-1.)
[28]	Zhao, L.-J.; Li, B.; Yong, G.-P. CrystEngComm 2023, 25, 2813.
[29]	Rao, P. A.; Padhy, H.; Bandyopadhyay, K.; Rao, A. V.; Ganta, R.; Bevara, S.; Singh, B. P.; Kundrapu, B.; Saha, S.; Malla, R. R.; Mukkamala, S. B. J. Fluoresc. 2025, 35, 2243.
[30]	Ahlawat, D.; Pachisia, S.; Aashish; Gupta, R. Chem. Asian J. 2025, e202401213.
[31]	Murphy, R. D.; Cosgrave, M.; Judge, N.; Tinajero‐Diaz, E.; Portale, G.; Wu, B.; Heise, A. Small 2024, 20, 2405578.
[32]	Zhang, J.; Hu, Q.; Wang, S.; Tao, J.; Gou, M. Int. J. Bioprinting 2019, 6, 242.
[33]	Chaudhary, R.; Akbari, R.; Antonini, C. Polymers 2023, 15, 287.
[34]	Xu, F.; Jin, H.; Wu, H.; Jiang, A.; Qiu, B.; Liu, L.; Gao, Q.; Lin, B.; Kong, W.; Chen, S.; Sun, D. Scientific Reports 2024, 14, 15695.
[35]	Lu, X.; Li, Y.-F.; Wang, C.-L.; Gao, J.-Y.; Zhou, Y.; Zhang, C.-L. Inorg. Chem. Front. 2024, 11, 5685.
[36]	Xing, B.-B.; Wang, Y.-S.; Zhang, T.; Liu, J.-Y.; Jiao, H.; Xu, L. Mater. Adv. 2025, 6, 756.
[37]	Cho, I.; Kang, J.-G.; Sohn, Y. J. Lumin. 2015, 157, 264.
[38]	Cui, H.; Zhu, P.-F.; Zhu, H.-Y.; Li, H.-D.; Cui, Q.-L. Chin. Phys. B 2014, 23, 057801.
[39]	Gupta, B. K.; Haranath, D.; Saini, S.; Singh, V. N.; Shanker, V. Nanotechnology 2010, 21, 055607.
[40]	Gao, L.; Jiao, C.; Chai, H.; Ren, Y.; Zhang, G.; Yu, H.; Tang, L. J. Solid State Chem. 2020, 284, 121199.
[41]	Yang, Y.; Chen, L.; Jiang, F.; Wu, M.; Pang, J.; Wan, X.; Hong, M. CrystEngComm 2019, 21, 321. doi: 10.1039/c8ce01875h
[42]	Zhang, J.; Peh, S. B.; Wang, J.; Du, Y.; Xi, S.; Dong, J.; Karmakar, A.; Ying, Y.; Wang, Y.; Zhao, D. Chem. Commun. 2019, 55, 4727.
[43]	Wang, J.; Wang, J.; Wu, J.; Li, Y.; Zheng, L.; Lin, Y.-Y. Inorg. Chem. Commun. 2020, 120, 108167.
[44]	Zuo, H.; Li, Y.; Liao, Y. ACS Appl. Mater. Interfaces 2019, 11, 39201.
[45]	Xu, L.; Xu, Y.; Li, X.; Wang, Z.; Sun, T.; Zhang, X. Dalton Trans. 2018, 47, 16696.
[46]	Wang, J.; Wang, J.; Li, Y.; Jiang, M.; Zhang, L.; Wu, P. New J. Chem. 2016, 40, 8600.
[47]	Wang, J.-J.; Si, P.-P.; Yang, J.; Zhao, S.-S.; Li, P.-P.; Li, B.; Wang, S.-Y.; Lu, M.; Yu, S. Polyhedron 2019, 162, 255.
[48]	Mahalakshmi, G.; Balachandran, V. Spectrochim. Acta A 2014, 124, 535.
[49]	Zhu, Y.; Chen, Z.; Wang, C.; Yao, S. X.; Jin, Q.; Zhou, J.; Li, P.; Liu, B.; Liu, Y.; Xu, H. ChemistrySelect 2024, 9, e202402571.