Recognition Performance of 3D Printed Eu-MOFs Hydrogel for Acetone and 4-Nitroaniline (PNA)

doi:10.6023/A25020047

Abstract

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

Cite this article

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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Fig. & Tab. 6

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

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

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

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

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

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

References 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.

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