基于ZIF-8/PAN复合薄膜的柔性丙酮气体传感器

doi:10.6023/A22020093

摘要/Abstract

ZIF-8是一种Zn基金属有机骨架材料, 可以吸附丙酮气体从而作为电容式丙酮传感器的气敏材料, 然而ZIF-8的传统使用形式为粉末态, 这导致其不能成为具备柔性的整体, 从而限制了传感器的柔性. 结合包埋种子和二次生长法将ZIF-8与纳米纤维结合成纤维型柔性材料, 并将其作为气敏层制备了柔性电容式丙酮气体传感器. 该传感器在9种常见挥发性有机化合物中表现出良好的选择性, 对250~2000 cm³/m³的丙酮气体具有灵敏的响应、良好的循环响应及长期稳定性. 值得注意的是该柔性传感器不仅在室温下进行传感, 而且在弯折180°的状态下对丙酮气体的响应值与不弯折(0°)状态下几乎一致, 在200次以内的180°弯折-恢复后同样表现出了传感性能的稳定, 表明了其在柔性传感器方面的潜力.

关键词: 金属有机骨架材料, 纳米纤维, 挥发性有机化合物(VOCs)气体传感器, 电容, 柔性, 包埋种子法

ZIF-8 is a Zn-based metal organic framework material which can adsorb acetone gas, so it can be used as the gas sensing material of capacitive acetone sensor. In addition, it can be combined with electrospinning nanofibers to form a fibrous gas sensitive material, so that the acetone sensor using it as the gas sensing material has excellent flexibility and this kind of excellent flexibility cannot be achieved in the research of flexible acetone sensor at present. In this work, ZIF-8/ polyacrylonitrile (PAN) nanofiber membrane composite with excellent flexibility was prepared by seed embedding method and secondary growth method. The key to the material preparation process is to prepare 2-methylimidazol/PAN composite membrane firstly by blended electrospinning and use the 2-methylimidazole embedded in the nanofiber membrane as the site for the growth of ZIF-8 on the surface of the nanofiber membrane. Then the metal salts and ligands needed for the growth of ZIF-8 were provided by the secondary growth method in stages and finally the fibrous gas sensitive material ZIF-8/PAN could be obtained. After that, a capacitive acetone sensor using flexible ZIF-8/PAN composite material as flexible gas sensing layer and carbon nanotubes as flexible electrode was prepared. The sensor has excellent flexibility, high porosity and fully exposed active site. Due to these characteristics, the sensor has a sensitive response to acetone gas in the range of 250~2000 cm³/m³, and the response shows good linearity (R²=0.99659). In addition, the sensor has good cyclic response, long-term stability, and shows good selectivity for acetone among nine common volatile organic compounds. It is worth noting that due to the excellent flexibility of the fibrous gas sensitive layer ZIF-8/PAN, the response value of the sensor to acetone gas under 180° bending state is almost the same as that to acetone under 0° unbending state, and the sensor also shows a stable response to acetone after 180° bending-recovery within 200 times. Besides these excellent performances in flexibility, the use temperature of the sensor is room temperature. These characteristics make it have the development potential to combine with clothing to form a portable flexible acetone sensor.

Key words: metal-organic framework, nanofiber, volatile organic compounds (VOCs) gas sensor, capacitance, flexibility, seed embedding method

引用此文

牛犇, 翟振宇, 郝肖柯, 任婷莉, 李从举. 基于ZIF-8/PAN复合薄膜的柔性丙酮气体传感器[J]. 化学学报, 2022, 80(7): 946-955.

Ben Niu, Zhenyu Zhai, Xiaoke Hao, Tingli Ren, Congju Li. Flexible Acetone Gas Sensor based on ZIF-8/Polyacrylonitrile (PAN) Composite Film[J]. Acta Chimica Sinica, 2022, 80(7): 946-955.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 12

图1. (a, b) ZIF-8/PAN复合膜合成及(c)柔性丙酮传感器制备示意图

Figure 1. Schematic diagrams of (a, b) synthesis of ZIF-8/PAN composite membrane and (c) preparation of flexible acetone sensor

图2. (a) 2-MIM/PAN的SEM图像、(b, c)不同放大倍数下的ZIF-8/PAN的SEM图像、(d) ZIF-8/PAN的EDX分析及(e) ZIF-8/PAN和碳纳米管制备的柔性丙酮气体传感器

Figure 2. (a) SEM image of 2-MIM/PAN, (b, c) SEM image of ZIF-8/PAN at different magnification, (d) EDX analysis of ZIF-8/PAN and (e) flexible acetone gas sensor prepared by ZIF-8/PAN and carbon nanotubes

图3. PAN、2-MIM/PAN、ZIF-8/PAN和标准ZIF-8的XRD图像

Figure 3. XRD images of PAN, 2-MIM/PAN, ZIF-8/PAN and simulated ZIF-8

图4. PAN、2-MIM/PAN、ZIF-8/PAN和ZIF-8粉末的FTIR谱图

Figure 4. FTIR spectra of PAN, 2-MIM/PAN, ZIF-8/PAN and ZIF-8 powder

图5. 2-MIM/PAN和ZIF-8/PAN的热重图像

Figure 5. Thermogravimetry curves of 2-MIM/PAN and ZIF-8/PAN

图6. (a) 2-MIM/PAN和ZIF-8/PAN的N2吸附-脱附曲线以及(b) ZIF-8/PAN的孔径分布

Figure 6. (a) N2 adsorption-desorption curves of 2-MIM/PAN and ZIF-8/PAN and (b) pore size distribution of ZIF-8/PAN

图7. (a)基于三种不同的气敏层的传感器对于500 cm3/m3丙酮及(b)基于ZIF-8/PAN气敏层的传感器对于不同浓度丙酮的响应

Figure 7. Response of sensors based on (a) three different gas-sensitive layers to 500 cm3/m3 acetone and (b) ZIF-8/PAN gas sensitive layer to different concentrations of acetone

图8. (a)传感器的循环响应测试及(b)传感器对于500及1000 cm3/m3丙酮响应的长期稳定性测试

Figure 8. (a) Cyclic response test of the sensor and (b) long-term stability testing of sensors in response to 500 and 1000 cm3/m3 acetone

图9. 传感器对500 cm3/m3丙酮的响应/恢复时间

Figure 9. Sensor response/recovery time to 500 cm3/m3 acetone

图10. 传感器对于浓度为1000 cm3/m3的9种不同VOCs的响应

Figure 10. Sensor response to 9 different VOCs of 1000 cm3/m3

图11. (a)传感器180°弯折示意图、(b) ZIF-8/PAN在200次180°弯折-恢复后弯折处的SEM图像、(c)传感器在180°弯折状态下对不同浓度丙酮测试响应及与0°非弯折状态下对比和(d)传感器在200次以内180°弯折-恢复后对于两种浓度丙酮气体响应值

Figure 11. (a) Schematic diagram of the sensor bending at 180°, (b) ZIF-8/PAN SEM image of the bend after 200 times of 180° bending-recovery, (c) response of the sensor to different concentrations of acetone at 180° bending and compared with 0° non-bending and (d) response of the sensor to the two concentrations of acetone gas after bending at 180° for up to 200 times

图12. 测试系统原理图

Figure 12. Schematic diagram of the testing system

参考文献 42

[1]	Li, X. Q.; Zhang, L.; Yang, Z. Q.; Wang, P.; Yan, Y. F.; Ran, J. Y. Sep. Purif. Technol. 2020, 235, 116213. doi: 10.1016/j.seppur.2019.116213
[2]	Yang, C. T.; Miao, G.; Pi, Y. H.; Xia, Q. B.; Wu, J. L.; Li, Z.; Xiao, J. Chem. Eng. J. 2019, 370, 1128. doi: 10.1016/j.cej.2019.03.232
[3]	Gardner, J. W.; Shin, H. W.; Hines, E. L. Sens. Actuators, B 2000, 70, 19.
[4]	Liu, D.; Pervaiz, E.; Adimi, S.; Thomas, T.; Qu, F.; Huang, C.; Wang, R.; Jiang, H.; Yang, M. Appl. Surf. Sci. 2021, 566, 150642. doi: 10.1016/j.apsusc.2021.150642
[5]	Wang, C. X.; Cai, D. P.; Liu, B.; Li, H.; Wang, D. D.; Liu, Y.; Wang, L. L.; Wang, Y. R.; Li, Q. H.; Wang, T. H. J. Mater. Chem. A 2014, 2, 10623. doi: 10.1039/c4ta00844h
[6]	Cavallari, M. R.; Izquierdo, J. E. E.; Braga, G. S.; Dirani, E. a. T.; Pereira-Da-Silva, M. A.; Rodríguez, E. F. G.; Fonseca, F. J. Sensors 2015, 15, 9592. doi: 10.3390/s150409592 pmid: 25912354
[7]	Cao, R.; Zhao, S. Y.; Li, C. J. ACS Appl. Electron. Mater. 2019, 1, 2301. doi: 10.1021/acsaelm.9b00483
[8]	Zhang, X. L.; Na, J. W.; Xing, Y.; Li, C. J. Glob. Chall. 2019, 3, 1900070.
[9]	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
[10]	Impeng, S.; Junkaew, A.; Maitarad, P.; Kungwan, N.; Zhang, D.; Shi, L.; Namuangruk, S. Appl. Surf. Sci. 2019, 473, 820. doi: 10.1016/j.apsusc.2018.12.209
[11]	Hazra, A.; Das, S.; Kanungo, J.; Sarkar, C. K.; Basu, S. Sens. Actuators, B 2013, 183, 87.
[12]	Paliwal, A.; Sharma, A.; Tomar, M.; Gupta, V. Sens. Actuators, B 2017, 250, 679.
[13]	Li, Z.; Zhang, Y.; Zhang, H.; Yi, J. X. Sens. Actuators, B 2021, 344, 130182.
[14]	Andrés, M. A.; Vijjapu, M. T.; Surya, S. G.; Shekhah, O.; Salama, K. N.; Serre, C.; Eddaoudi, M.; Roubeau, O.; Gascón, I. ACS Appl. Mater. Interfaces 2020, 12, 4155. doi: 10.1021/acsami.9b20763
[15]	Zeinali, S.; Homayoonnia, S.; Homayoonnia, G. Sens. Actuators, B 2019, 278, 153.
[16]	Scott, A. J.; Majdabadifarahani, N.; Stewart, K. M. E.; Duever, T. A.; Penlidis, A. Macromol. React. Eng. 2020, 14, 2000004. doi: 10.1002/mren.202000004
[17]	Lan, K. B.; Wang, Z.; Yang, X. D.; Wei, J. Q.; Qin, Y. X.; Qin, G. X. Nanotechnology 2022, 33, 155502. doi: 10.1088/1361-6528/ac46b3
[18]	Andrysiewicz, W.; Krzeminski, J.; Skarżynski, K.; Marszalek, K.; Sloma, M.; Rydosz, A. Electron. Mater. Lett. 2020, 16, 146. doi: 10.1007/s13391-020-00199-z
[19]	Zhang, L.; Guo, Y. Y. H.; Liu, G. Y.; Tan, Q. L. IEEE Access 2020, 8, 171568. doi: 10.1109/ACCESS.2020.3023028
[20]	Zhang, J. W.; Li, P.; Zhang, X. N.; Ma, X. J.; Wang, B. Acta Chim. Sinica 2020, 78, 597. (in Chinese) doi: 10.6023/A20050153
	(张晋维, 李平, 张馨凝, 马小杰, 王博, 化学学报, 2020, 78, 597.) doi: 10.6023/A20050153
[21]	Li, C.; Li, N.; Chang, L. M.; Gu, Z. G.; Zhang, J. Acta Chim. Sinica 2022, 80, 340. (in Chinese) doi: 10.6023/A21120545
	(李崇, 李娜, 常立美, 谷志刚, 张健, 化学学报, 2022, 80, 340.) doi: 10.6023/A21120545
[22]	Qi, Y.; Ren, S. S.; Che, Y.; Ye, J. W.; Ning, G. L. Acta Chim. Sinica 2020, 78, 613. (in Chinese) doi: 10.6023/A20040126
	(齐野, 任双颂, 车颖, 叶俊伟, 宁桂玲, 化学学报, 2020, 78, 613.) doi: 10.6023/A20040126
[23]	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.) doi: 10.6023/A19070259
[24]	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. 2022, 428, 131720. doi: 10.1016/j.cej.2021.131720
[25]	Zhang, X. L.; Hao, X. K.; Zhai, Z. Y.; Wang, J. N.; Li, H. Y.; Sun, Y. X.; Qin, Y.; Niu, B.; Li, C. Appl. Surf. Sci. 2022, 573, 151446. doi: 10.1016/j.apsusc.2021.151446
[26]	Szilágyi, P. Á.; Westerwaal, R. J.; Van De Krol, R.; Geerlings, H.; Dam, B. J. Mater. Chem. C 2013, 1, 8146. doi: 10.1039/c3tc31749h
[27]	Chen, B. L.; Yang, Z. X.; Zhu, Y. Q.; Xia, Y. D. J. Mater. Chem. A 2014, 2, 16811. doi: 10.1039/C4TA02984D
[28]	Peng, L, C.; Zhang, X, L..; Sun, Y, X.; Xing, Y.; Li, C, J. Environ. Res. 2020, 188, 109742. doi: 10.1016/j.envres.2020.109742
[29]	Venkatesh, M. R.; Sachdeva, S.; El Mansouri, B.; Wei, J.; Bossche, A.; Bosma, D.; De Smet, L. C. P. M.; Sudhölter, E. J. R.; Zhang, G. Q. Sensors 2019, 19, 888. doi: 10.3390/s19040888
[30]	Sun, Y. X.; Zhang, X. L.; Xi, H. L.; Li, C. J. Fine Chem. 2020, 37, 1334. (in Chinese)
	(孙亚昕, 张秀玲, 习海玲, 李从举, 精细化工, 2020, 37, 1334.)
[31]	Yao, A.; Jiao, X.; Chen, D.; Li, C. ACS Appl. Mater. Interfaces 2020, 12, 18437. doi: 10.1021/acsami.9b22242
[32]	Ma, K. K.; Wang, Y. F.; Chen, Z. J.; Islamoglu, T.; Lai, C. L.; Wang, X. W.; Fei, B.; Farha, O. K.; Xin, J. H. ACS Appl. Mater. Interfaces 2019, 11, 22714. doi: 10.1021/acsami.9b04780
[33]	Ma, K.; Idrees, K. B.; Son, F. A.; Maldonado, R.; Wasson, M. C.; Zhang, X.; Wang, X.; Shehayeb, E.; Merhi, A.; Kaafarani, B. R.; Islamoglu, T.; Xin, J. H.; Farha, O. K. Chem. Mater. 2020, 32, 7120. doi: 10.1021/acs.chemmater.0c02379
[34]	Hao, X. K.; Zhai, Z. Y.; Sun, Y. X.; Li, C. J. Acta Chim. Sincia 2022, 80, 49. (in Chinese)
	(郝肖柯, 翟振宇, 孙亚昕, 李从举, 化学学报, 2022, 80, 49.) doi: 10.6023/A21080402
[35]	Zhang, X. L.; Fan, W.; Li, H.; Zhao, S. Y.; Wang, J. N.; Wang, B.; Li, C. J. J. Mater. Chem. A 2018, 6, 21458. doi: 10.1039/C8TA07884J
[36]	Cao, R.; Wang, J. N.; Zhao, S. Y.; Yang, W.; Yuan, Z. Q.; Yin, Y. Y.; Du, X. Y.; Li, N. W.; Zhang, X. L.; Li, X. Y.; Wang, Z. L.; Li, C. J. Nano Res. 2018, 11, 3771. doi: 10.1007/s12274-017-1951-2
[37]	Lee, S.; Franklin, S.; Hassani, F. A.; Yokota, T.; Someya, T. Science 2020, 370, 966. doi: 10.1126/science.abc9735
[38]	Homayoonnia, S.; Zeinali, S. Sens. Actuators, B 2016, 237, 776.
[39]	Tung, T. T.; Tran, M. T.; Feller, J.-F.; Castro, M.; Van Ngo, T.; Hassan, K.; Nine, M. J.; Losic, D. Carbon 2020, 159, 333. doi: 10.1016/j.carbon.2019.12.010
[40]	Bahri, M.; Haghighat, F.; Kazemian, H.; Rohani, S. Chem. Eng. J. 2017, 313, 711. doi: 10.1016/j.cej.2016.10.004
[41]	Huang, X. C.; Lin, Y. Y.; Zhang, J. P.; Chen, X. M. Angew. Chem., Int. Ed. 2006, 45, 1557. doi: 10.1002/anie.200503778
[42]	Shekhah, O.; Eddaoudi, M. Chem. Commun. 2013, 49, 10079. doi: 10.1039/c3cc45343j