Humidity-resistant ammonia sensor based on PTFE/ZnO/Ti3C2Tx composite films
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摘要: 开发基于半导体功能材料的抗湿性室温气体传感器一直都是气体传感器领域的研究热点和难点。本文从金属氧化物半导体的高灵敏度和稳定性、MXene (Ti3C2Tx)的室温气敏性以及聚四氟乙烯(PTFE)的疏水性出发,以MXene薄膜为基体,采用磁控溅射法分别将ZnO和PTFE沉积到Ti3C2Tx表面,制备了PTFE/ZnO/MXene复合薄膜,同时构筑了基于复合薄膜的气体传感器。通过SEM、TEM和XPS对复合薄膜进行了表征,并对气体传感器的气敏性能和抗湿性能进行了研究。研究结果表明:基于PTFE/ZnO/Ti3C2Tx复合薄膜的气体传感器在室温下对氨气具有良好的选择性、较高的灵敏度和优异的循环稳定性。随着PTFE薄膜厚度的增加,基于复合薄膜的气体传感器的抗湿性能逐渐增加,但灵敏度有所下降。
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关键词:
- PTFE/ZnO/MXene复合薄膜 /
- 抗湿性 /
- 磁控溅射 /
- 气体传感器 /
- 氨气
Abstract: The development of moisture-resistant room-temperature gas sensors based on semiconductor functional materials has always been a hot and difficult research topic in the field of gas sensors. Considering the high sensitivity and stability of metal oxide semiconductor, the room-temperature gas-sensing behaviors of MXene (Ti3C2Tx) and the hydrophobicity of polytetrafluoroethylene (PTFE), the PTFE/ZnO/MXene composite films were prepared by depositing the PTFE and ZnO layers orderly onto the MXene film surface via a magnetron sputtering method, followed by the construction of the gas sensors based on the composite films. The PTFE/ZnO/MXene composite films were characterized by SEM, TEM and XPS, and the gas-sensing and humidity-resistant properties of the composite films-based gas sensors were investigated. Results show that the PTFE/ZnO/Ti3C2Tx composite films-based gas sensors exhibite good selectivity, high sensitivity, and excellent reproducibility towards ammonia at room temperature. With the increase of the thickness of the PTFE layers, the humidity resistance of the composite films-based gas sensors gradually increases, but at the cost of sensitivity.-
Key words:
- PTFE/ZnO/MXene composite films /
- moisture resistance /
- magnetron sputtering /
- gas sensor /
- ammonia
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图 5 不同传感器的气敏响应测试:(a) 对100×10−6氨气的响应图;(b) 对100×10−6氨气的响应/恢复时间;(c) 对不同挥发性有机化合物的响应雷达图(100×10−6氨气、500×10−6异丙醇、乙醇、丙酮和甲醛);(d) 对5×10−6~500×10−6氨气的动态响应曲线;(e) 对不同浓度氨气的响应保持率(传感器均在室温下相对湿度为 30%的条件下监测)
Figure 5. Air sensitive response testing of different sensors: (a) Response to 100×10−6 ammonia; (b) Response/recovery time to 100×10−6 ammonia; (c) Radar plots of the response to different volatile organic compounds (100×10−6 ammonia, 500×10−6 isopropanol, ethanol, acetone, and formaldehyde); (d) Dynamic response curves of the response to ammonia from 5×10−6-500×10−6; (e) Response retention curves of different concentrations of ammonia (All sensors were tested at room temperature with 30% relative humidity)
图 6 传感器的稳定性测试:(a) PTZ-4传感器对100×10−6氨气的循环响应图;(b) PTZ-4传感器对100×10−6氨气循环响应的灵敏度点线图;(c) TZ传感器25天内对100×10−6氨气响应图;(d) TZ传感器和PTZ-4传感器25天内对100×10−6氨气响应的灵敏度点线图;(e) PTZ-4传感器25天内对100×10−6氨气响应图;(f) 25天的初始电阻变化率图(Ran是传感器第n天的初始电阻)
Figure 6. Stability testing of the sensors: (a) Plot of the cyclic response of the PTZ-4 sensor to 100×10−6 ammonia; (b) Dot line plot of the sensitivity of the PTZ-4 sensor to the cyclic response of 100×10−6 ammonia; (c) Plot of the response of the TZ sensor to 100×10−6 ammonia over 25 days; (d) Sensitivity dot line plot of the response of both the TZ and PTZ-4 sensors to 100×10−6 ammonia over 25 days; (e) Plot of PTZ-4 sensor response to 100×10−6 ammonia over 25 days; (f) Plot of initial resistance change rate over 25 days (Ran is the initial resistance of the sensor on n days)
图 7 传感器在室温下对100×10−6氨气在不同相对湿度(RH)条件下响应-恢复曲线以及对应的水接触角(WCA):((a), (b)) TZ;((c), (d)) PTZ-3;((e), (f)) PTZ-4;((g), (h)) PTZ-5;((i), (j)) PTZ-8;(k) 传感器在30%~90%相对湿度范围内的变化指数(CV)值
Figure 7. Sensor response-recovery curves for 100×10−6 ammonia at room temperature under different relative humidity (RH) conditions and corresponding water contact angle (WCA): ((a), (b)) TZ; ((c), (d)) PTZ-3; ((e), (f)) PTZ-4; ((g), (h)) PTZ-5; ((i), (j)) PTZ-8; (k) Coeffficient of variation (CV) of the sensor in the range of 30%-90% RH
表 1 传感器命名
Table 1. Sensor naming
Sample PTFE sputtering time/min PZT-3 3 PZT-4 4 PZT-5 5 PZT-8 8 Notes: PZT—PTFE/ZnO/Ti3C2Tx; PTFE—Polytetrafluoroethylene. -
[1] 张文宇, 丁园, 孙宇凡, 等. 新型二维气敏材料的研究进展[J]. 陶瓷学报, 2023, 44(1): 1-11ZHANG Wenyu, DING Yuan, SUN Yufan, et al. Research progress of new two-dimensional gas sensing materials[J]. Journal of Ceramics, 2023, 44(1): 1-11(in Chinese). [2] WU M, HE M, HU Q, et al. Ti3C2 MXene-based sensors with high selectivity for NH3 detection at room temperature[J]. ACS Sensors, 2019, 4(10): 2763-2770. doi: 10.1021/acssensors.9b01308 [3] ZHANG H F, XUAN J Y, ZHANG Q, et al. Strategies and challenges for enhancing performance of MXene-based gas sensors: A review[J]. Rare Metals, 2022, 41(12): 3976-3999. doi: 10.1007/s12598-022-02087-x [4] 刘寿达, 刘娟娟, 刘潞潞, 等. 二维MXene负载MoO3/Ni-NiO异质结催化材料用于高效碱性电催化析氢反应[J]. 复合材料学报, 2024, 41(5): 2546-2558.LIU Shouda, LIU Juanjuan, LIU Lulu, et al. Two-dimensional MXene supported MoO3/Ni-NiO heterostructures for high-performance hydrogen evolution reaction at alkaline condition[J]. Acta Materiae Compositae Sinica, 2024, 41(5): 2546-2558(in Chinese). [5] JIANG Y, XI H, LI L, et al. Mechanism of action of the heterojunction structure of the photocatalyst ZnO-g-C3N4@TiO2 and its application to the degradation of acetaminophen[J]. Journal of Photochemistry and Photobiology A: Chemistry, 2023, 445: 115010. [6] DING M, HAN C, YUAN Y, et al. Advances and promises of 2D MXenes as cocatalysts for artificial photosynthesis[J]. Solar RRL, 2021, 5(12): 2100603. [7] SUN S B, WANG M W, CHANG X T, et al. W18O49/Ti3C2Tx MXene nanocomposites for highly sensitive acetone gas sensor with low detection limit[J]. Sensors and Actuators B: Chemical, 2020, 304: 127274. [8] WU X N, GONG Y J, YANG B J, et al. Fabrication of SnO2-TiO2-Ti3C2Tx hybrids with multipletype heterojunctions for enhanced gas sensing performance at room temperature[J]. Applied Surface Science, 2022, 581: 245584155. [9] YANG J, GUI Y, WANG Y, et al. NiO/Ti3C2T x MXene nanocomposites sensor for ammonia gas detection at room temperature[J]. Journal of Industrial and Engineering Chemistry, 2023, 119: 476-484. doi: 10.1016/j.jiec.2022.11.070 [10] LIU M, WANG Z, SONG P, et al. In2O3 nanocubes/Ti3C2T x MXene composites for enhanced methanol gas sensing properties at room temperature[J]. Ceramics International, 2021, 47(16): 23028-23037. doi: 10.1016/j.ceramint.2021.05.016 [11] ZHU X, CHANG X, TANG S, et al. Humidity tolerant chemiresistive gas sensors based on hydrophobic CeO2/SnO2 heterostructure films[J]. ACS Applied Materials & Interfaces, 2022, 14(22): 25680-25692. [12] YANG X, SALLES V, KANETI Y V, et al. Fabrication of highly sensitive gas sensor based on Au functionalized WO3 composite nanofibers by electrospinning[J]. Sensors and Actuators B: Chemical, 2015, 220: 1112-1119. doi: 10.1016/j.snb.2015.05.121 [13] HE T, LIU W, LYU T, et al. MXene/SnO2 heterojunction based chemical gas sensors[J]. Sensors and Actuators B: Chemical, 2021, 329: 129275. [14] HALIM J, COOK K M, NAGUIB M, et al. X-ray photoelectron spectroscopy of select multilayered transition metal carbides (MXenes)[J]. Applied Surface Science, 2016, 362: 406-417. doi: 10.1016/j.apsusc.2015.11.089 [15] WU X, GONG Y, YANG B, et al. Fabrication of SnO2-TiO2-Ti3C2Tx hybrids with multiple-type heterojunctions for enhanced gas sensing performance at room temperature[J]. Applied Surface Science, 2022, 581: 152364. [16] 李仕友, 胡俊毅, 贺俊钦, 等. MXene/SA凝胶微球的制备及对U(VI)的吸附性能[J]. 复合材料学报, 2022, 39(10): 4868-4878.LI Shiyou, HU Junyi, HE Junqin, et al. Preparation of MXene/SA gel microspheres and its adsorption performance for U(VI)[J]. Acta Materiae Compositae Sinica, 2022, 39(10): 4868-4878(in Chinese). [17] LI J, HAN K, HUANG J, et al. Polarized nucleation and efficient decomposition of Li2O2 for Ti2C MXene cathode catalyst under a mixed surface condition in lithium-oxygen batteries[J]. Energy Storage Materials, 2021, 35: 669-678. doi: 10.1016/j.ensm.2020.12.004 [18] WU L, YUAN X, TANG Y, et al. MXene sensors based on optical and electrical sensing signals: From biological, chemical, and physical sensing to emerging intelligent and bionic devices[J]. PhotoniX, 2023, 4(1): 1-56. [19] KIM H M, SOHN S, AHN J S. Transparent and superhydrophobicproperties of PTFE films coated on glass substrate using RF-magnetron sputtering and Cat-CVD methods[J]. Surface and Coatings Technology, 2013, 228: S389-S392. doi: 10.1016/j.surfcoat.2012.05.085 [20] KIM H J, LEE J H. Highly sensitive and selective gas sensors using p-type oxide semi-conductors: Overview[J]. Sensors and Actuators B: Chemical, 2014, 192: 607-627. [21] PARK B H, LEE M H, KIM S B, et al. Evaluation of the surface properties of PTFE foam coating filter media using XPS and contact angle measurements[J]. Applied Surface Science, 2011, 257(8): 3709-3716. doi: 10.1016/j.apsusc.2010.11.116 [22] 中国石油化工集团有限公司. 石油化工可燃气体和有毒气体检测报警设计标准: GB/T 50493—2019[S]. 北京: 中国计划出版社, 2019.China Petroleum and Chemical Corporation. Design standard for petrochemical combustible and toxic gas detection and alarm: GB/T 50493—2019[J]. Beijing: China Planning Press, 2019(in Chinese). [23] KOVSKI A. EPA unveils plan on controls of green house gases and VOCs from oil and gas upstream[J]. Oil & Gas Journal, 2021, 119(11b): 17. [24] LIU M, WANG S, JIANG L. Nature-inspired superwettability systems[J]. Nature Reviews Materials, 2017, 2(7): 17036. [25] SIMONENKO E P, SIMONENKO N P, MO KRUSHIN A S, et al. Application of titanium carbide MXenes in chemiresistive gas sensors[J]. Nanomaterials, 2023, 13(5): 850. [26] PAUL R, DAS B, GHOSH R. Novel approaches towards design of metal oxide based heterostructures for room temperature gas sensor and its sensing mechanism: A recent progress[J]. Journal of Alloys and Compounds, 2023, 941: 168943. [27] LEE E, VAHIDMOHAMMADI A, PRORO B C, et al. Room temperature gas sensing of two dimensional titanium carbide (MXene)[J]. ACS Applied Materials & Interfaces, 2017, 9(42): 37184-37190. [28] KIM S J, KOH H J, REN C E, et al. Metallic Ti3C2T x MXene gas sensors with ultrahigh signal-to-noise ratio[J]. ACS Nano, 2018, 12(2): 986-993. doi: 10.1021/acsnano.7b07460 [29] CHOI B, SHIN D, LEE H S, et al. Nanoparticle design and assembly for p-type metal oxide gas sensors[J]. Nanoscale, 2022, 14(9): 3387-3397. doi: 10.1039/D1NR07561F [30] DAS S, MOJUMDER S, SAHA D, et al. Influence of major parameters on the sensing mechanism of semiconductor metal oxide based chemiresistive gas sensors: A review focused on personalized healthcare[J]. Sensors and Actuators B: Chemical, 2022, 352: 131066. [31] 杨俊超, 潘勇, 秦墨林, 等. 金属氧化物半导体气敏传感器研究进展[J]. 化学传感器, 2022, 42(2): 10-18. doi: 10.3969/j.issn.1008-2298.2022.02.002YANG Junchao, PAN Yong, QIN Molin, et al. Research progress of metal oxide semiconductor gas sensor[J]. Chemical Sensors, 2022, 42(2): 10-18(in Chinese). doi: 10.3969/j.issn.1008-2298.2022.02.002 [32] LI N, JIANG Y, ZHOU C, et al. High performance humidity sensor based on urchinlike composite of Ti3C2 MXene derived TiO2 nanowires[J]. ACS Applied Materials & Interfaces, 2019, 11(41): 38116-38125. [33] ZHANG R, DENG Z, CHANG J, et al. Bifunctional role of PDMS membrane in designing humidity tolerant H2S chemiresistors with high selectivity[J]. Chemical Communications, 2023, 59(12): 1689-1692. doi: 10.1039/D2CC05880DIF:4.9Q2 -