基于硝化纳米纤维素/琼脂的高灵敏度湿度传感器

doi:10.16085/j.issn.1000-6613.2021-1115

化工进展 ›› 2022, Vol. 41 ›› Issue (5): 2604-2614.DOI: 10.16085/j.issn.1000-6613.2021-1115

基于硝化纳米纤维素/琼脂的高灵敏度湿度传感器

陈博¹(), 陈伟香¹, 唐丽荣¹^,²(), 洪祺祺¹, 严雪², 靳江涛¹, 吕日新³, 黄彪¹

^1.福建农林大学材料工程学院，福建福州 350000
^2.福建农林大学金山学院，福建福州 350000
^3.福建农林大学生命科学学院，福建福州 350000

收稿日期:2021-05-26 修回日期:2021-07-25 出版日期:2022-05-05 发布日期:2022-05-24
通讯作者: 唐丽荣
作者简介:陈博（1997—），男，硕士研究生，研究方向为生物质化学与材料工程。E-mail：1357307704@qq.com。
基金资助:
国家自然科学基金(32001267);福建省高等学校“竹资源创新利用”科技创新团队项目(KJG200031A);福建农林大学国际科技合作与交流项目(KXGH17008)

A highly sensitivity humidity sensor based on nitrocellulose nanocrystals/agar

CHEN Bo¹(), CHEN Weixiang¹, TANG Lirong¹^,²(), HONG Qiqi¹, YAN Xue², JIN Jiangtao¹, LYU Rixin³, HUANG Biao¹

^1.College of Material Engineering, Fujian Agriculture and Forestry University, Fuzhou 350000, Fujian, China
^2.Jinshan College, Fujian Agriculture and Forestry University, Fuzhou 350000, Fujian, China
^3.College of Life Sciences, Fujian Agriculture and Forestry University, Fuzhou 350000, Fujian, China

Received:2021-05-26 Revised:2021-07-25 Online:2022-05-05 Published:2022-05-24
Contact: TANG Lirong

摘要/Abstract

摘要：

湿敏材料是决定湿度传感器性能的关键，本研究将具有特殊化学结构的纤维素和琼脂这两种生物质材料有机结合起来，制备具有不同湿度敏感性的硝化纳米纤维素/琼脂（nitrocellulose nanocrystals/Agar，NCNCs/Agar）复合敏感膜材料，基于石英晶体微天平（quartz crystal microbalance，QCM）制备出具有高灵敏度的湿度传感器。结果表明，NCNCs/Agar复合敏感膜修饰的QCM湿度传感器的灵敏度和频率响应值较单一材料敏感膜修饰的QCM均有较明显的提高。经过优化测试，得到NCNCs与琼脂的最佳质量比为1∶25，涂覆2.049μg敏感材料的QCM传感器（QCM-b）性能最优异。在相对湿度（RH）11%~84%下，QCM-b具有良好的线性（R²=0.9933），灵敏度为32.54Hz/%RH。在RH 11%~97%下，QCM-b响应值可达到-5820Hz，具有优异的对数拟合系数（R²=0.9994），恢复时间短（5s），并且具有良好的重现性和长期稳定性，显示出在湿度探测领域的良好应用前景。

关键词: 石英晶体微天平, 湿度传感器, 硝化纳米纤维素, 琼脂, 灵敏度

Abstract:

Humidity sensitive materials are crucial for the humidity sensors. In this study, a novel idea of combing two biomass products with unique chemical structures, cellulose and agar, to prepare nitrocellulose nanocrystals/agar (NCNCs/Agar) composite sensitive film materials with different humidity sensitivity was presented. Based on the above-mentioned sensitive film materials, a high sensitivity quartz crystal microbalance (QCM) humidity sensor was developed. The results revealed that the sensitivity and frequency response of the NCNCs/Agar-based QCM humidity sensor were significantly higher than those of the sensor based on a single-component sensitive film. The results confirmed that the humidity sensor with NCNCs/Agar (optimum NCNCs to agar mass ratio of 1∶25) loading of 2.049μg (QCM-b) exhibited the excellent performance. In addition, the sensor showed excellent linearity (R² =0.9933) in 11%—84% relative humidity (RH) and high sensitivity (32.54Hz/%RH). In 11%—97% RH, the humidity sensor showed high response value (-5820Hz), excellent logarithmic linearity (R² =0.9994), short recovery time (5s), good reproducibility and long-term stability. In conclusion, these results indicated that the NCNCs/Agar-based QCM sensor demonstrated great promise for practical use in humidity detection.

Key words: quartz crystal microbalance (QCM), humidity sensor, nitrocellulose nanocrystals (NCNCs), agar, sensitivity

中图分类号:

TQ352.7

陈博, 陈伟香, 唐丽荣, 洪祺祺, 严雪, 靳江涛, 吕日新, 黄彪. 基于硝化纳米纤维素/琼脂的高灵敏度湿度传感器[J]. 化工进展, 2022, 41(5): 2604-2614.

CHEN Bo, CHEN Weixiang, TANG Lirong, HONG Qiqi, YAN Xue, JIN Jiangtao, LYU Rixin, HUANG Biao. A highly sensitivity humidity sensor based on nitrocellulose nanocrystals/agar[J]. Chemical Industry and Engineering Progress, 2022, 41(5): 2604-2614.

图/表 12

参考文献 38

1	WANG D Y, HUANG Y, CAI W T, et al. Functionalized multi-wall carbon nanotubes/silicone rubber composite as capacitive humidity sensor[J]. Journal of Applied Polymer Science, 2014, 131(11): 40342.
2	FARAHANI H, WAGIRAN R, HAMIDON M N. Humidity sensors principle, mechanism, and fabrication technologies: a comprehensive review[J]. Sensors, 2014, 14(5): 7881-7939.
3	DAI J X, ZHANG T, ZHAO H R, et al. Preparation of organic-inorganic hybrid polymers and their humidity sensing properties[J]. Sensors and Actuators B: Chemical, 2017, 242: 1108-1114.
4	赵晨. 基于改性碳纳米管的QCM型湿度传感器的研究[D]. 长春: 吉林大学, 2018.
	ZHAO Chen. Study on QCM humidity sensor based on modified carbon nanotubes[D]. Changchun: Jilin University, 2018.
5	LIN J B, GAO N B, LIU J M, et al. Superhydrophilic Cu(OH)₂ nanowire-based QCM transducer with self-healing ability for humidity detection[J]. Journal of Materials Chemistry A, 2019, 7(15): 9068-9077.
6	MANNELLI I, MINUNNI M, TOMBELLI S, et al. Quartz crystal microbalance (QCM) affinity biosensor for genetically modified organisms (GMOs) detection[J]. Biosensors and Bioelectronics, 2003, 18(2/3): 129-140.
7	WU Z Q, CHEN X D, ZHU S B, et al. Enhanced sensitivity of ammonia sensor using graphene/polyaniline nanocomposite[J]. Sensors and Actuators B: Chemical, 2013, 178: 485-493.
8	LAHRECH K, SAFOUANE A, PEYRELLASSE J. Sol state formation and melting of agar gels rheological study[J]. Physica A: Statistical Mechanics and Its Applications, 2005, 358(1): 205-211.
9	李亚男, 吴建美, 宋登鹏, 等. 纤维素/琼脂糖复合膜的制备、表征及其形状记忆性能研究[J]. 功能材料, 2021, 52(3): 3086-3091, 3097.
	LI Yanan, WU Jianmei, SONG Dengpeng, et al. Preparation, characterization and shape memory properties of cellulose/agarose composite film[J]. Journal of Functional Materials, 2021, 52(3): 3086-3091, 3097.
10	LI H J, ZHENG H, TAN Y J, et al. Development of an ultrastretchable double-network hydrogel for flexible strain sensors[J]. ACS Applied Materials & Interfaces, 2021, 13(11): 12814-12823.
11	HOU W W, SHENG N N, ZHANG X H, et al. Design of injectable agar/NaCl/polyacrylamide ionic hydrogels for high performance strain sensors[J]. Carbohydrate Polymers, 2019, 211: 322-328.
12	YANG B W, YUAN W Z. Highly stretchable and transparent double-network hydrogel ionic conductors as flexible thermal-mechanical dual sensors and electroluminescent devices[J]. ACS Applied Materials & Interfaces, 2019, 11(18): 16765-16775.
13	CAO Y, MORRISSEY T G, ACOME E, et al. A transparent, self-healing, highly stretchable ionic conductor[J]. Advanced Materials, 2017, 29(10): 1605099.
14	CHEN Q, ZHU L, ZHAO C, et al. A robust, one-pot synthesis of highly mechanical and recoverable double network hydrogels using thermoreversible sol-gel polysaccharide[J]. Advanced Materials, 2013, 25(30): 4171-4176.
15	WANG J L, LIU Y, SU S H, et al. Ultrasensitive wearable strain sensors of 3D printing tough and conductive hydrogels[J]. Polymers, 2019, 11(11): 1873.
16	PRESTI D LO, MASSARONI C, PIEMONTE V, et al. Agar-coated fiber Bragg grating sensor for relative humidity measurements: influence of coating thickness and polymer concentration[J]. IEEE Sensors Journal, 2019, 19(9): 3335-3342.
17	BASIRI S, MEHDINIA A, JABBARI A. A sensitive triple colorimetric sensor based on plasmonic response quenching of green synthesized silver nanoparticles for determination of Fe²⁺, hydrogen peroxide, and glucose[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2018, 545: 138-146.
18	YANG J, XIA Y F, XU P, et al. Super-elastic and highly hydrophobic/superoleophilic sodium alginate/cellulose aerogel for oil/water separation[J]. Cellulose, 2018, 25(6): 3533-3544.
19	WHITE R J, BRUN N, BUDARIN V L, et al. Always look on the “light” side of life: sustainable carbon aerogels[J]. ChemSusChem, 2014, 7(3): 670-689.
20	BARANDUN G, SOPRANI M, NAFICY S, et al. Cellulose fibers enable near-zero-cost electrical sensing of water-soluble gases[J]. ACS Sensors, 2019, 4(6): 1662-1669.
21	ZHOU J, BUTCHOSA N, JAYAWARDENA H S N, et al. Synthesis of multifunctional cellulose nanocrystals for lectin recognition and bacterial imaging[J]. Biomacromolecules, 2015, 16(4): 1426-1432.
22	ESMAEILI C, ABDI M M, MATHEW A P, et al. Synergy effect of nanocrystalline cellulose for the biosensing detection of glucose[J]. Sensors, 2015, 15(10): 24681-24697.
23	SADASIVUNI K K, KAFY A, ZHAI L D, et al. Transparent and flexible cellulose nanocrystal/reduced graphene oxide film for proximity sensing[J]. Small, 2015, 11(8): 994-1002.
24	ZHENG Z, TANG C X, YEOW J T W. A high-performance CMUT humidity sensor based on cellulose nanocrystal sensing film[J]. Sensors and Actuators B: Chemical, 2020, 320: 128596.
25	YANG H, CHOIS E, KIM D, et al. Color-spectrum-broadened ductile cellulose films for vapor-pH-responsive colorimetric sensors[J]. Journal of Industrial and Engineering Chemistry, 2019, 80: 590-596.
26	YAO Y, HUANG X H, ZHANG B Y, et al. Facile fabrication of high sensitivity cellulose nanocrystals based QCM humidity sensors with asymmetric electrode structure[J]. Sensors and Actuators B: Chemical, 2020, 302: 127192.
27	WANG D C, YU H Y, QI D M, et al. Supramolecular self-assembly of 3D conductive cellulose nanofiber aerogels for flexible supercapacitors and ultrasensitive sensors[J]. ACS Applied Materials & Interfaces, 2019, 11(27): 24435-24446.
28	TANG L R, CHEN W X, CHEN B, et al. Sensitive and renewable quartz crystal microbalance humidity sensor based on nitrocellulose nanocrystals[J]. Sensors and Actuators B: Chemical, 2021, 327: 128944.
29	CHEN L H, LI T, CHAN C C, et al. Chitosan based fiber-optic Fabry-Perot humidity sensor[J]. Sensors and Actuators B: Chemical, 2012, 169: 167-172.
30	ZHAO Y, TONG R J, CHEN M Q, et al. Relative humidity sensor based on hollow core fiber filled with GQDs-PVA[J]. Sensors and Actuators B: Chemical, 2019, 284: 96-102.
31	ZHU P H, LIU Y, FANG Z Q, et al. Flexible and highly sensitive humidity sensor based on cellulose nanofibers and carbon nanotube composite film[J]. Langmuir, 2019, 35(14): 4834-4842.
32	PANG Y, JIAN J M, TU T, et al. Wearable humidity sensor based on porous graphene network for respiration monitoring[J]. Biosensors and Bioelectronics, 2018, 116: 123-129.
33	MANJUNATHA S, MACHAPPA T, RAVIKIRAN Y T, et al. Polyaniline based stable humidity sensor operable at room temperature[J]. Physica B: Condensed Matter, 2019, 561: 170-178.
34	WU J, SUN Y M, WU Z X, et al. Carbon nanocoil-based fast-response and flexible humidity sensor for multifunctional applications[J]. ACS Applied Materials & Interfaces, 2019, 11(4): 4242-4251.
35	YAO Y, HUANG X H, CHEN Q, et al. High sensitivity and high stability QCM humidity sensors based on polydopamine coated cellulose nanocrystals/graphene oxide nanocomposite[J]. Nanomaterials, 2020, 10(11): 2210.
36	YUAN Q, GENG W C, LI N, et al. Study on humidity sensitive property of K₂CO₃-SBA-15 composites[J]. Applied Surface Science, 2009, 256(1): 280-283.
37	ZHAO H R, LIN X Z, QI R R, et al. A composite structure of in situ cross-linked poly(ionic liquid)s and paper for humidity-monitoring applications[J]. IEEE Sensors Journal, 2019, 19(3): 833-837.
38	WANG Y, ZHANG L N, ZHOU J P, et al. Flexible and transparent cellulose-based ionic film as a humidity sensor[J]. ACS Applied Materials & Interfaces, 2020, 12(6): 7631-7638.

编号	频率变化值/Hz	薄膜质量/μg	敏感膜质量的标准偏差/%	灵敏度/Hz·%^-1	平均膜厚/nm	膜厚的标准偏差/%
QCM-a	-7365	1.023	1.42	21.56	174	19.60
QCM-b	-14744	2.049	1.06	32.54	216	10.20
QCM-c	-22374	3.109	2.59	58.17	320	17.89
QCM-d	-29538	4.104	1.23	59.68	358	13.27
QCM-e	-36713	5.101	2.69	82.76	486	24.98

编号	频率变化值/Hz	薄膜质量/μg	敏感膜质量的标准偏差/%	灵敏度/Hz·%^-1	平均膜厚/nm	膜厚的标准偏差/%
QCM-a	-7365	1.023	1.42	21.56	174	19.60
QCM-b	-14744	2.049	1.06	32.54	216	10.20
QCM-c	-22374	3.109	2.59	58.17	320	17.89
QCM-d	-29538	4.104	1.23	59.68	358	13.27
QCM-e	-36713	5.101	2.69	82.76	486	24.98

材料	输出信号	测试范围/%RH	灵敏度	响应/恢复时间/s	文献
Chitosan	波长	20~95	0.13nm·%RH	0.38	Chen等^［29］
GQDs-PVA	波长	11.3~81.34	0.11725nm·%RH	—	Zhao等^［30］
NFC/CNT	电流	11~95	69.9%（?I/I₀）	330/377	Zhu等^［31］
GO/graphene，PEBOT：PSS/graphene，AC/ graphene	电阻	12~97	0.0321	31/72	Pang等^［32］
PANI/TaS₂	电阻	11~97	—	36/49	Manjunatha等^［33］
CNCs	电阻	4~95	0.16%RH	1.9/1.5	Wu等^［34］
PDA@CNC/GO	频率	11.3~97.39	5.466×10^-6	11/4（11.3%~48%RH） 37/5（48%~97.39%RH）	Yao等^［35］
Paper	频率	11~90	14.5%（?f/f₀）	240/360	Yuan等^［36］
PILs/paper	阻抗	11~95	961.3（Z₀/Z_g）	25/113	Zhao等^［37］
CKF	电阻	11.3~97.3	—	6.0/10.8	Wang等^［38］
NCNCs/Agar	频率	11~97	82.76Hz/%RH（QCM-e）	17/5（11%~84%RH）	本文

材料	输出信号	测试范围/%RH	灵敏度	响应/恢复时间/s	文献
Chitosan	波长	20~95	0.13nm·%RH	0.38	Chen等^［29］
GQDs-PVA	波长	11.3~81.34	0.11725nm·%RH	—	Zhao等^［30］
NFC/CNT	电流	11~95	69.9%（?I/I₀）	330/377	Zhu等^［31］
GO/graphene，PEBOT：PSS/graphene，AC/ graphene	电阻	12~97	0.0321	31/72	Pang等^［32］
PANI/TaS₂	电阻	11~97	—	36/49	Manjunatha等^［33］
CNCs	电阻	4~95	0.16%RH	1.9/1.5	Wu等^［34］
PDA@CNC/GO	频率	11.3~97.39	5.466×10^-6	11/4（11.3%~48%RH） 37/5（48%~97.39%RH）	Yao等^［35］
Paper	频率	11~90	14.5%（?f/f₀）	240/360	Yuan等^［36］
PILs/paper	阻抗	11~95	961.3（Z₀/Z_g）	25/113	Zhao等^［37］
CKF	电阻	11.3~97.3	—	6.0/10.8	Wang等^［38］
NCNCs/Agar	频率	11~97	82.76Hz/%RH（QCM-e）	17/5（11%~84%RH）	本文

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基于硝化纳米纤维素/琼脂的高灵敏度湿度传感器

A highly sensitivity humidity sensor based on nitrocellulose nanocrystals/agar

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