Application research of multi-functional sensor based on cellulose nanocrystals
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摘要: 纤维素纳米晶体(CNC)是具有优异力学性能、光学性能和表面化学性能的纳米材料,近年来受到了研究者们的广泛关注。基于CNC的传感器具有对外部环境刺激的单重、双重及多重响应,如湿度、气体、pH、溶剂、温度、光等驱动传感,这使其在信息加密、健康检测、食品、环境监测、储能、可穿戴等领域中显示出巨大的应用潜力。本文对CNC的关键特性进行了简要介绍,并重点分析了基于CNC的多功能传感器的重要应用发展研究机制,最后总结了CNC基传感器材料在制备过程中存在的主要问题和面临的挑战,为提高其性能和功能化创新应用提供参考。Abstract: Cellulose nanocrystals (CNC) are nanomaterials with excellent mechanical properties, optical properties and surface chemical properties, which have attracted wide attention from researchers in recent years. CNC-based sensors have a single, double and multiple response to external environmental stimuli, such as humidity, gas, pH, solvent, temperature, light and other drive sensing, which makes it in the information encryption, health detection, food, environmental monitoring, energy storage, wearable and other fields show great application potential. In this paper, the key characteristics of CNC are briefly introduced, and the important application development and research mechanism of multi-functional sensors based on CNC are analyzed. Finally, the main problems and challenges in the preparation process of CNC-based sensor materials are summarized, and the reference is provided for improving their performance and functional innovative applications.
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Key words:
- cellulose nanocrystals /
- structural color /
- chiral nematic structure /
- sensor /
- application
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图 2 (a) 酸水解数控加工及其透射电镜分析[18-19];(b) 通过倾斜角度自组装方法生产的具有彩虹色调和双灵巧光学反射的自组织CNC薄膜[22]
Figure 2. (a) Manufacturing of CNC by acid hydrolysis and the corresponding TEM image[18-19]; (b) Self-organized CNC films with rainbow hues and ambidextrous optical reflection, produced via tilted-angle self-assembly method[22]
RCP—Right-handed circularly polarized; LCP—Left-handed circularly polarized
图 4 (a) 不同目标质量比的CNCs/PEDOT:PSS (CPx)电致变色涂层的制备示意图;(b) CP2和CP3电致变色涂层分别在彩色和漂白状态下的照片[39]
Figure 4. (a) Schematic illustration of the preparation with targeted weight ratios of CNCs/PEDOT:PSS (CPx) electrochromic coatings; (b) Photographs of the CP2 and CP3 electrochromic coatingss in colored and bleached states, respectively[39]
ITO—Indium tin oxide
图 5 (a) CNC与含动态共价二硫化物键的水性聚氨酯(SSWPU)在蒸发自组装过程中的结合机制;(b) 不同溶剂配比下具有自愈能力的柔性光子薄膜(FPFS)的颜色变化示意图;(c) FPFS的溶剂响应机制图;(d) 绘制加密图案的示意图[42]
Figure 5. (a) Combination mechanism of CNC and SSWPU during the evaporation-induced self-assembly; (b) Illustration of color change of flexible photonic film with self-healing ability (FPFS) under different ratio of solvents; (c) Solvents response mechanism diagram of FPFS; (d) Schematic illustrations of drawing encryption pattern[42]
EISA—Evaporation-induced self-assembly; DMF—Dimethylformamide; CSW—CNC/SSWPU; L-CPL—Under the left-handed polarizer; R-CPL—Under the right-handed polarizer
图 6 (a) 通过蒸发诱导自组装(EISA)策略制备CNC/氧化淀粉(OS)/单宁酸(TA)薄膜的示意图[50];(b) 聚β-环糊精(PCD)的合成及具有手性向列结构的光子CNC-PCD薄膜的制备示意图[51]
Figure 6. (a) Illustration of the preparation of CNCs/OS/TA films via the evaporation-induced self-assembly (EISA) strategy[50]; (b) Schematic illustration of the synthesis of PCD and preparation of photonic CNC-PCD film with a chiral nematic structure[51]
图 7 CNCs -聚苯胺(PANI)膜的两面照片:(a) CNCs;(b) PANI;(c) 基于CNC-PANI薄膜的工作电路;(d) 电致变色设备(ECD)示意图;(e) 不同电压下的ECD;(f) 不同电压下CNC薄膜的ECD照片;5次循环后(g)和通过圆偏振滤光片观察(h)的ECD和CNC薄膜的照片[12]
Figure 7. Photographs of two sides of the CNC-PANI film: (a) CNCs; (b) PANI; (c) Working circuit based on CNC-PANI film; (d) Schematic representation of electrochromic device (ECD); Photographs of ECD at different voltages (e) and ECD with CNC films at different voltages (f); Photographs of ECD with CNC films after 5 cycles (g) and when viewed through a circularly polarized filter (h)[12]
表 1 用于响应式CNC光子学的不同刺激及应用机制分析
Table 1. Analysis of different stimuli and application mechanism analysis for responsive CNC photonics
Ingredients Adulterant Matrix form Response type Application Application mechanism analysis Ref. CNC OS, TA, PEDOT:PSS Coating Electrochemistry Information
encryptionElectrochromic and
chiral combination[39] CNC SiO2 Film Optics Information
encryptionPhotochromism [40] CNC PVA Hydrogel Solvent Information
encryptionLocal solvent displacement builds
cryptographic characters and patterns[43] CNC PAA Coating Humidness Information
encryptionPattern the coating according to RA and RH [41] CNC SSWPU Film Solvent Information
encryptionEthanol is used as ink to draw programmable
structural color patterns on the surface of
photonic paper[42] CNC Polyethylene glycol
derivative/
polyacrylamideHydrogel Stress,
temperatureInformation
encryptionAnisotropic hydrogels show different
colors by applying different stresses[44] CNC OS, TA Film Solvent Health
detectionChemical tuning is performed according
to the obvious swelling properties of the film
in different solvents[50] CNC PCD Film Solvent Health
detectionColorimetric identification of homologous alcohols [51] CNC CS, DChN Film pH Food Alkaline TVBN increases the pitch of the film [52] CNC HPG, IL,
AnthFilm pH Food The color of the film changes with the content of TVBN [53] CNC CA, starch/
CSFilm Optics Food Reflectance shift causes color change [15] CNC — Film Gas Environmental monitoring Reversible motion in response to
formaldehyde[56] CNC Glucose, PANI Film Humidness,
pH, solventEnvironmental monitoring The pattern has a chiral nematic structure [12] CNC LLA Film Humidness Environmental monitoring Multidimensional regulation of CNC
cholesteric structure[55] Notes: OS—Oxidized starch; TA—Tannic acid; PEDOT:PSS—Poly(3, 4-ethylenedioxythiophene):poly(styrene sulfonate); PVA—Polyvinyl alcohol; PAA—Polyacrylic acid; SSWPU—Waterborne polyurethanes containing dynamic covalent disulfide bonds; PCD—Polymer beta-cyclodextrin; CS—Chitosan; DChN—Deacetylated chitin nanofibers; HPG—Hydroxypropyl guar gum; IL—Ionic liquid; Anth—Anthocyanin; CA—Citric acid; PANI—Polyaniline; LLA—L-lactic acid; RH—Relative humidity; RA—Rotation angle; TVBN—Total volatile basic nitrogen. -
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