基于晶体复合策略构筑的偶氮苯/聚偏二氟乙烯-六氟丙烯紫外光响应执行器

doi:10.6023/A25050177

化学学报 ›› 2025, Vol. 83 ›› Issue (10): 1166-1173.DOI: 10.6023/A25050177 上一篇下一篇

研究论文

基于晶体复合策略构筑的偶氮苯/聚偏二氟乙烯-六氟丙烯紫外光响应执行器

汪莎莎, 李浩然, 李妍, 张伟昊, 解淑婷, 陈玉刚, 谭懿, 张景瑞, 高欢^*(), 解令海^*()

南京邮电大学柔性电子国家重点实验室先进材料研究院化学与生命科学学院南京 210023

投稿日期:2025-05-18 发布日期:2025-07-21
通讯作者: 高欢, 解令海
基金资助:
南京邮电大学自然科学基金(NY224121); 南京邮电大学自然科学基金(NY222157); 南京邮电大学自然科学基金(2024XZZ05); 有机电子与信息显示国家重点实验室(GZR2022010008); 国家基础科学中心(62288102); 江苏省研究生科研与实践创新计划项目(KYCX24_1144); 大学生创新创业训练计划项目(202410293163Y)

Fabrication of Azobenzene/poly(vinylidenefluoride-co-hexafluoropropylene) UV Light-Responsive Actuator based on Crystalline Composite Strategy

Shasha Wang, Haoran Li, Yan Li, Weihao Zhang, Shuting Xie, Yugang Chen, Yi Tan, Jingrui Zhang, Huan Gao^*(), Linghai Xie^*()

State Key Laboratory of Flexible Electronics (LoFE), Institute of Advanced Materials (IAM), School of Chemistry and Life Sciences, Nanjing University of Posts and Telecommunications, Nanjing 210023, China

Received:2025-05-18 Published:2025-07-21
Contact: Huan Gao, Linghai Xie
Supported by:
Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY224121); Natural Science Foundation of Nanjing University of Posts and Telecommunications(NY222157); Natural Science Foundation of Nanjing University of Posts and Telecommunications(2024XZZ05); State Key Laboratory of Organic Electronics and Information Display(GZR2022010008); National Basic Science Foundation of China(62288102); Postgraduate Research & Practice Innovation Program of Jiangsu Province(KYCX24_1144); College Students' Innovative Entrepreneurial Training Plan Program(202410293163Y)

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摘要/Abstract

发展快速且大位移的光响应执行器, 对人工肌肉在非接触和远程控制方面的应用具有关键意义. 本工作验证了光异构偶氮苯(Azo)分子的光响应现象, 并研究了Azo在单晶、微晶状态下的光响应行为. 基于Azo纳晶, 通过结合聚偏二氟乙烯-六氟丙烯(PVDF-HFP), 成功制备了Azo/PVDF-HFP复合薄膜并用于紫外光响应执行器的高效构筑. 研究发现, 由于Azo纳晶的有序结构在光刺激下产生了应力累加现象, 与Azo/PVDF-HFP无定形复合薄膜相比, 采用晶体复合策略制备的Azo/PVDF-HFP纳晶复合薄膜展现出更大的形变和更稳定的响应特性. 进一步通过优化复合薄膜中Azo纳晶的质量分数(40%), 执行器在8 s内可快速实现44.45°的弯曲形变.

关键词: 偶氮苯, 紫外光响应执行器, 聚偏二氟乙烯-六氟丙烯, 晶体复合策略, 应力累加

The development of fast, large-displacement photoresponsive actuator is of significant importance for promoting the application of artificial muscle in the fields of non-contact and remote control. In this study, we initially verified the photoresponsive behavior of the azobenzene (Azo) molecule through Ultraviolet-visible (UV-vis) spectroscopy, Fourier transform infrared spectroscopy (FTIR), and nuclear magnetic resonance hydrogen spectroscopy (¹H NMR). Subsequently, Azo single crystals and microcrystals were prepared via liquid-phase diffusion and reprecipitation methods, and their morphology and photoresponsive properties were characterized using optical microscope and X-ray diffraction (XRD). Finally, by incorporating Azo nanocrystals with poly(vinylidenefluoride-co-hexafluoropropylene) (PVDF-HFP), we successfully fabricated high-performance Azo/PVDF-HFP UV light-responsive actuator. Specifically, a particular proportion of Azo powder and poly(vinylidenefluoride-co-hexafluoropropylene) particles were thoroughly dissolved in N,N-dimethylformamide (DMF) under heating at 80 ℃. Subsequently, by regulating the aggregation states of Azo molecules in the PVDF-HFP matrix (crystalline and amorphous states) via drop-coating and spin-coating methods, we successfully prepared Azo/PVDF-HFP nanocrystal composite films and Azo/PVDF-HFP amorphous composite films. These composite films were then utilized for the efficient construction of UV light-responsive actuator. By precisely controlling the volume of solution, drying temperature, spin-coating speed, these films were carefully controlled to a consistent size in length, width (0.2 cm×2.5 cm), and thickness (20 μm). Then, a 76 mW/cm² UV lamp with a wavelength of 365 nm was placed horizontally 1 cm away from the side of the composite film to explore the crystallization effect of photoisomerized Azo molecules on the performance of the photoactuator. The experimental results indicated that, compared with Azo/PVDF-HFP amorphous composite film, Azo/PVDF-HFP nanocrystal composite film prepared by using crystalline composite strategy exhibits significantly greater light-driven bending deformation and enhanced light response stability. The improvement is attributed to the ordered structure of Azo crystals in the nanocrystalline state, which promote stress accumulation under light stimulation. Finally, by optimizing the mass fraction of Azo in the nanocrystalline composite film to 40% (w), a high-performance Azo/PVDF-HFP UV-responsive actuator was successfully constructed. The actuator achieved a rapid bending deformation of 44.45° within 8 s, exhibiting the optimal response rate. By implementing crystalline composite strategy to integrate the robust optomechanical responsiveness of dynamic molecular crystals with the flexibility of polymers, we successfully realized a novel approach for the fabrication of high-performance artificial muscles, which provides a new idea for the development of soft robots in the future.

Key words: azobenzene, UV light-responsive actuator, poly(vinylidenefluoride-co-hexafluoropropylene), crystalline composite strategy, stress accumulation

引用此文

汪莎莎, 李浩然, 李妍, 张伟昊, 解淑婷, 陈玉刚, 谭懿, 张景瑞, 高欢, 解令海. 基于晶体复合策略构筑的偶氮苯/聚偏二氟乙烯-六氟丙烯紫外光响应执行器[J]. 化学学报, 2025, 83(10): 1166-1173.

Shasha Wang, Haoran Li, Yan Li, Weihao Zhang, Shuting Xie, Yugang Chen, Yi Tan, Jingrui Zhang, Huan Gao, Linghai Xie. Fabrication of Azobenzene/poly(vinylidenefluoride-co-hexafluoropropylene) UV Light-Responsive Actuator based on Crystalline Composite Strategy[J]. Acta Chimica Sinica, 2025, 83(10): 1166-1173.

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图/表 4

图1. (a) Azo分子顺反异构反应; (b) Azo的UV-vis吸收光谱; (c) Azo的FTIR光谱(4000~500 cm−1); (d) Azo的FTIR光谱(1100~600 cm−1)

Figure 1. (a) cis-trans isomerization reaction of Azo; (b) UV-vis absorption spectra of Azo; (c) FTIR spectra of Azo (4000~500 cm−1); (d) FTIR spectrum of Azo (1100~600 cm−1)

图2. (a~c) Azo微晶在紫外光照射1、2 min前后的光学显微镜形貌图; (d) trans-Azo 微晶与单晶模拟的XRD对比图谱; (e) Azo微晶光致响应行为探究实验设置示意图

Figure 2. (a~c) Optical microscopy image of Azo microcrystals before and after UV light exposure for 1 and 2 min; (d) XRD comparison diagram between trans-Azo microcrystals and trans-Azo single crystal simulated; (e) Schematic diagram of experimental set-up for investigating photoresponse behavior of Azo microcrystals

图3. (a) Azo/PVDF-HFP-drop casting薄膜的TEM图; (b) Azo/PVDF-HFP-drop casting薄膜的HR-TEM图, 插图内为SAED图; (c~e) PVDF-HFP, Azo/PVDF-HFP-spin coating, Azo/PVDF-HFP-drop casting薄膜的XRD, UV-vis图谱以及弯曲角度随时间变化曲线图; (f) Azo/PVDF-HFP-drop casting薄膜的循环弯曲曲线图

Figure 3. (a) TEM image of Azo/PVDF-HFP-drop casting film; (b) HR-TEM image of Azo/PVDF-HFP-drop casting film, with the inset showing SAED image; (c~e) XRD diagram, UV-vis spectra and bending angle curves change with time; (f) Cyclic bending curve of Azo/PVDF-HFP-drop casting film

图4. (a, b)不同Azo质量分数的Azo/PVDF-HFP-drop casting薄膜弯曲角度随时间变化曲线图与最大弯曲角度统计图; (c)质量分数为40%的Azo/PVDF-HFP-drop casting薄膜的执行过程

Figure 4. (a, b) Bending angle curves change with time and maximum bending angle statistical diagram of Azo/PVDF-HFP-drop casting films with different Azo mass ratios; (c) Actuation process of Azo/PVDF-HFP-drop casting film with 40% mass ratio of Azo content

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基于晶体复合策略构筑的偶氮苯/聚偏二氟乙烯-六氟丙烯紫外光响应执行器

Fabrication of Azobenzene/poly(vinylidenefluoride-co-hexafluoropropylene) UV Light-Responsive Actuator based on Crystalline Composite Strategy

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