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

doi:10.6023/A25050177

Acta Chimica Sinica ›› 2025, Vol. 83 ›› Issue (10): 1166-1173.DOI: 10.6023/A25050177 Previous Articles Next Articles

Article

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)

1. .pdf(1176KB)

Abstract

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

Cite this article

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.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 4

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)

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

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

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

References 45

[1]	Yin S.-K.; Yao D.-R.; Song Y.; Heng W.-Z.; Ma X.-T.; Han H.; Gao W. Chem. Rev. 2024, 20, 11585.
[2]	Mendes P.-M. Chem. Soc. Rev. 2008, 37, 2512. doi: 10.1039/b714635n pmid: 18949123
[3]	Xiao K.; Xie G.-H.; Li P.; Liu Q.; Hou G.-L.; Zhang Z.; Ma J.; Tian Y.; Wen L.-P.; Jiang L. Adv. Mater. 2014, 26, 6560.
[4]	Wang B.; Lu Y. Nano-Micro Lett. 2024, 16, 155. doi: 10.1007/s40820-024-01379-4 pmid: 38499833
[5]	Wei Y.; Peng Q.; Zhong C.-X.; Ma S.-W.; Wang T.; Pu Y.-T.; Zhang W.-H.; Wang S.-S.; Xie L.-H. Dyes Pigm. 2024, 225, 112097.
[6]	Zhang D.-J.; Liu J.; Chen B.; Wang J.-X.; Jiang L. Acta Chim. Sinica 2018, 76, 425 (in Chinese). doi: 10.6023/A18010035
	(张大杰, 刘捷, 陈波, 王京霞, 江雷, 化学学报, 2018, 76, 425.)
[7]	Wang G.-G.; Zhang J.-Z.; Liu S.-R.; Wang X.-H.; Liu X.-Y.; Chen J.-Z. Acta Polym. Sin. 2021, 52, 124 (in Chinese).
	(王格格, 张居中, 刘水任, 王向红, 刘旭影, 陈金周, 高分子学报, 2021, 52, 124.)
[8]	Madani Z.; Silva P.; Baniasadi H.; Vaara M.; Das S.; Arias J.-C.; Seppälä J.; Sun Z.-P.; Vapaavuori J. Adv. Mater. 2024, 36, 2405917.
[9]	Qing X.; Lv J.-A.; Yu Y.-L. Acta Polym. Sin. 2017, 11, 1679 (in Chinese).
	(卿鑫, 吕久安, 俞燕蕾, 高分子学报, 2017, 11, 1679.)
[10]	Ma J.-Z.; Wang Y.-P.; Sun J.-H.; Yang Z.-Q. Adv. Funct. Mater. 2024, 2402403.
[11]	Wang S.-S.; Meng P.-H.; Li Y.; Deng H.-C.; Guo Z.-X.; Liu Y.-R.; Shi N.-E.; Wei Y.; Xie L.-H. Acta Chim. Sinica 2024, 82, 570 (in Chinese).
	(汪莎莎, 孟鹏辉, 李阳, 邓慧婵, 郭志翔, 刘一任, 石乃恩, 魏颖, 解令海, 化学学报, 2024, 82, 570.)
[12]	Wang S.-S.; Li Y.-A.; Deng H.-C.; Guo Z.-X.; Kan Y.-H.; Cao H.-T.; Xie L.-H. Chin. Sci. Bull. 2024, 69, 578 (in Chinese).
	(汪莎莎, 李延昂, 邓慧婵, 郭志翔, 阚玉和, 曹洪涛, 解令海, 科学通报, 2024, 69, 578.)
[13]	Yue W.; Xu R.-X.; Sui F.-P.; Gao Y.; Lin L.-W. Adv. Funct. Mater. 2024, 34, 2401159.
[14]	Tang G.-Q.; Zhao X.; Liu S.-L.; Mei D.; Zhao C.; Li L.-J.; Wang Y.-J. Adv. Funct. Mater. 2024, 2412254.
[15]	Zhou X.-S.; Li M.-X.; Cao X.-T.; Dong X.; Fang S.-L.; Li L.-Z.; Yuan N.-Y.; Ding J.-N.; Baughman R.-H. Adv. Funct. Mater. 2024, 2409634.
[16]	Liang H.; Zhang Y.-B.; He E.-J.; Yang Y.; Liu Y.-W.; Xu H.-T.; Yang Z.-J.; Wang Y.-X.; Wei Y.; Ji Y. Adv. Mater. 2024, 2400286.
[17]	Tan M.; Wang H.; Gao D.; Huang P.-W.; Lee P.-S. Chem. Soc. Rev. 2024, 53, 3485.
[18]	Qin Z.-H.; Jiang Y.; Soh S. Nat. Mater. 2025, 24, 14.
[19]	Zhang M.-C.; Pal A.; Lyu X.-L.; Wu Y.-D.; Sitti M. Nat. Mater. 2024, 23, 560.
[20]	Kitagawa D.; Nishi H.; Kobatake S. Angew. Chem. Int. Ed. 2013, 52, 9320. doi: 10.1002/anie.201304670 pmid: 23873738
[21]	Li C.; Iscen A.; Palmer L.-C.; Schatz G.-C.; Stupp S.-I. J. Am. Chem. Soc. 2020, 142, 8447.
[22]	Tong F.; Xu W.; Al-Haidar M.; Kitagawa D.; Al-Kaysi R.-O.; Bardeen C.-J. Angew. Chem. Int. Ed. 2018, 57, 7080. doi: 10.1002/anie.201802423 pmid: 29660217
[23]	Uchida E.; Azumi R.; Norikane Y. Nat. Commun. 2015, 6, 7310. doi: 10.1038/ncomms8310 pmid: 26084483
[24]	Naumov P.; Karothu D.-P.; Ahmed E.; Catalano L.; Commins P.; Halabi K.-M.; Al-Handawi M.-B.; Li L. J. Am. Chem. Soc. 2020, 142, 13256. doi: 10.1021/jacs.0c05440 pmid: 32559073
[25]	Zhou B.; Yan D.-P. Appl. Phys. Rev. 2021, 8, 041310.
[26]	Saha S.; Mishra M.-K.; Reddy C.-M.; Desiraju G.-R. Acc. Chem. Res. 2018, 51, 2957.
[27]	Wei X.; Li B.; Yang Z.-Q.; Zhong R.-L.; Wang Y.-F.; Chen Y.-A.; Ding Z.-Y.; Men G.-W.; Yang Z.-R.; Zhang H.-Y.; Yang B.; Xu W.-Q.; Jiang S.-M. Chem. Sci. 2021, 12, 15588.
[28]	Rath B.-B.; Vittal J.-J. J. Am. Chem. Soc. 2020, 142, 20117.
[29]	Karothu D.-P.; Weston J.; Desta I.-T.; Naumov P. J. Am. Chem. Soc. 2016, 138, 13298. pmid: 27618207
[30]	Al-Handawi M.-B.; Dushaq G.; Commins P.; Karothu D.-P.; Rasras M.; Catalano L.; Naumov P. Adv. Mater. 2022, 34, 2109374.
[31]	Shi Y.-X.; Zhang W.-H.; Abrahams B.-F.; Braunstein P.; Lang J.-P. Angew. Chem. Int. Ed. 2019, 58, 9453.
[32]	Singh M.; Abhijitha V.-G.; Nanda B.-R.; Pareek D.; Nath S.; Anwar S.; Kumar A.; Nanda P.-K.; Sahoo S.-C. Chem. Eng. J. 2023, 464, 142665.
[33]	Yu Q.; Yang X.-J.; Chen Y.; Yu K.-Q.; Gao J.; Liu Z.-F.; Cheng P.; Zhang Z.-J.; Aguila B.; Ma S.-Q. Angew. Chem. Int. Ed. 2018, 57, 10192.
[34]	Lan T.; Chen W. Angew. Chem. Int. Ed. 2013, 52, 6496.
[35]	Vetrakov. L.; Ladanyi. V.; Anshori. J.-A.; Dvorak. P.; Wirz. J.; Heger. D. Photochem. Photobiol. Sci. 2017, 16, 1749.
[36]	Koshima H.; Ojima N.; Uchimoto H. J. Am. Chem. Soc. 2009, 131, 6890. doi: 10.1021/ja8098596 pmid: 19453188
[37]	Koshima H.; Ojima N. Dyes Pigm. 2012, 92, 798.
[38]	Taniguchi T.; Fujisawa J.; Shiro M.; Koshima H.; Asahi T. Chem. Eur. J. 2016, 22, 7950.
[39]	Hao Y.; Huang S.; Guo Y.; Zhou L.; Hao H.; Barrett C.-J.; Yu H.-F. J. Mater. Chem. C 2019, 7, 503.
[40]	Norikane Y.; Hayashino M.; Ohnuma M.; Abe K.; Kikkawa Y.; Saito K.; Manabe K.; Miyake K.; Nakano M.; Takada N. Front. Chem. 2021, 9, 684767
[41]	Saikawa M.; Manabe K.; Saito K.; Kikkawa Y.; Norikane Y. CrystEngComm 2024, 26, 6274.
[42]	Ghafari M.; Sanaee Z.; Babaei A.; Mohajerzadeh S. J. Power Sources 2025, 652, 237608.
[43]	Nie R.-P.; Tang W.-B.; Chen C.; Huang H.-D.; Li Y.; Dai K.; Lei J.; Li Z.-M. J. Mater. Chem. C 2021, 9, 12239.
[44]	Koptyaev A.-I.; Travkin V.-V.; Sachkov Y.-I.; Romanenko Y.-V.; Pakhomov G.-L. J. Mater. Sci.: Mater. Electron. 2021, 32, 17791.
[45]	Ishizaki K.; Sugimoto R.; Hagiwara Y.; Koshima H.; Taniguchi T.; Asahi T. CrystEngComm 2021, 23, 5839. doi: 10.1039/d1ce00208b

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

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 4

References 45

Related Articles 11

Recommended Articles

Metrics

Comments

[1]	Luocong Wang, Zhewei Li, Caiwei Yue, Peihuan Zhang, Ming Lei, Min Pu. Theoretical Study on the Isomerization Mechanism of Azobenzene Derivatives under Electric Field [J]. Acta Chimica Sinica, 2022, 80(6): 781-787.
[2]	Bo Wu, Chong Wang, Baolin Li, Chunru Wang. Light-driven Molecular Magnetic Switch for a Metallofullerene^※ [J]. Acta Chimica Sinica, 2022, 80(2): 101-104.
[3]	Liu Xiaojun, Qin Lang, Zhan Yuanyuan, Chen Meng, Yu Yanlei. Phototuning of Structural Colors in Cholesteric Liquid Crystals [J]. Acta Chimica Sinica, 2020, 78(6): 478-489.
[4]	Ding Yanchun, Yu Yanlei, Wei Jia. Synthesis and Self-assembly Behavior of Photo-responsive Diblock Copolymers with Different Hydrophilic/Hydrophobic Ratios [J]. Acta Chimica Sinica, 2014, 72(5): 602-608.
[5]	FENG Xiao-Zhong, YAN Li-Jun, ZHANG Chi-Gong, YAN Fu-Feng, DOU Jun, LI Pan-Shan, ZHENG Xian-Jun. DNA Immobilization onto the Self-assembled Monolayer of Azobenzene Modified by Amino Group [J]. Acta Chimica Sinica, 2010, 68(10): 931-935.
[6]	Wang Guojie Wang. The Study of Azobenzene Self-Assembled Monolayers Fabricated by Chemical Adsorption and Its Superhydrophobic Surface [J]. Acta Chimica Sinica, 2009, 67(13): 1417-1420.
[7]	. Preparation of Photosensitive Azobenzene Monolayer and Its Protein Adsorption Behavior [J]. Acta Chimica Sinica, 2009, 67(12): 1401-1405.
[8]	TANG Xin-De*^,1,2; GAO Long-Cheng²; HAN Nian-Feng; FAN Xing-He²; ZHOU Qi-Feng². Synthesis and Characterization of Tri-arm Star Side-chain Liquid Crystalline Polymers Containing Azobenzene via Atom Transfer Radical Polymerization [J]. Acta Chimica Sinica, 2007, 65(16): 1736-1740.
[9]	TANG Xin-De^1,2,ZHANG Qi-Zhen*^,1,LI Ai-Xiang FAN Xing-He³,CHEN Xiao-Fang³,ZHOU Qi-Feng³. Study on a Novel Pentaerythritol-based Carbosilane Liquid Crystalline Dendrimer of the Third Generation [J]. Acta Chimica Sinica, 2005, 63(2): 138-142.
[10]	GUO Lin, ZHANG Xuan, JIANG Yun-Bao. Design of a Fluoride-Selective Colorimetric Receptor and Its Fluoride Recognition Mechanism [J]. Acta Chimica Sinica, 2004, 62(18): 1811-1814.
[11]	LI Qiang, LI Zhong. Ion Exchange Adsorption of Montmorillonite/Cation Azobenzene Dye Nanocomplexes [J]. Acta Chimica Sinica, 2004, 62(15): 1409-1414.