纳米ZnO-SiO2自清洁增透薄膜的制备及其性能

郭昭龙; 赵海新; 赵卫

doi:10.7498/aps.65.064206

摘要

以乙酸锌醇热法ZnO纳米粒子为基料, 通过溶胶-凝胶浸渍提拉法制备纳米ZnO-SiO2自清洁增透薄膜. 采用透射电镜, 光谱椭偏仪, 扫描电镜, X-射线衍射, 差热分析仪和UV-vis等技术对样品进行表征, 以亚甲基蓝的光催化降解为目标反应, 评价其光催化活性. 结果表明, ZnO纳米粒子为球粒状结构, 直径约12-20 nm, 特征紫外吸收波长位于375 nm 处; 与未涂覆纳米ZnO-SiO2自清洁增透薄膜的石英玻璃基底相比, 涂覆后石英玻璃在400-800 nm波长范围内平均透光率提升达4.17%, 具有良好的宽光谱增透行为; 且在紫外光激发下对亚甲基蓝染料具有光催化降解特性, 进而具备良好的自清洁性能.

关键词:

Abstract

Unlike the general anti-reflection and self-cleaning film such as SiO2 and TiO2-SiO2, the ZnO-SiO2 nanometric film used as a substrate of excellent transparency in visible region and effective photo-catalytic self-cleaning under UV illumination is seldom studied in the application as a substrate; however, it has a lot of advantages including high transmittance and low refractivity. In this paper, a self-cleaning and anti-reflection ZnO-SiO2 nanometric film is successfully fabricated by using a sol-gel dip-coating method. The morphology, crystal structure, surface microstructure and light transmittance of the obtained products are characterized by techniques such as TEM, SAD, XRD, SEM, DTA and UV-vis. Photo-catalytic degradation of the methylene blue (MB) in aqueous solution is used as probe reaction to evaluate the photo-catalytic activity of ZnO-SiO2 nanometric film. The TEM images reveal that the as-prepared ZnO nanoparticles are spherical grains with diameters of 12-20 nm, the average grain diameter is about 14.51 nm. ZnO nanoparticles obtained are of hexagonal wurtzite structure revealed by XRD pattern and there exist no other diffraction peaks, Furthermore, the SAD results show that ZnO microstructurs have good crystallinity. In addition, the ZnO grain size is about 14.41 nm by using the Scherrer formula calculation, which is consistent with the TEM results by the Gauss simulation. The UV-vis spectra reveal that the ultraviolet characteristic absorption peak of ZnO-SiO2 composite films is located at 368 nm and 375 nm after annealing at different temperatures such as 300℃ and 450℃, corresponding to the band gaps of 3.37 eV and 3.31 eV, respectively. It is highly consistent with that obtained from pure ZnO nanoparticles. Increasing the annealing temperature results in a lower refractive index and the increases of the porosity in of the ZnO-SiO2 composite films. It has a uniformly refractive index value about 1.23-1.25 and a high porosity value about 50.3-54.7% when the annealing temperature is 450 ℃. Experimental results show that the ZnO-SiO2 composite film can enhance the light transmittance of the quartz substrate, due to its lower reflective index and higher porosity. Compared with the quartz substrate, the average optical transmission rate of the quartz glass coated with ZnO-SiO2composite films is increased by about 4.17% at 400-800 nm, which favors greatly anti-reflection characteristics in a wide spectrum range. Meanwhile, the ZnO-SiO2 composite films are found to be efficient for photo-catalytically degradation of methylene blue dye under UV illumination, which favors greatly the self-cleaning function.

Keywords:

nano ZnO /
SiO2film /
sol-gel /
photo-catalytic

作者及机构信息

1.
中国科学院西安光学精密机械研究所, 瞬态光学与光子技术国家重点实验室, 西安 710119;

2.
中国科学院大学, 北京 100049

通信作者: 郭昭龙, gzlxjtu@opt.ac.cn;weiz@opt.ac.cn ; 赵卫, gzlxjtu@opt.ac.cn;weiz@opt.ac.cn

基金项目: 陕西省科学技术研究发展计划(批准号: S2014GY2700)、陕西省科技统筹创新工程计划(批准号: 2015KTCQ01-63)和西安市科技计划(批准号: GX14021-05)资助的课题.

Authors and contacts

1.
State Key Laboratory of Transient Optics and Photonics, Xi'an Institute of Optics and Precision Mechanics, Chinese Academy of Sciences, Xi'an 710119, China;

2.
University of the Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Guo Zhao-Long, gzlxjtu@opt.ac.cn;weiz@opt.ac.cn ; Zhao Wei, gzlxjtu@opt.ac.cn;weiz@opt.ac.cn

Funds: Project supported by the Science Technology Research Development of Shaanxi Province, China (Grant No. S2014GY2700), the Science Technology Plan of Innovation of Shaanxi Province, China (Grant No. 2015KTCQ01-63), and the Science Technology Project of Xi'an, China (Grant No. GX14021-05).

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施引文献

[1]	Choi S J, Huh S Y 2010 Macromol. Rapid Commun. 31 539
[2]	Ye L Q, Zhang Y L, Zhang X X, Hu T, Ji R, Ding B, Jiang B 2013 Sol. Energ. Mat. Sol. C 111 160
[3]	Jiang B, Duan X C, Zhou Z C, Cheng Y J, Liu G C, Liu Y L 2011 J. Inorg. Mater. 26 375 (in Chinese) [蒋波, 段学臣, 周志超, 程亚娟, 刘国聪, 刘杨林 2011 无机材料学报 26 375]
[4]	Mao Q Q, Zeng D W, Xu K, Xie C 2014 RSC Adv. 4 58101
[5]	Zhu J J, Zhao Y L, Zhu L, Gu X Q, Qiang Y H 2014 Chin. Phys. B 23 048104
[6]	Yuan Z H, Tang C C, Fan S S 2001 Chin. Phys. Lett. 18 1520
[7]	Jia X H, Zheng Y J, Yin L C, Huang H L, Jiang H W, Zhu R H 2014 Acta Phys. Sin. 63 166802 (in Chinese) [贾相华, 郑友进, 尹龙承, 黄海亮, 姜宏伟, 朱瑞华 2014 物理学报 63 166802]
[8]	Cao M M, Zhao X R, Duan L B, Liu J R, Guan M M, Guo W R 2014 Chin. Phys. B 23 047805
[9]	Wei W, Dai Y, Huang B B, Jacob T 2013 J. Chem. Phys. 139 144703
[10]	Go B N, Kim Y D, Kim C, Baek S W, Oh K S, Lee H 2015 Mater. Express 5 49
[11]	She G W, Chen X, Wang Y, Qi X P, Mu L X, Shi W S 2012 J. Nanosci. Nanotechno. 12 2756
[12]	Peng F, Chen S H, Zhang L, Wang H J, Xie Z Y 2005 Acta Phys. Chim. Sin. 21 944
[13]	Shang H K, Zhang X Q, Yao Z G, Teng X Y, Wang Y S, Huang S H 2006 Spectrosc. Spect. Anal. 26 415 (in Chinese) [商红凯, 张希清, 姚志刚, 腾小瑛, 王永生, 黄世华 2006 光谱学与光谱分析 26 415]
[14]	Ali M A, Adel A I, Rasha N, Ali A H 2014 J. Photoch. Photobio. A 275 37
[15]	Xue H, Xu X L, Chen Y, Zhang G H, Ma S Y 2009 J. Function Mater. 40 700 (in Chinese) [薛华, 徐小丽, 陈彦, 张国恒, 马书懿 2009 功能材料 40 700]
[16]	Kaneva N V, Siuleiman S A, Bojinova A S, Papazova K I, Dimitrov D T, Gracheva I, Karpova S, Moshnikov V A 2013 Bulg. Chem. Commun. 45 611
[17]	Zhai J, Tao X, Pu Y, Zeng X F, Chen J F 2010 Appl. Surf. Sci. 257 393
[18]	Yan T F, Li Y, Kang J J, Zhou P Y, Sun B Q, Zhang K, Yan S S, Zhang X H 2015 Chin. Phys. Lett. 32 077801
[19]	Yuan N Y, He Z J, Zhao C N, Li F, Zhou Y, Li J H 2008 Acta Phys. Sin. 57 2537 (in Chinese) [袁宁一, 何泽军, 赵常宁, 李峰, 周懿, 李金华 2008 物理学报 57 2537]
[20]	Wang J P, Wang Z Y, Huang B B, Ma Y D, Liu Y Y, Qin X Y, Zhang X Y, Dai Y 2012 ACS Appl. Mater. Interfaces 4 4024
[21]	Liu X C, Chen Z Z, Shi E W, Liao D Q, Zhou K J 2011 Chin. Phys. B 20 037501
[22]	Pei Z L, Zhang X B, Wang T G, Gong J, Sun C, Wen L S 2005 Acta Metal. Sin. 41 84 (in Chinese) [裴志亮, 张小波, 王铁钢, 宫骏, 孙超, 闻立时 2005 金属学报 41 84]
[23]	Gao Y Q, Gereige I, Labban A E, Cha D, Isimjan T T, Beaujuge P M 2014 ACS Appl. Mater. Interfaces 6 2219
[24]	Wang S 2010 Mater. Rev 24 47 (in Chinese) [王珊 2010 材料导报 24 47]
[25]	Zhang X X, Zhuang M Y, Lin M Y, Ye L Q, Jiang B 2014 J. Function Mater. 45 133 (in Chinese) [张欣向, 庄梦云, 林明月, 叶龙强, 江波 2014 功能材料 45 133]
[26]	Hattori H 2001 Adv. Mater. 13 51
[27]	Cai G, Ye J F, Chen S Y, Zhao X W, Zhang D Y, Chen S 2012 Energy Environ. Sci. 5 7575
[28]	Liu TJ, Wang Q, Jiang P 2013 RSC Adv. 3 12662
[29]	Gui Q F, Cui L, Pan J, Hu J G 2013 Acta Phys. Sin. 62 087103 (in Chinese) [桂青凤, 崔磊, 潘靖, 胡经国 2013 物理学报 62 087103]

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