TbW10-Agarose柔性自支持绿光薄膜的制备及化学响应荧光开关性能研究

doi:10.15541/jim20180506

无机材料学报 ›› 2019, Vol. 34 ›› Issue (8): 844-850.DOI: 10.15541/jim20180506 CSTR: 32189.14.10.15541/jim20180506

TbW₁₀-Agarose柔性自支持绿光薄膜的制备及化学响应荧光开关性能研究

王斌¹,郑金慧¹,王晓红¹,赵博²,许良¹,刘宗瑞¹()

^1. 内蒙古民族大学化学化工学院, 通辽 028043
^2. 长春理工大学化学与环境工程学院, 长春 130022

收稿日期:2018-10-26 修回日期:2018-12-10 出版日期:2019-08-20 网络出版日期:2019-05-29
作者简介:王斌(1986-), 男, 副教授, 博士研究生. E-mail: <email>blueleafage5@163.com</email>
基金资助:
国家自然科学基金(21501102);国家自然科学基金(21501014);内蒙古自治区自然科学基金(2015BS0207);内蒙古自治区高等学校“青年科技英才支持计划”(NJYT-18-B22);内蒙古民族大学“天然产物化学及功能分子合成自治区重点实验室”开放课题(MDK2016010)

Preparation and Chemically Responsive Luminescent Switching of the Flexible Self-supporting TbW₁₀-Agarose Green Emission Thin Films

WANG Bin¹,ZHENG Jin-Hui¹,WANG Xiao-Hong¹,ZHAO Bo²,XU Liang¹,LIU Zong-Rui¹()

^1. College of Chemistry and Chemical Engineering, Inner Mongolia University for the Nationalities, Tongliao 028043, China
^2. School of Chemistry & Environment Engineering, Changchun University of Science and Technology, Changchun 130022, China;

Received:2018-10-26 Revised:2018-12-10 Published:2019-08-20 Online:2019-05-29
Supported by:
National Natural Science Foundation of China(21501102);National Natural Science Foundation of China(21501014);Natural Science Foundation of Inner Mongolia, China(2015BS0207);Program for Young Talents of Science and Technology in Universities of Inner Mongolia Autonomous Region(NJYT-18-B22);Open Projects Founded by Inner Mongolia Key Laboratory for the Natural Products Chemistry and Functional Molecular Synthesis(MDK2016010)

摘要/Abstract

摘要：

基于功能互补原理, 以稀土多酸Na₉TbW₁₀O₃₆(TbW₁₀)为发光功能组分、琼脂糖为成膜基质, 通过溶胶-凝胶及Casting技术制备了稀土多酸柔性自支持绿光薄膜TbW₁₀-Agarose, 利用FT-IR、Raman光谱对薄膜的组成及结构进行表征, 利用SEM、AFM和TEM对薄膜的厚度、表面粗糙度和微结构进行研究, 考察TbW₁₀掺杂量对薄膜透光率及发光性能的影响。在HCl/NH₃刺激下, 实现了TbW₁₀-Agarose绿光薄膜可逆的化学响应荧光开关性质, 利用荧光动力学方法对绿光薄膜化学响应荧光开关的响应时间及可逆性进行研究; 并拓展了该绿光薄膜对HCl气体的荧光光谱检测, 检出限为0.2731 mmol·L ^-1。

关键词: 多金属氧酸盐, 刺激响应, 荧光开关, 薄膜传感器

Abstract:

Flexible self-supporting TbW₁₀-agarose composite thin films were prepared by combination of Sol-Gel and casting technique based on the functional complementarity between excellent green luminescence polyoxometalates TbW₁₀ and good film-forming matrix agarose. Composition and structure of the films were characterized by FT-IR and Raman spectrum. Thir thickness, surface roughness and microstructure were studied by SEM, AFM and TEM, respectively. And effects of different TbW₁₀ contents on the transmittance and luminescence properties were investigated. On this basis, the reversible chemically responsive luminescent switching performance of TbW₁₀-Agarose green luminescent film was realized under stimulation of HCl and NH₃. The response time and reversibility of chemically responsive luminescent switching performance were studied by fluorescence kinetics curves. And the fluorescence spectrum detection for HCl gas was extended based on the green luminescent thin film sensor with a detection limit of 0.2731 mmol·L ^-1.

Key words: polyoxometalates, stimuli-responsive, luminescent switch, thin film sensor

中图分类号:

O611

王斌, 郑金慧, 王晓红, 赵博, 许良, 刘宗瑞. TbW₁₀-Agarose柔性自支持绿光薄膜的制备及化学响应荧光开关性能研究[J]. 无机材料学报, 2019, 34(8): 844-850.

WANG Bin, ZHENG Jin-Hui, WANG Xiao-Hong, ZHAO Bo, XU Liang, LIU Zong-Rui. Preparation and Chemically Responsive Luminescent Switching of the Flexible Self-supporting TbW₁₀-Agarose Green Emission Thin Films[J]. Journal of Inorganic Materials, 2019, 34(8): 844-850.

图/表 10

图1 Na9TbW10O36粉末及模拟的XRD谱图

Fig. 1 XRD patterns of experimental and calculated powder

图2 薄膜制备过程的实物照片

Fig. 2 Physical photographs of film preparation process

图3 薄膜TbW10-Agarose的红外光谱(a)和拉曼光谱(b)

Fig. 3 FT-IR spectra (a) and Raman spectra (b) of the TbW10-Agarose film

图4 薄膜TbW10-Agarose的SEM(a)、AFM(b)照片及Agarose(c)与 TbW10-Agarose(d)的TEM照片

Fig. 4 SEM (a) and AFM (b) images of the TbW10-Agarose films, and TEM images of the Agarose (c) and TbW10-Agarose (d) films

图5 薄膜TbW10-Agarose的紫外-可见光谱(a)及荧光光谱(b)

Fig. 5 UV-Vis spectra (a) and luminescence spectra (b) of the TbW10-Agarose film

图6 不同TbW10含量TbW10-Agarose薄膜的紫外-可见光谱(a)及荧光光谱(b)

Fig. 6 UV-Vis spectra (a) and luminescence spectra (b) of the TbW10-Agarose films containing different TbW10 contents

图7 薄膜TbW10-Agarose在HCl、NH3气体中交替浸渍后的红外光谱(a)和拉曼光谱图(b)

Fig. 7 FT-IR spectra (a) and Raman spectra (b) of the TbW10-Agarose film alternately exposed in HCl and NH3 gas

图8 在不同条件下, 薄膜TbW10-Agarose的荧光光谱图(a)、实物照片(b)及荧光开关机理示意图(c)

Fig. 8 Luminescence spectra (a), corresponding photographs (b) and luminescent switch illustration (c) of TbW10-Agarose film in different conditions

图9 在HCl、NH3刺激下, 薄膜TbW10-Agarose在547 nm处的荧光强度随时间的变化曲线

Fig. 9 Luminescent intensity at 547 nm with time under the stimulation of HCl and NH3 gases

图10 薄膜TbW10-Agarose在不同HCl气体浓度下的荧光光谱, 插图为547 nm处荧光强度的对数对HCl气体浓度作图

Fig. 10 Luminescent spectra of TbW10-Agarose film with different HCl gas concentration and the inset shows the logarithm of luminescent intensities at 547 nm as a function of HCl gas concentration

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TbW₁₀-Agarose柔性自支持绿光薄膜的制备及化学响应荧光开关性能研究

Preparation and Chemically Responsive Luminescent Switching of the Flexible Self-supporting TbW₁₀-Agarose Green Emission Thin Films

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