PPy-CeO_2复合薄膜柔性NO_2传感器的制备与气敏特性研究
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摘要
以吡咯(Py)单体为前驱液,六水合三氯化铁(FeCl_3·6H_2O)为氧化剂,通过化学氧化聚合法与自组装相结合工艺在柔性聚酰亚胺(PI)衬底上制备聚吡咯-二氧化铈(PPy-CeO_2)复合薄膜。通过紫外-可见吸收光谱(UV-Vis)、傅立叶红外光谱(FTIR)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)及X射线衍射(XRD)、X射线电子能谱分析(XPS)对纯PPy和PPyCeO_2复合材料进行了表征分析,结果表明PPy-CeO_2呈典型的核-壳结构。在室温条件下研究了纯PPy薄膜和PPy-CeO_2复合薄膜对二氧化氮(NO2)的响应特性,结果表明,PPy-CeO_2复合薄膜传感器显示出更优的响应特性,灵敏度为纯PPy薄膜传感器的12.6倍,且具有良好的重复性和选择性。最后讨论分析了PPy-CeO_2复合薄膜传感器的NO2敏感机理。
Polypyrrole-cerium dioxide(PPy-CeO_2) composite thin film on polyimide(PI) flexible substrate was prepared by combining the chemical oxidation polymerization with self-assembly method using pyrrole(Py) as precursor and FeCl_3·6 H_2O as oxidizing agent. The obtained PPy and PPy-CeO_2 were characterized and analyzed by Ultraviolet-visible absorption spectrometer(UV-Vis),Fourier transform infrared spectroscopy(FTIR),Scanning electron microscope(SEM),Transmission electron microscope(TEM) and X-ray diffraction(XRD),X ray electron spectroscopy analysis(XPS).The results showed that PPy-CeO_2 exhibited a typical core-shell structure. The NO2-sensing properties of pure PPy and PPy-CeO_2 composite thin film sensors were investigated at room temperature,and the results indicated that the composite thin film sensor showed the superior response characteristics. The sensitivity is 12. 6 times larger than that of pure PPy film one. Furthermore,the PPy-CeO_2 film sensor possessed good repeatability and selectivity. Finally,the NO2-sensingmechanism of PPy-CeO_2 film sensor was analyzed and discussed.
Polypyrrole-cerium dioxide(PPy-CeO_2) composite thin film on polyimide(PI) flexible substrate was prepared by combining the chemical oxidation polymerization with self-assembly method using pyrrole(Py) as precursor and FeCl_3·6 H_2O as oxidizing agent. The obtained PPy and PPy-CeO_2 were characterized and analyzed by Ultraviolet-visible absorption spectrometer(UV-Vis),Fourier transform infrared spectroscopy(FTIR),Scanning electron microscope(SEM),Transmission electron microscope(TEM) and X-ray diffraction(XRD),X ray electron spectroscopy analysis(XPS).The results showed that PPy-CeO_2 exhibited a typical core-shell structure. The NO2-sensing properties of pure PPy and PPy-CeO_2 composite thin film sensors were investigated at room temperature,and the results indicated that the composite thin film sensor showed the superior response characteristics. The sensitivity is 12. 6 times larger than that of pure PPy film one. Furthermore,the PPy-CeO_2 film sensor possessed good repeatability and selectivity. Finally,the NO2-sensingmechanism of PPy-CeO_2 film sensor was analyzed and discussed.
引文
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[2]宋晓岚,闫程印,张颖,等.气敏材料的研究进展及展望[J].材料导报,2012,26(11):36-39,44.
[3]李远,肖文海,陈静,等.基于RGD多肽掺杂聚吡咯铟锡氧化物的仿生微电极构建及用于细胞生物学行为的电化学阻抗谱检测[J].传感技术学报,2017,30(2):174-183.
[4]洪利杰.聚吡咯及其纳米复合敏感材料的制备及气湿敏特性研究[D].杭州:浙江大学,2012.
[5]Chougule M A,Dalavi D S,Mali Sawanta,et al.Novel Method for Fabrication of Room Temperature Polypyrrole-Zn O Nanocomposite NO2Sensor[J].Measurement,2012,45(8):1989-1996.
[6]Nalage S R,Mane A T,Pawar R C,et al.Polypyrrole-Ni O Hybrid Nanocomposite Films:Highly Selective,Sensitive,and Reproducible NO2Sensors[J].Ionics,2014,20(11):1607-1616.
[7]耿丽娜,王淑荣,李鹏,等.聚吡咯-二氧化锡杂化材料的制备及气敏性研究[J].无机化学学报,2005(7):977-981.
[8]Hiroshi I S,Kishimoto M,Yakabe H,et al.6-Highly Selective Molecularly Imprinted Overoxidized Polypyrrole Colloids One-Step Preparation Technique[J].The International Journal of Analytical Sciences,2002,18(1):41-44.
[9]Navale S T,Mane A T,Ghanwat A A,et al.Camphor Sulfonic Acid(CSA)Doped Polypyrrole(PPy)Films_Measurement of Microstructural and Optoelectronic Properties[J].Measurement,2014,50:363-369.
[10]Mane A T,Navale S T,Pawar R C,et al.Microstructural,Optical and Electrical Transport Properties of WO3Nanoparticles Coated Polypyrrole Hybrid Nanocomposites[J].Synthetic Metals,2015,199:187-195.
[11]李耀刚,陆元元,陈龙,等.原位聚合法制备纳米氧化铬-聚吡咯复合材料[J].稀有金属材料与工程,2007(S2):286-288.
[12]Mane A T,Navale S T,Sen S,et al.Nitrogen Dioxide(NO2)Sensing Performance of p-Polypyrrole/n-Tungsten Oxide Hybrid Nanocomposites at Room Temperature[J].Organic Electronics,2015,16:195-204.
[13]Santhosh P,Michael J.Polypyrrole Functionalized with Fe Pc TSA for NO(2)Sensor Application[J].Sensors and Actuators B-CHEMICAL,2009,140(2):439-444.
[14]Lamdhade G T,Raulkar K B,Yawale S S,et al.Fabrication of Multilayer Sn O2-Zn O-PPy Sensor for Ammonia Gas Detection[J].Indian Journal of Physics,2015,89(10):1025-1030.
[15]余秋香.α-Fe2O3@Sn O2核壳纳米管异质结构的制备及其气敏性能研究[D].武汉:华中师范大学,2015.
[16]太惠玲.导电聚合物纳米复合薄膜的制备及其氨敏特性研究[D].成都:电子科技大学,2008.
[17]Sun Jianhua,Shu Xin,Tian Yanli,et al.Preparation of Polypyrrole@WO3Hybrids with p-n Heterojunction and Sensing Performance to Triethylamine at Room Temperature[J].Sensors and Actuators B:Chemical,2017,238:510-517.
[18]Navale S T,Khuspe G D,Chougule M A,et al.Polypyrrole,AlphaFe2O3and Their Hybrid Nanocomposite Sensor:An Impedance Spectroscopy Study[J].Organic Electronics,2014,15(10):2159-2167.
[19]Ge Hailin,Qi Guojun,Kang Entang,et al.Study of Overoxidized Polypyrrole Using X-Ray Photoelectron Spectroscopy[J].Polymer,1994,35(3):504-508.
[20]张林飞.金-二氧化铈及其复合材料的可控合成-表征与催化性能研究[D].南昌:江西师范大学,2012.
[21]Shilpa J,Narayan K,Akshara S,et al.Ammonia Detection of 1-D Zn O_Polypyrrole Nanocomposite_Effect of CSA Doping and Their Structural,Chemical,Thermal and Gas Sensing Behavior[J].Applied Surface Science,2017,396:1317-1325.
[22]Mane A T,Navale S T,Patil V B.Room Temperature NO2Gas Sensing Properties of DBSA Doped PPy-WO3Hybrid Nanocomposite Sensor[J].Organic Electronics,2015,19:15-25.
[23]Yang Ying,Tian Chungui,Sun Li,et al.Growth of Small Sized Ce O2Particles in the Interlayers of Expanded Graphite for HighPerformance Room Temperature NOx Gas Sensors[J].Journal of Materials Chemistry a,2013,1(41):11274-12742.
[24]Heponiemi Anne,Azalim S,Hu Tao,et al.Cerium Oxide Based Catalysts for Wet Air Oxidation of Bisphenol a[J].Topics in Catalysis,2015,58(14-17):1043-1052.
[25]Liu Jiangyang,Dai Mingjun,Wang Tianshuang,et al.Enhanced Gas Sensing Properties of Sn O2hollow Spheres Decorated With Ce O2Nanoparticles Heterostructure Composite Materials[J].ACS Applied Materials and Interfaces,2016,8(10):6669-6677.
[26]Jiang Xinxin,Tai Huiling,Ye Zongbiao,et al.Novel p-n Heterojunction-Type r GO-Ce O2Bilayer Membrane for Roomtemperature Nitrogen Dioxide Detection[J].Materials Letters,2017,186:49-52.
[27]Wang Lingling,Huang Hui,Xiao Songhua,et al.Enhanced Sensitivity and Stability of Room-Temperature NH3Sensors Using CoreShell Ce O2Nanoparticles@Cross-Kinked PANI With p-n Heterojunctions[J].ACS Applied Materials and Interfaces,2014,6(16):14131-14140.
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