Polypyrrole Coated Carbon Nanotubes: Preparation, Characterization, and Gas-sensing Properties

doi:10.3724/SP.J.1077.2011.00961

Abstract

Abstract: A nanocomposite (PPy/F-MWCNTs) were successfully synthesized by the in-situ chemical oxidation polymerization with acid-treated multi-walled carbon nanotubes (F-MWCNTs) and polypyrroles(PPy). The as-prepared composite was characterized by Fourier transformed infrared spectra (FT-IR), UV-Vis diffuse refflection spectroscope (UV-Vis DRS), thermal gravimetric analysis (TGA), X-ray diffraction (XRD), Branauer- Emmett-Teller analysis (BET), field-emission scanning electron microscope (FE-SEM) and transmission electron microscope (TEM). The results reveal that the F-MWCNTs is well coated with about 25-40nm thick polypyrrole, and the surface specific areas of PPy/F-MWCNTs is about three times than that of pure PPy. The sensors fabricated by PPy/F-MWCNTs exhibit higher sensitivity, better response/reproducibility towards NH₃ vapor at room temperature than that fabricated by pure PPy or F-MWCNTs. The sensitivity is 1.9 even to 200×10^-6 of NH₃and the response time is 135s. In addition, compared with MWCNTs untreated with acid, the as-prepared PPy/F-MWCNTs also exhibits higher sensitivity than that prepared without acid-treated MWCNTs.

Key words: gas sensor, carbon nanotubes, PPy/F-MWCNTs, nanocomposites, NH₃

CLC Number:

TB331

WANG Zhi-Min, TANG Xin-Cun, XIAO Yuan-Hua, YU Xiao-Jing, ZHANG Liang, JIA Dian-Zeng, CHEN Gu-Chun. Polypyrrole Coated Carbon Nanotubes: Preparation, Characterization, and Gas-sensing Properties[J]. Journal of Inorganic Materials, 2011, 26(9): 961-968.

References

[1] Jin G, Norrish J, Too C, et al. Polypyrrole -lament sensors for gases and vapours. Curr. Appl. Phys., 2004, 4(2/3/4): 366-369.

[2] Doleman B J, Lewis N S. Comparison of odor detection thresholds and odor discriminablities of a conducting polymer composite electronic nose versus mammalian olfaction. Sensors and Actuators B: Chem., 2001, 72(1): 41-50.

[3] Hopkins A R, Lewis N S. Detection and classi-cation characteristics of arrays of carbon black/organic polymer composite chemiresistive vapor detectors for the nerve agent simulants dimethylmethylphosphonate and diisopropylmethylphosponate. Anal. Chem., 2001, 73(5): 884-892.

[4] Ha S C, Kim Y S, Yang Y, et al. Integrated and microheater embedded gas sensor array based on the polymer composites dispensed in micromachined wells. Sensors and Actuators B:Chem., 2005, 105(2): 549-555.

[5] Snow E S, Perkins F K, Houser E J, et al. Chemical detection with a single-walled carbon nanotube capacitor. Science, 2005, 307(5717): 1942-1945.

[6] Takao Y, Miyazaki K, Shimizu Y, et al. High ammonia sensitive semiconductor gas sensors with double-layer structure and interface electrodes. J. Electrochem. Soc., 1994, 141(4): 1028-1034.

[7] 张红芹, 谢英南, 蒋登高, 等. 聚苯胺气敏材料的研究进展. 化工新型材料, 2007, 35(11): 11-13.

[8] Chen Y S, Li Y, Wang H C, et al. Gas sensitivity of a composite of multi-walled carbon nanotubes and polypyrrole prepared by vapor phase polymerization. Carbon, 2007, 45(2): 357-363.

[9] Iijima S. Helical microtubules of graphitic carbon. Nature, 1991, 354(6348): 56-68.

[10] Ajayan P M, Zhou O Z. Applications of carbon nanotubes. Topics Appl. Phys., 2001, 80: 391-425.

[11] Treacy M M J, Ebbesen T W, Gibson J M. Exceptionally high Young’s modulus observed for individual carbon nanotubes. Nature, 1996, 381(20): 678-680.

[12] Nguyen V H, Nguyen Q D, Phuong D T, et al. Thin -lm polypyrrole/SWCNTs nanocomposites-based NH3 sensor operated at room temperature. Sensors and Actuators B: Chem., 2009, 140(2): 500-507.

[13] Shin H C, Liu M L, Sadanadan B, et al. Electrochemical insertion of lithium into multiwalled carbon nanotubes prepared by catalytic decomposition. J. Power Sources, 2002, 112(1): 216-221.

[14] Canobre S C, Almeida D A L, Fonseca C P, et al. Synthesis and characterization of hybrid composites based on carbon nanotubes. Electrochim. Acta, 2009, 54(26): 6383-6388.

[15] Long Y Z, Yin Z H, Chen Z J. Low temperature magnetoresistance studies on composite films of conducting polymer and multiwalled carbon nanotubes. J. Phys. Chem. C, 2008, 112(30): 11507-11512.

[16] Qian D, Dickey E C, Andrews R, et al. Load transfer and deformation mechanisms in carbon nanotubepolystyrene composites. Appl. Phys. Lett., 2000, 76 (20): 2868-2870.

[17] Lu Y, Li T, Zhao X Q, et al. Electrodeposited polypyrrole/carbon nanotubes composite -lms electrodes for neural interfaces. Biomaterials, 2010, 31(19): 5169-5181.

[18] Gong X Y, Liu J, Baskaran S, et al. Surfactant-assisted processing of carbon nanotube/polymer composites. Chem. Mater., 2000, 12(4): 1049-1052.

[19] Zhang L, Tao T, Li C Z. Formation of polymer/carbon nanotubes nano-hybrid shish–kebabvia non-isothermal crystallization. Polymer, 2009, 50(15): 3835-3840.

[20] Sandra C H, Debangshu C, Wilfred C, et al. Single polypyrrole nanowire ammonia gas sensor. Electroanalysis, 2007, 19(19/20): 2125-2130.

[21] Wu T M, Lin Y W, Liao C S. Preparation and characterization of polyaniline/multi-walled carbon nanotube composites. Carbon, 2005, 43(4): 734-740.

[22] Zhang X T, Zhang J, Wang R M, et al. Cationic surfactant directed polyaniline/CNT nanocables:synthesis, characterization, and enhanced electrical properties. Carbon, 2004, 42(8/9): 1455-1461.

[23] Kay H A, Seung Y J, Ha R H, et al. Enhanced sensitivity of a gas sensor incorporating single-walled carbon nanotube-polypyrrole nanocomposites. Adv. Mater., 2004, 16(12): 1005-1009.

[24] 宿凯. 聚苯胺/碳纳米管原位聚合. 哈尔滨: 黑龙江大学硕士论文, 2008.

[25] Zou W, Du Z J, Liu Y X, et al. Functionalization of MWNTs using polyacryloyl chloride and the properties of CNT–epoxy matrix nanocomposites. Composites Science and Technology, 2008, 68(15/16): 3259-3264.

[26] Zhang J, Zou H L, Qing Q, et a1. Effect of chemical oxidation on the structure of single-walled carbon nanotubes. J. Phys. Chem. B, 2003, 107(161): 3712-3718.

[27] Mawhinney D B, Naumenko V, Kuznetsova A, et al. Infrared Spectral evidence for the etching of carbon nanotubes: ozone oxidation at 298K. J. Am. Chem. Soc., 2000, 122(10): 2383-2384.

[28] Zhang X T, Zhang J, Song W H, et al. Controllable synthesis of conducting polypyrrole nanostructures. J. Phys. Chem. B, 2006, 110(3): 1158-1165

[29] Nanda G S, Yong C J, Hyang H S, et al. Polypyrrole coated carbon nanotubes: synthesis, characterization, and enhanced electrical properties. Synthetic Metals, 2007, 157(8/9): 374-379

[30] Long Y Z, Chen Z J, Zhang X T, et al. Electrical properties of multi-walled carbon nanotube/polypyrrole nanocables: percolation- dominated conductivity. J. Phys. D: Appl. Phys., 2004, 37(14): 1965-1969.

[31] Wu T M, Lin S H. Characterization and electrical properties of polypyrrole/multiwalled carbon nanotube composites synthesized by in situ chemical oxidative polymerization. J. Polym. Sci. B Polym. Phys., 2006, 44(10): 1413-1418.

[32] Sing K S W, Everett D H, Haul R A W, et al. Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity. Pure & Appl. Chem, 1985, 57(4): 603-619.

[33] Zhang X T, Zhang J, Wang R M, et al. Surfactant-directed polypyrrole/CNT nanocables: synthesis, characterization, and enhanced electrical properties. Chem. Phys. Chem., 2004, 5(7): 998-1002.

[34] 肖元化, 唐新村, 王志敏, 等(XIAO Yuan-Hua, et al). 分级结构聚苯胺/多壁碳纳米管纳米复合物的制备、表征及其气敏性能研究.无机材料学报(Journal of Inorganic Materials), 2010, 25(10): 1092-1098.

[35] Gustafsson G, Lundstormi I, Liedberg B, et al. The interactimn between ammonia and poly (pyrrmle). Synth. Met., 1989, 31(2): 163-179.

[36] 王会才. 高分子纳米复合气敏材料及气敏传感器. 杭州: 浙江大学博士论文, 2007.

[37] Zhang T, Mubeen S, Myung N V, et al. Recent progress in carbon nanotube-based gas sensors. Nanotechnology, 2008, 19(13): 332001-1-14.