介孔ZnO材料的制备及气敏性能的研究
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摘要
ZnO气敏传感器以其响应速度快、恢复时间短、选择性好及对环境污染小等特点成为气敏传感器领域研究的热点,引起人们的广泛关注。其中,ZnO薄膜表面的孔结构,对于气体的检测有着极大的优化作用。
本文主要利用溶胶-凝胶法,以醋酸锌(Zn(CH_3COO)_2·2H_2O)为原料,聚乙二醇PEG为模板剂,合成了具有孔结构的ZnO薄膜,考察了各种工艺参数对ZnO薄膜的微观结构、表面形貌及其气敏性能的影响,从而得到了以下一些结果:
1.络合剂的加入可以有效地抑制Zn(CH_3COO)_2·2H_2O强烈水解,由二乙醇胺(DEA)做络合剂所得溶胶合成的ZnO薄膜具有较好的孔结构;醋酸锌浓度及PEG的加入量对ZnO晶粒尺寸影响不明显;煅烧时间比煅烧温度对晶粒尺寸的影响大;ZnO晶粒尺寸随水浴温度的升高而增大,增幅不明显。
2.具有孔结构的ZnO薄膜,其孔径大小随醋酸锌浓度的增大而增大,孔密度先增大后减小;低分子量薄膜孔径小,且孔密度较高;孔径随PEG加入量的增大而增大;500℃时,薄膜的表面疏松多孔,孔密度较大;70℃的水浴有利孔结构的形成。
3.采用静态配气法在气敏测试仪上通过对元件性能进行气敏测试发现:样品存在一个最佳加热电压,且对乙醇的灵敏度高于丙酮;最佳烧结温度为500℃;醋酸锌浓度为0.6 mol/L时为宜;随着PEG的加入,元件的灵敏度先升高后降低,最佳加入量为0.7 g;乙醇和丙酮的灵敏度都随着其浓度的升高而增大。
The thin film gas sensor made of ZnO has advantages of fast response, short recovery time, good selectivity and pollution to environment and so on. ZnO, which is in the field of extensive application of gas-sensitive material. Nano ZnO film of high quality attracts more and more attention in recent years. ZnO thin film surface pore structure makes great effects on its performance.
In this paper, nano ZnO thin film is prepared by sol-gel method. Highly-ordered nanocrystaline ZnO porous films are synthesized using zinc acetate Zn(CH3COO)2·2H2O as precursor and organic surfactant (polyethylene glycol (PEG)) as templates . The influence of experimental parameters on the microstructure, surface topography and gas sensitivity of ZnO films is studied.
The following is some results:
1. The hydrolyzing effect of Zn(CH3COO)2·2H2O is obviously reduced after complex agent’s addition . Moreover, a better porous structure is obtained using diethanolamine (DEA) as complex agent .The influence of calcination time is greater than the influence of calcination temperature. The ZnO grain size with increase water temperature rising is not obvious.
2. The pore size of the ZnO film with pore structure is more large as Zn(CH_3COO)_2 concentration is increasing. The pore density increases and decreases. The pore size of low molecular weight film is small and the pore density is higher. The pore diameter is large with the addition of PEG. When the temperature is 500℃, the surface of ZnO film is poor porosity holes and the pore density is higher . When the temperature is 70℃, it is favorable to form pore structure.
3. Using static prepared gas, we have detected sensor’s sensing character with an optimum heating voltage, and the sensitivity to ethanol is higher than to acetone. The best sintering temperature is 500℃. And the best concentration of Zn(CH_3COO)_2 is 0.6 mol/L . With the addition of PEG, the sensitivity of the gas sensor rises first and then reduces. The best optimal dosage is 0.7 g. The Sensitivity of both ethanoc and acetone is rising with the increase of its concentration.
本文主要利用溶胶-凝胶法,以醋酸锌(Zn(CH_3COO)_2·2H_2O)为原料,聚乙二醇PEG为模板剂,合成了具有孔结构的ZnO薄膜,考察了各种工艺参数对ZnO薄膜的微观结构、表面形貌及其气敏性能的影响,从而得到了以下一些结果:
1.络合剂的加入可以有效地抑制Zn(CH_3COO)_2·2H_2O强烈水解,由二乙醇胺(DEA)做络合剂所得溶胶合成的ZnO薄膜具有较好的孔结构;醋酸锌浓度及PEG的加入量对ZnO晶粒尺寸影响不明显;煅烧时间比煅烧温度对晶粒尺寸的影响大;ZnO晶粒尺寸随水浴温度的升高而增大,增幅不明显。
2.具有孔结构的ZnO薄膜,其孔径大小随醋酸锌浓度的增大而增大,孔密度先增大后减小;低分子量薄膜孔径小,且孔密度较高;孔径随PEG加入量的增大而增大;500℃时,薄膜的表面疏松多孔,孔密度较大;70℃的水浴有利孔结构的形成。
3.采用静态配气法在气敏测试仪上通过对元件性能进行气敏测试发现:样品存在一个最佳加热电压,且对乙醇的灵敏度高于丙酮;最佳烧结温度为500℃;醋酸锌浓度为0.6 mol/L时为宜;随着PEG的加入,元件的灵敏度先升高后降低,最佳加入量为0.7 g;乙醇和丙酮的灵敏度都随着其浓度的升高而增大。
The thin film gas sensor made of ZnO has advantages of fast response, short recovery time, good selectivity and pollution to environment and so on. ZnO, which is in the field of extensive application of gas-sensitive material. Nano ZnO film of high quality attracts more and more attention in recent years. ZnO thin film surface pore structure makes great effects on its performance.
In this paper, nano ZnO thin film is prepared by sol-gel method. Highly-ordered nanocrystaline ZnO porous films are synthesized using zinc acetate Zn(CH3COO)2·2H2O as precursor and organic surfactant (polyethylene glycol (PEG)) as templates . The influence of experimental parameters on the microstructure, surface topography and gas sensitivity of ZnO films is studied.
The following is some results:
1. The hydrolyzing effect of Zn(CH3COO)2·2H2O is obviously reduced after complex agent’s addition . Moreover, a better porous structure is obtained using diethanolamine (DEA) as complex agent .The influence of calcination time is greater than the influence of calcination temperature. The ZnO grain size with increase water temperature rising is not obvious.
2. The pore size of the ZnO film with pore structure is more large as Zn(CH_3COO)_2 concentration is increasing. The pore density increases and decreases. The pore size of low molecular weight film is small and the pore density is higher. The pore diameter is large with the addition of PEG. When the temperature is 500℃, the surface of ZnO film is poor porosity holes and the pore density is higher . When the temperature is 70℃, it is favorable to form pore structure.
3. Using static prepared gas, we have detected sensor’s sensing character with an optimum heating voltage, and the sensitivity to ethanol is higher than to acetone. The best sintering temperature is 500℃. And the best concentration of Zn(CH_3COO)_2 is 0.6 mol/L . With the addition of PEG, the sensitivity of the gas sensor rises first and then reduces. The best optimal dosage is 0.7 g. The Sensitivity of both ethanoc and acetone is rising with the increase of its concentration.
引文
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2田修营,何文,赵洪石,等.介孔材料的研究进展及应用前景[J].山东轻工业学院学报. 2008, 22(2): 20-24
3马正先,姜玉芝,韩跃新,张士成.纳米氧化锌制备原理与技术.中国轻工业出版社, 2010: 1-6
4张立德,牟季美.纳米材料和纳米结构.北京:科学出版社, 2001
5 M. R. De Guire, S. E. Dorris, R. B. Poeppel, et al. Coprecipitation Synthesis of Doped Lanthanum Chromite [J]. J. Mater.Res., 1993, 8(9): 2327-2335
6卫志贤,刘荣杰,郑岚.均匀沉淀法制备纳米氧化物工艺分析[J].西北大学学报(自然科学版), 1998, 28(5): 407-411
7辛显双,周百斌,刘双全.均匀沉淀法制备纳米氧化锌的工艺条件[J].化学与粘合, 2002, (5):203-205
8 S. Antonio, J. V. R. Maria. The Sol-Gel Production of Bioceramics. Key Engineering Materials, 2009, 391: 141-158
9曾燮榕,杨峰,陈大明.氧化锆纳米晶微粉的制备及性质[J].无机材料学报, 1995, 10(3) : 356-358
10 Q. Yitai, X. Yi, L. Jing, et al. Hydrothermal Preparation and Characterization of Ultrafine Powders of Ferrite Spinels MFe2O4[J]. Mater. Sci. Eng. B, 1995, 34(1): 11-13
11景志红,吴世华.纳米晶γ-Fe2O3的微乳液法制备及其气敏性.应用化学, 2007, 24 (2): 148-151
12 F. A. Deorsola, D. Vallauri. Study of the Process Parameters in the Synthesis of TiO2 Nanospheres through Reactive Microemulsion Precipitation. Powder Technology, 2009, 190(3): 304-309
13 Y. H. Li, V. P. Kotzeva, D. J. Fray. Electrochemical Performance of CdS Nanomaterials Synthesized by Microemulsion Techniques. Materials Letters, 2006, 60(21-22): 2743-2746
14徐甲强,潘庆谊,孙雨安.纳米氧化锌的乳液合成/结构表征与气敏特性.无机化学学报, 1998, 14(3): 355-359
15李春忠,胡黎明. AlN粉末的制备方法[J].硅酸盐通报, 1994, (5): 42-47
16梁博,黄政仁,江东亮.化学气相沉积法制备SiC纳米粉[J].无机材料学报, 1996, 11(3):441-447
17 Z. R. Huang, et al. Proceeding 5th. International Symposium on Ceramic Materials & Compounds for Engines. Shanghai,China,May 1994
18冯丽娟.大孔高比表面积催化剂及其载体的制备方法-超临界流体干燥法[J].天然气化工, 1994, 19(6): 41-45
19 IUPAC Manual of Symbols and Terminology. Pure Appl. Chem., 1972, 31: 578-638
20 C. T. Kresge, M. E. Leonowicz, W. J. Roth, et al. Ordered Mesoporous Molecular Sieves Synthesized by a Liquid-Crystal Template Mechanism. Nature, 1992, 359: 710-712
21 R. Ryoo, J. M. Kim, C. H. Shin, et al. Disorderd Molecular Sieve with Branched Mesoporous Channel Network. J. Phys. Chem. 1996, 100: 17718-17721
22吴壮志,王德志,徐兵.以聚乙二醇为模板剂制备MoS2空心微球.物理化学学报, 2008, 24(10): 1927-1931
23曹渊,魏红娟,王晓.介孔材料的调孔方法及机理.材料导报,2010, 24(6): 27-31
24 D. M. Antonelli, J.Y. Ying. A Review of the Rheology of the Lamellar Phase in Surfactant Systems, Angew. Chem. Int. ED. Engl., 1995, 34: 2014-2020
25 S. A. Bagshaw, E. Prouzet, T. J. Pinnavaia. Templating of Mesoporous Molecular Sieves by Nonionic Polyethylene Oxide Surfactants. Science, 1995, 269:1242-1244
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