还原温度对氧化石墨烯的湿度-甲醛交叉敏感性能的影响

doi:10.11949/j.issn.0438-1157.20180681

化工学报 ›› 2019, Vol. 70 ›› Issue (1): 309-318.DOI: 10.11949/j.issn.0438-1157.20180681

• 材料化学工程与纳米技术 • 上一篇下一篇

还原温度对氧化石墨烯的湿度-甲醛交叉敏感性能的影响

雷德会^1,^2,³(),彭同江^2,³(),孙红娟^2,³,汤光平⁴,杨建召^2,³,任亚周^1,^2,³,王丽丽⁴

1. 西南科技大学理学院，四川绵阳 621010
2. 西南科技大学固体废物处理与资源化教育部重点实验室，四川绵阳 621010
3. 西南科技大学矿物材料及应用研究所，四川绵阳 621010
4. 中国工程物理研究院机械制造工业研究所，四川绵阳 621900

收稿日期:2018-06-21 修回日期:2018-10-15 出版日期:2019-01-05 发布日期:2019-01-05
通讯作者: 彭同江
作者简介:雷德会（1994—），女，硕士研究生，<email>leidehui1118@163.com</email>|彭同江（1958—），男，教授，博士生导师，<email>tjpeng@swust.edu.cn</email>
基金资助:
国家自然科学基金项目(U1630132, 41772036);四川省科技厅项目(2016GZ0428, 2017GZ0114);西南科技大学研究生创新基金(17ycx072)

Influence of reduction temperature of graphene oxide on cross sensitivity between humidity and formaldehyde

Dehui LEI^1,^2,³(),Tongjiang PENG^2,³(),Hongjuan SUN^2,³,Guangping TANG⁴,Jianzhao YANG^2,³,Yazhou REN^1,^2,³,Lili WANG⁴

1. School of Science, Southwest University of Science & Technology, Mianyang 621010, Sichuan，China
2. Education Ministry Key Laboratory of Solid Waste Treatment and Resource Recycle, Southwest University of Science and Technology, Mianyang 621010, Sichuan，China
3. Institute of Mineral Materials and Application, Southwest University of Science and Technology, Mianyang 621010, Sichuan，China
4. Institute of Mechanical Manufacturing Industry, Chinese Academy of Engineering Physics, Mianyang 621900, Sichuan，China

Received:2018-06-21 Revised:2018-10-15 Online:2019-01-05 Published:2019-01-05
Contact: Tongjiang PENG

摘要/Abstract

摘要：

以氧化石墨烯溶胶为前体，通过旋涂工艺制备薄膜型气敏元件，在低温80～180℃下进行热处理，获得系列不同还原程度的还原氧化石墨烯气敏元件，采用XRD、AFM、FT-IR、XPS对样品的层结构、薄膜厚度及含氧官能团变化属性进行表征，将气敏薄膜元件在相对湿度为11.3%～93.6%的范围内进行预湿处理，并测定元件对甲醛气氛的敏感性能。结果表明：随热还原处理温度的升高，氧化石墨烯的结构逐渐向类石墨结构转变，含氧官能团逐渐脱失，缺陷增多，薄膜的方块电阻呈数量级地减小，从41 MΩ减小至928 Ω；经不同湿度预处理的气敏元件置于甲醛气氛中产生了水分子与甲醛分子的竞争吸附，从而导致电阻的明显变化；在10^?4甲醛气氛下，未还原或热还原温度较低的气敏元件适用于低、高湿环境下甲醛气氛的气敏测试，最大灵敏度为69.1%，而还原温度适中的元件则适用于中湿环境的甲醛测试，最大灵敏度为80.3%。

关键词: 氧化石墨烯, 还原, 含氧官能团, 化学分析, 吸附, 脱附, 交叉灵敏

Abstract:

As precursors, graphite oxide samples are exfoliated and used to prepare graphene oxide thin films by gas spin coating with Ag-Pd integrated electronic device (Ag-Pd IED). The graphene oxide thin films are annealed at 80—180℃ to obtain a series of reduced graphene oxide gas sensing element samples with different reduction degrees, and the layer structures, film thickness and functional groups change properties of all the samples are investigated by X-ray diffraction spectroscopy, Fourier transform infrared spectroscopy, Atomic force microscope and X-ray photoelectron spectroscopy. The prehumidification treatment with the relative humidity from 11.3% to 93.6%, the gas sensitivity tests are carried out to reduced graphene oxide thin film gas sensing element. Then the formaldehyde gas sensing measurement are also implemented. The results show that the structure of the graphene oxide samples are transformed to the graphitic structure after reduction at different thermal treatment temperatures. The oxygen functional groups on the surface of graphene oxide gradually pyrolyzed, the defects increase, the structure of graphene gradually changes to similar to graphite, and the resistance of the samples were significantly reduced in magnitude with 41 MΩ to 928 Ω. The samples with different relative humidity pretreated produced competitive adsorption of water molecules and formaldehyde molecules in formaldehyde atmosphere, leading to obvious changes in resistance. When exposed to the 10^?4 formaldehyde gas at room temperature, unreduced or the reduced products at low temperature show good sensitivity of 69.1% to formaldehyde gas in high humidity environment. In medium humidity environment, the reduced products at medium temperature which exhibit a best sensitivity of 80.3% are suitable for the test of formaldehyde gas.

Key words: graphene oxide, reduction, oxygen-containing functional groups, chemical analysis, adsorption, desorption, cross sensitivity

中图分类号:

TQ 110.3 O 647.3

雷德会, 彭同江, 孙红娟, 汤光平, 杨建召, 任亚周, 王丽丽. 还原温度对氧化石墨烯的湿度-甲醛交叉敏感性能的影响[J]. 化工学报, 2019, 70(1): 309-318.

Dehui LEI, Tongjiang PENG, Hongjuan SUN, Guangping TANG, Jianzhao YANG, Yazhou REN, Lili WANG. Influence of reduction temperature of graphene oxide on cross sensitivity between humidity and formaldehyde[J]. CIESC Journal, 2019, 70(1): 309-318.

图/表 9

图1 气敏元件的制备及测试过程

Fig.1 Gas sensor preparation and testing process

图2 样品的AFM图及其厚度分析

Fig.2 AFM images and thickness analysis of samples

图3 GOS和热还原样品GOS-T的XRD谱图

Fig.3 XRD patterns of GOS and GOS-T samples

图4 GOS和热还原样品GOS-T的FT-IR谱图

Fig.4 FT-IR spectra of GOS and GOS-T samples

图5 GOS和系列GOS-T样品的XPS全谱图(a),C/O原子比关系图(b)和C 1s谱的分峰拟合图谱(c)

Fig.5 XPS survey(a), curve of relationship between the mass of oxidant and C/O atom ratio(b) and C 1s spectra(c) of GOS and rGO-T samples

图6 热还原样品GOS-T的电阻-温度

Fig.6 Relationship between resistance and ambient temperature of GOS-T samples

图7 在不同预处理湿度条件下，GOS和系列GOS-T气敏元件的灵敏度-还原温度的关系

Fig.7 Relationship between sensitivity and reduction temperature of GOS and GOS-T sensitive elements in diffirent prehumidification relative humidity

图8 低还原温度和较高还原温度处理的GOS元件对水分子、甲醛分子的吸附机理模型

Fig.8 Adsorption mechanism model of water and formaldehyde molecules with low and high reduction temperature of GOS elements

图9 不同湿度预处理后GOS-T薄膜在10?4甲醛气氛中响应机理示意图

Fig.9 Response mechanism of GOS-T films after different prehumidification treatment in 10?4 formaldehyde atmosphere

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还原温度对氧化石墨烯的湿度-甲醛交叉敏感性能的影响

Influence of reduction temperature of graphene oxide on cross sensitivity between humidity and formaldehyde

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