基于ZIF8/rGO的高性能NO2室温传感器

doi:10.15541/jim20210120

无机材料学报 ›› 2021, Vol. 36 ›› Issue (12): 1277-1282.DOI: 10.15541/jim20210120

所属专题：【信息功能】敏感陶瓷；【能源环境】金属有机框架材料

基于ZIF8/rGO的高性能NO₂室温传感器

李豪¹^,²(), 唐志红¹, 卓尚军², 钱荣²()

1.上海理工大学材料科学与工程学院, 上海 200093
2.中国科学院上海硅酸盐研究所, 国家大型科学仪器中心上海无机质谱中心, 上海200050

收稿日期:2021-03-02 修回日期:2021-03-23 出版日期:2021-12-20 网络出版日期:2021-05-10
通讯作者: 钱荣,研究员. E-mail: qianrong@mail.sic.ac.cn
作者简介:李豪(1996-), 男, 硕士研究生. E-mail: lh960714211@163.com
基金资助:
国家自然科学基金(21775156);上海市政府间国际合作项目(19520712000);上海市科技创新行动计划(20142201100);上海无机材料测试技术平台(19DZ2290700)

High Performance of Room-temperature NO₂ Gas Sensor Based on ZIF8/rGO

LI Hao¹^,²(), TANG Zhihong¹, ZHUO Shangjun², QIAN Rong²()

1. School of Material Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200093, China
2. National Center for Inorganic Mass Spectrometry Center, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2021-03-02 Revised:2021-03-23 Published:2021-12-20 Online:2021-05-10
Contact: QIAN Rong, professor. E-mail: qianrong@mail.sic.ac.cn
About author:LI Hao (1996-), male, Master candidate. E-mail: lh960714211@163.com
Supported by:
National Natural Science Foundation of China(21775156);Shanghai Intergovernmental International Cooperation Project(19520712000);Shanghai Science and Technology Innovation Action Project(20142201100);Shanghai Technical Platform of Testing on Inorganic Materials(19DZ2290700)

摘要/Abstract

摘要：

二氧化氮气体是一种常见的大气污染物, 对自然环境和人类健康造成严重的危害, 开发检测该类有毒有害气体的高效检测设备势在必行。新型复合薄膜气体传感器可以在常温下对二氧化氮进行高选择性、高灵敏度检测, 为自然环境和人类健康保驾护航。本工作采用化学沉淀法和超声法制备了多孔、高比表面积的ZIF8/还原氧化石墨烯(ZIF8/rGO)复合材料, 以此为气敏材料构建NO₂传感器, 并系统研究了其在室温下对NO₂的气敏性能, 进一步探讨了ZIF8/rGO气敏传感器感应NO₂的可能机理。气敏实验结果表明：ZIF8/rGO气敏传感器对50×10^-6 NO₂的响应达到34.77%, 是纯rGO气敏传感器的3.2倍。ZIF8/rGO传感器在4个可逆循环测试中表现出较好的可重复性, RSD(Relative Standard Deviation)为3.9%。此外, ZIF8/rGO传感器表现出优秀的长期稳定性(RSD为2.5%)、选择性和低的检出限(3.8×10^-8)。室温下灵敏感应NO₂的气敏性能主要归因于ZIF8的多孔结构和超大的比表面积以及rGO的优越性能。本工作将为ZIF8/rGO作为气敏材料检测有毒有害的NO₂气体提供新思路。

关键词: 气体传感器, ZIF8, 还原氧化石墨烯, NO₂

Abstract:

As a common air pollutant, nitrogen dioxide (NO₂) gas does serious harm to the natural environment and human health. Therefore, it is imperative to develop efficient detection methods for detecting such toxic and harmful gases. Developing a new type of composite film gas sensor to achieve high selectivity and high sensitivity detection of nitrogen dioxide at room temperature has become a research hotspot. Here, we prepared zeolitic imidazolate framework 8 /reduced graphene oxide (ZIF8/rGO) composite with porosity and large specific surface area through chemical precipitation and ultrasonic method. Based on this materials, an NO₂ sensor was constructed and then evaluated at room-temperature. Its possible mechanism of sensing NO₂ was explored. The results showed that ZIF8/rGO sensor presented a response of 34.77% toward 50×10^-6 NO₂, which was 3.2-fold of pure rGO senor. Meanwhile it exhibited excellent repeatability after 4 reversible cycles with the relative standard deviation (RSD) only 3.9% and remarkable long-term stability in four-week test with the RSD of 2.5%, accompanied outstanding selectivity toward NO₂ and a low limit of detection of 3.8×10^-8. These hypersensitive properties at room temperature were attributed to its porous structure and large specific surface and high performance of rGO. This work offers a new idea for efficiently detecting poisonous NO₂ based on ZIF8/rGO.

Key words: gas sensor, zeolitic imidazolate framework 8, reduced graphene oxide, NO₂

中图分类号:

O649

李豪, 唐志红, 卓尚军, 钱荣. 基于ZIF8/rGO的高性能NO₂室温传感器[J]. 无机材料学报, 2021, 36(12): 1277-1282.

LI Hao, TANG Zhihong, ZHUO Shangjun, QIAN Rong. High Performance of Room-temperature NO₂ Gas Sensor Based on ZIF8/rGO[J]. Journal of Inorganic Materials, 2021, 36(12): 1277-1282.

图/表 7

图1 ZIF8/rGO的制备流程图

Fig. 1 Preparation of ZIF8/rGO

图2 气敏测试装置示意图

Fig. 2 Schematic diagram of gas-sensing test device (MFC, Mass Flow Controller)

图3 ZIF8/rGO的SEM照片(a~d)和元素分布图(e~h)

Fig. 3 SEM images (a-d) and corresponding elemental mappings (e-h) of ZIF8/rGO

图4 ZIF8/rGO的XRD图谱(a)和拉曼表征(b)

Fig. 4 XRD pattern (a) and Raman characterization (b) of ZIF8/rGO

图5 ZIF8/rGO传感器对不同浓度NO2的响应-恢复曲线(a)和ZIF8/rGO传感器响应值与NO2浓度的关系(b)

Fig. 5 Response-recovery curve toward various concentration of NO2 of ZIF8/rGO sensor (a), and response of ZIF8/rGO sensor to the concentration of NO2 (b)

图6 ZIF8/rGO传感器和rGO传感器对50×10-6 NO2的响应恢复对比(a)以及ZIF8/rGO传感器的可重复性(b)

Fig. 6 Comparison of response and recovery between ZIF8/rGO sensor and rGO sensor toward 50×10-6 NO2 (a) and repeatability of ZIF8/rGO sensor (b)

图7 ZIF8/rGO传感器的长期稳定性(a)和气体选择性(b)

Fig. 7 Long-term stability (a) and selectivity (b) of ZIF8/rGO sensor

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基于ZIF8/rGO的高性能NO₂室温传感器

High Performance of Room-temperature NO₂ Gas Sensor Based on ZIF8/rGO

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