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对氢气具有优异选择性的氧化锌@沸石咪唑酯骨架材料-8核壳结构气体传感器

ZnO@ZIF-8 Core-Shell Structure Gas Sensors with Excellent Selectivity to H.

作者信息

Lv Ruonan, Zhang Qinyi, Wang Wei, Lin Yaojun, Zhang Shunping

机构信息

School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China.

School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.

出版信息

Sensors (Basel). 2021 Jun 12;21(12):4069. doi: 10.3390/s21124069.

Abstract

As the energy crisis becomes worse, hydrogen as a clean energy source is more and more widely used in industrial production and people's daily life. However, there are hidden dangers in hydrogen storage and transportation, because of its flammable and explosive features. Gas detection is the key to solving this problem. High quality sensors with more practical and commercial value must be able to accurately detect target gases in the environment. Emerging porous metal-organic framework (MOF) materials can effectively improve the selectivity of sensors as a result of high surface area and coordinated pore structure. The application of MOFs for surface modification to improve the selectivity and sensitivity of metal oxides sensors to hydrogen has been widely investigated. However, the influence of MOF modified film thickness on the selectivity of hydrogen sensors is seldom studied. Moreover, the mechanism of the selectivity improvement of the sensors with MOF modified film is still unclear. In this paper, we prepared nano-sized ZnO particles by a homogeneous precipitation method. ZnO nanoparticle (NP) gas sensors were prepared by screen printing technology. Then a dense ZIF-8 film was grown on the surface of the gas sensor by hydrothermal synthesis. The morphology, the composition of the elements and the characters of the product were analyzed by X-ray diffraction analysis (XRD), transmission electron microscope (TEM), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Brunauer-Emmett-Teller (BET) and differential scanning calorimetry (DSC). It is found that the ZIF-8 film grown for 4 h cannot form a dense core-shell structure. The thickness of ZIF-8 reaches 130 nm at 20 h. Through the detection and analysis of hydrogen (1000 ppm), ethanol (100 ppm) and acetone (50 ppm) from 150 °C to 290 °C, it is found that the response of the ZnO@ZIF-8 sensors to hydrogen has been significantly improved, while the response to ethanol and acetone was decreased. By comparing the change of the response coefficient, when the thickness of ZIF-8 is 130 nm, the gas sensor has a significantly improved selectivity to hydrogen at 230 °C. The continuous increase of the thickness tends to inhibit selectivity. The mechanism of selectivity improvement of the sensors with different thickness of the ZIF-8 films is discussed.

摘要

随着能源危机日益加剧,氢气作为一种清洁能源在工业生产和人们的日常生活中得到越来越广泛的应用。然而,由于氢气具有易燃、易爆的特性,其储存和运输存在安全隐患。气体检测是解决这一问题的关键。具有更高实用价值和商业价值的高质量传感器必须能够准确检测环境中的目标气体。新兴的多孔金属有机框架(MOF)材料因其高比表面积和规整的孔结构,能够有效提高传感器的选择性。MOF用于表面修饰以提高金属氧化物传感器对氢气的选择性和灵敏度已得到广泛研究。然而,MOF修饰膜厚度对氢气传感器选择性的影响鲜有研究。此外,MOF修饰膜提高传感器选择性的机理仍不明确。在本文中,我们采用均匀沉淀法制备了纳米级ZnO颗粒。通过丝网印刷技术制备了ZnO纳米颗粒(NP)气体传感器。然后通过水热合成法在气体传感器表面生长了致密的ZIF-8膜。利用X射线衍射分析(XRD)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、能谱仪(EDS)、比表面积分析仪(BET)和差示扫描量热法(DSC)对产物的形貌、元素组成和特性进行了分析。发现生长4小时的ZIF-8膜不能形成致密的核壳结构。20小时时ZIF-8的厚度达到130nm。通过对150℃至290℃下氢气(1000ppm)、乙醇(100ppm)和丙酮(50ppm)的检测分析,发现ZnO@ZIF-8传感器对氢气的响应显著提高,而对乙醇和丙酮的响应降低。通过比较响应系数的变化,当ZIF-8厚度为130nm时,气体传感器在230℃下对氢气的选择性显著提高。膜厚度的持续增加倾向于抑制选择性。探讨了不同厚度ZIF-8膜的传感器选择性提高的机理。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/7768/8231508/3a4085d16742/sensors-21-04069-g001.jpg

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