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ZIF-67修饰WO3纳米片的制备及其气敏性能

桂阳海 钱琳琳 田宽 郭会师 张景浩 万程涛 杨晓艳

桂阳海, 钱琳琳, 田宽, 等. ZIF-67修饰WO3纳米片的制备及其气敏性能[J]. 复合材料学报, 2022, 40(0): 1-10
引用本文: 桂阳海, 钱琳琳, 田宽, 等. ZIF-67修饰WO3纳米片的制备及其气敏性能[J]. 复合材料学报, 2022, 40(0): 1-10
Yanghai GUI, Linlin QIAN, Kuan TIAN, Huishi GUO, Jinghao ZHANG, Chengtao WAN, Xiaoyan Yang. Gas sensing performance and preparation of WO3 nanosheets decorated by ZIF-67[J]. Acta Materiae Compositae Sinica.
Citation: Yanghai GUI, Linlin QIAN, Kuan TIAN, Huishi GUO, Jinghao ZHANG, Chengtao WAN, Xiaoyan Yang. Gas sensing performance and preparation of WO3 nanosheets decorated by ZIF-67[J]. Acta Materiae Compositae Sinica.

ZIF-67修饰WO3纳米片的制备及其气敏性能

基金项目: 国家自然科学基金(U1904213,U20041102);河南省科技攻关项目(202102210260).
详细信息
    通讯作者:

    桂阳海,博士,教授,硕士生导师,从事纳米及功能材料的研究 E-mail: yhgui@zzuli.edu.cn

  • 中图分类号: TP212.2

Gas sensing performance and preparation of WO3 nanosheets decorated by ZIF-67

  • 摘要: 金属氧化物半导体气敏传感器在有毒有害气体检测领域逐渐表现出巨大的应用前景,但是金属氧化物半导体传感器通常在检测时受环境湿度影响较大,这极大的限制了其应用。本文采用水热法成功在陶瓷管表面原位生长WO3纳米片,并以此为基底,在其表面生长ZIF-67多孔材料,通过调控W和Co的比例制备了不同比例的ZIF-67/WO3复合材料,利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、红外(FT-IR)和比表面积测试仪(BET)等方法对所制备的材料进行物相和形貌表征。针对其不同比例的复合材料的气敏性能进行了研究,结果表明,ZIF-67/WO3 (1:1)复合材料性能最好,在220℃对三乙胺表现出优异的选择性,对体积分数为100×10-6的三乙胺的响应值可达140.34,响应/恢复时间分别为9 s和7 s。研究了空气相对湿度 (RH) 对ZIF-67/WO3 (1:1)传感器的影响,结果表明,在高达75%RH环境下该材料仍能保持较好的响应值,相对于纯WO3气敏材料具有较好的抗湿性能。

     

  • 图  1  ZIF-67、WO3以及复合材料的XRD图谱

    Figure  1.  XRD patterns of ZIF-67, WO3 and different composites

    图  2  WO3、ZIF-67、ZIF-67/WO3复合材料的 SEM图

    Figure  2.  SEM images of WO3, ZIF-67 and ZIF-67/WO3(1:1) composite

    图  3  ZIF-67、WO3以及复合材料的FT-IR图

    Figure  3.  FT-IR spectra of ZIF-67, WO3 and different composites

    图  4  不同复合材料的气敏性能图:(a) 不同复合材料对三乙胺的温度-灵敏度曲线;(b) 不同复合材料对多种气体的选择性图

    Figure  4.  Gas sensing properties of different composites: (a) Temperature-sensitivity curves of different composites to triethylamine; (b) Response of the different composites to various gases

    图  5  (a) ZIF-67/WO3(1:1)元件对100×10-6三乙胺的响应曲线;(b)不同元件在220℃对三乙胺的响应恢复时间

    Figure  5.  (a) Response curve of the ZIF-67/WO3(1:1) sensor to 100×10-6 triethylamine; (b) Response/Recovery time of different sensors to triethylamine at 220℃

    图  6  (a) ZIF-67/WO3(1:1)元件在220℃对不同浓度三乙胺的动态响应曲线(插图为低浓度的放大图); (b) 体积分数1×10-6~50×10-6的响应线性关系

    Figure  6.  (a) Dynamic response curves of the ZIF-67/WO3(1:1) sensor to different concentrations of triethylamine at 220℃ (inset is an enlarged view of low concentration); (b) Linear relation of volume fraction 1×10-6~50×10-6

    图  7  ZIF-67/WO3(1:1)传感器的长期稳定性测试

    Figure  7.  Long-term stability tests of the ZIF-67/WO3 (1:1) sensor

    图  8  ZIF-67/WO3(1:1)和纯WO3元件在220℃对100×10-6三乙胺的湿度稳定性曲线

    Figure  8.  Humidity stability curve of the ZIF-67/WO3 (1:1) sensor and pure WO3 sensor to 100×10-6 triethylamine at 220℃

    图  9  ZIF-67/WO3异质结在空气和三乙胺中的传感机制示意图

    Figure  9.  Schematic diagram of sensing mechanism for ZIF-67/WO3 composites in air and TEA, respectively

    表  1  ZIF-67/WO3复合材料的原料配比

    Table  1.   Raw material ratios of ZIF-67/WO3 composites

    SamplesMolar ratio n(W): n(Co)
    ZIF-67/WO3(5:1)5:1
    ZIF-67/WO3(1:1)1:1
    ZIF-67/WO3(1:5)1:5
    下载: 导出CSV

    表  2  不同敏感材料对于三乙胺气敏性能对比

    Table  2.   Compared TEA sensing performance of different sensing materials

    MaterialVolume fraction /10−6Response (Ra/Rg)Temperature
    /℃
    Tres/Trec/sRef.
    ZnO50832808/23[30]
    WO3/h-BN-5500390.62608/60[31]
    WO350162201.5/22[32]
    Pd NPs-In2O35047.562204/17[33]
    SnO2/SiO2508.27280--/--[34]
    SnO25054.923526/13[1]
    2%Ga-doped Co3O4501081803/15[35]
    ZIF-67/WO3(1:1)50118.082209/7This work
    Notes: Ra and Rg denoted the resistance of the sensor in air and target gas, respectively; Tres and Trec are the response and recovery time, respectively, which defined as the time required to reaching 90% of the total resistance change after exposure to the target gas and air, respectively.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-01-06
  • 录用日期:  2022-03-18
  • 修回日期:  2022-02-21
  • 网络出版日期:  2022-04-02

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