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具有优异光激发NO2气敏性能和MB光催化降解效率的ZnO-MoS2纳米复合材料

孙翼飞 余飞 袁欢 徐明 张秋平 宋曼 黎健鸿 柏明辉

孙翼飞, 余飞, 袁欢, 等. 具有优异光激发NO2气敏性能和MB光催化降解效率的ZnO-MoS2纳米复合材料[J]. 复合材料学报, 2023, 40(6): 3428-3440. doi: 10.13801/j.cnki.fhclxb.20220906.003
引用本文: 孙翼飞, 余飞, 袁欢, 等. 具有优异光激发NO2气敏性能和MB光催化降解效率的ZnO-MoS2纳米复合材料[J]. 复合材料学报, 2023, 40(6): 3428-3440. doi: 10.13801/j.cnki.fhclxb.20220906.003
SUN Yifei, YU Fei, YUAN Huan, et al. ZnO-MoS2 nano-composites with excellent light-activated NO2 gas sensitivity and MB photocatalytic degradation efficiency[J]. Acta Materiae Compositae Sinica, 2023, 40(6): 3428-3440. doi: 10.13801/j.cnki.fhclxb.20220906.003
Citation: SUN Yifei, YU Fei, YUAN Huan, et al. ZnO-MoS2 nano-composites with excellent light-activated NO2 gas sensitivity and MB photocatalytic degradation efficiency[J]. Acta Materiae Compositae Sinica, 2023, 40(6): 3428-3440. doi: 10.13801/j.cnki.fhclxb.20220906.003

具有优异光激发NO2气敏性能和MB光催化降解效率的ZnO-MoS2纳米复合材料

doi: 10.13801/j.cnki.fhclxb.20220906.003
基金项目: 西南民族大学研究生创新型科研项目(CX2021 SZ44);国家自然科学基金青年科学基金(61901401)
详细信息
    通讯作者:

    余飞,博士,副教授,硕士生导师,研究方向为氧化物功能材料 E-mail: yufei@swun.edu.cn

    袁欢,博士,副教授,硕士生导师,研究方向为光敏传感器件 E-mail: yuanh@uestc.edu.cn

  • 中图分类号: O643.3,TB34;TB331

ZnO-MoS2 nano-composites with excellent light-activated NO2 gas sensitivity and MB photocatalytic degradation efficiency

Funds: Southwest Minzu University Graduate Innovative Research Fund (CX2021 SZ44); National Natural Science Foundation of China (61901401)
  • 摘要: 实现对有毒、有害气体的有效监测和对有机污染物的快速降解,对于减少大气污染和水污染所带来的危害至关重要。本研究采用超声复合方法将溶胶凝胶法制备的ZnO和水热法制备的MoS2复合到一起,成功制备了ZnO-MoS2纳米复合材料。采用XRD、SEM、TEM、XPS等手段对材料结构、形貌和表面化学组分进行表征。结果表明,多层片状MoS2均匀负载到了ZnO纳米颗粒当中,复合材料具有较好的结晶性和丰富的表面缺陷。利用紫外-可见(UV-vis)漫反射光谱、光致发光光谱(PL)和表面光电压(SPV)对材料的光电性能进行了测试。结果表明,ZnO与MoS2的复合在提升光利用率的同时,能够促进光生载流子的更有效分离。以NO2作为目标气体的室温紫外光辅助气敏测试表明,本方法制备的ZnO-MoS2气体传感器具有良好的灵敏度、恢复性、稳定性和选择性,可在室温下实现对低浓度NO2的有效响应,MoS2复合量为5wt%的ZnO-MoS2传感器对0.47 mg/m3 NO2的响应值为19.6%。同时,气敏性能研究还发现空气中O2分子在材料表面的吸附会对传感器的气敏性能产生较大的影响,ZnO-MoS2传感器在无氧条件下对NO2具有更高的气敏响应。此外,在模拟太阳光下进行的光催化降解亚甲基蓝(MB)的实验表明,依靠吸附和光催化降解的共同作用,ZnO-MoS2复合材料能够在40 min内实现水溶液当中较高浓度MB (15 mg/L)的快速清除,MoS2复合量为10wt%的ZnO-MoS2样品的反应速率常数达到了0.032 min−1。对机制的分析表明,MoS2较好的吸附性和复合所导致的光生载流子分离率的提升是ZnO-MoS2复合材料气敏和光催化性能提升的关键。

     

  • 图  1  气敏测试示意图

    Figure  1.  Schematic diagram of gas sensitivity test

    LED—Light emitting diode; UV—Ultra violet

    图  2  ZnO和ZnO-MoS2样品的XRD图谱

    Figure  2.  XRD patterns of ZnO and ZnO-MoS2 samples

    图  3  ZnO (a)、MoS2 (b)、ZnO-5MoS2 ((c), (d))、ZnO-10MoS2 ((e), (f)) 和ZnO-20MoS2 ((g), (h)) 的SEM图像

    Figure  3.  SEM images of ZnO (a), MoS2 (b), ZnO-5MoS2 ((c), (d)), ZnO-10MoS2 ((e), (f)) and ZnO-20MoS2 ((g), (h))

    图  4  ZnO-20MoS2样品的TEM图像

    Figure  4.  TEM images of ZnO-20MoS2 sample

    图  5  ZnO-20MoS2样品的XPS图谱:(a) Zn2p;(b) O1s;(c) S2p;(d) Mo3d

    Figure  5.  XPS spectra of ZnO-20MoS2 sample: (a) Zn2p; (b) O1s; (c) S2p; (d) Mo3d

    OL—Lattice oxygen; OV—Vacant oxygen; OC—Chemisorbed oxygen

    图  6  ZnO和ZnO-MoS2样品的UV-vis吸收图谱

    Figure  6.  UV-vis absorption spectra of ZnO and ZnO-MoS2 samples

    图  7  ZnO和ZnO-MoS2样品的光致发光图谱

    Figure  7.  Photoluminescence spectra of ZnO and ZnO-MoS2 samples

    图  8  ZnO和ZnO-MoS2样品的表面光电压图谱

    Figure  8.  Surface photovoltage spectra of ZnO and ZnO-MoS2 samples

    图  9  (a) 室温紫外光照射下,ZnO和ZnO-MoS2传感器对0.47~2.35 mg/m3浓度NO2的动态响应曲线(干燥空气作为背景气体);(b) 4组传感器的响应-浓度曲线;(c) 4组传感器恢复率与浓度之间的关系

    Figure  9.  (a) Time-dependent response curves of ZnO, and ZnO-MoS2 sensors to 0.47-2.35 mg/m3 NO2 at room temperature with the irradiation of UV light (Dry air as background gas); (b) Response-concentration curves of four sensors; (c) Recovery rate-concentration plots of four sensors

    Rg—Measuring the resistance; R0—Initial resistance; Rec—Percentage of recovery rate; Response—Response intensity; C—Concentration

    图  10  (a) 室温紫外光照射下,ZnO和ZnO-MoS2传感器对2.35 mg/m3浓度NO2的5次重复动态响应曲线(干燥空气作为背景气体);(b) ZnO-5MoS2气体传感器对不同气体的选择性测试

    Figure  10.  (a) Repeated time-dependent response curves of ZnO and ZnO-MoS2 sensors to 2.35 mg/m3 NO2 in five cycles at room temperature with the irradiation of UV light (Dry air as background gas); (b) Selectivity test of ZnO-5MoS2 gas sensor for different gases

    图  11  ZnO-MoS2气敏机制图

    Figure  11.  Gas sensing mechanism illustration for ZnO-MoS2

    图  12  (a) 氮气作为背景气体四种传感器对0.47~2.35mg/m3 NO2的动态响应曲线;(b) ZnO-5MoS2气体传感器分别在空气与氮气作为背景气体时对0.47~2.35mg/m3的动态响应曲线

    Figure  12.  (a) Time-dependent response curves of the four sensors to 0.47~2.35 mg/m3 NO2 with nitrogen as background gas; (b) Time-dependent response curves of ZnO-5MoS2 gas sensor to 0.47~2.35 mg/m3 NO2 with air and nitrogen as background gas respectively

    图  13  (a) ZnO及ZnO-MoS2样品在暗环境中吸附和在模拟太阳光照射下光催化降解亚甲基蓝(MB)的曲线;(b) 光照20 min时4种样品对于MB的清除效率;(c) 光照前20 min 4种样品降解MB的反应速率常数;(d) 模拟太阳光照射下添加不同牺牲剂后ZnO-10MoS2样品降解MB的反应速率常数

    Figure  13.  (a) Dark adsorption and photocatalytic degradation of methylene blue (MB) with the ZnO and ZnO-MoS2 samples under simulated sunlight irradiation; (b) MB removal efficiency for four samples after 20 min irradiation; (c) Reaction rate constants of four samples for the first 20 min of irradiation; (d) Reaction rate constants of ZnO-10MoS2 for photodegradation of MB with different sacrificial agents under the simulated sunlight irradiation

    IPA—Isopropyl alcohol; EDTA-2Na—Edetate disodium; BQ—Benzoquinone; K—Reaction rate constant (min−1); C0—Initial concentration; Ct—Concentration at time t

    表  1  ZnO-MoS2 样品成分配比

    Table  1.   Composition proportion of ZnO-MoS2 samples

    Sample Mass of ZnO/g Mass of MoS2/g
    ZnO-5MoS2 0.95 0.05
    ZnO-10MoS2 0.90 0.10
    ZnO-20MoS2 0.80 0.20
    下载: 导出CSV

    表  2  不同复合材料的NO2气敏性能

    Table  2.   NO2 gas sensing performance of different composite materials

    Sensor materialsGas concentration/(mg·m3)Operation temperature/℃ResponseRef.
    ZnO-MoS2 NWs 94 200 31.2% [17]
    Ag-Fe2O3-MoS2 1.88 120 70.8% [34]
    MoS2-SnS2 9.4 25 60% [35]
    Au-MoS2 4.7 25 30% [36]
    CuO-ZnO 188 150 96% [37]
    ZnO-RGO 9.4 25 7% [38]
    ZnO-5MoS2 2.35 25 85.1% This work
    Notes: NWs—Nanowires; RGO—Reduced graphene oxide.
    下载: 导出CSV

    表  3  不同ZnO基材料光催化降解MB对比

    Table  3.   Comparison of photocatalytic efficiency of ZnO based composites for the degradation of MB

    PhotocatalystIrradiation
    Source
    Pollutant
    concentration/(mg·L−1)
    Irradiation time/minRef.
    ZnO-RGO UV 5 ~300 [41]
    ZnO-RGO-CdS UV 30 240 [42]
    ZnO-MoS2 Simulated sunlight 30 300 [19]
    ZnO-MoS2 Simulated sunlight 5 50 [20]
    ZnO-MoS2 UV 10 120 [21]
    ZnO-10MoS2 Simulated sunlight 15 40 This work
    下载: 导出CSV
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  • 收稿日期:  2022-07-12
  • 修回日期:  2022-08-25
  • 录用日期:  2022-08-26
  • 网络出版日期:  2022-09-07
  • 刊出日期:  2023-06-15

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