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ZnO@SnO2异质结复合纳米管的可控构筑及其光催化性能

高超民 于海瀚 赵悦含 张丽娜 葛慎光 于京华

高超民, 于海瀚, 赵悦含, 等. ZnO@SnO2异质结复合纳米管的可控构筑及其光催化性能[J]. 复合材料学报, 2021, 39(0): 1-12
引用本文: 高超民, 于海瀚, 赵悦含, 等. ZnO@SnO2异质结复合纳米管的可控构筑及其光催化性能[J]. 复合材料学报, 2021, 39(0): 1-12
Chaomin GAO, Haihan YU, Yuehan ZHAO, Lina ZHANG, Shenguang GE, Jinghua YU. Controllable construction of ZnO@SnO2 heterojunction composite nanotubes and their photocatalytic properties[J]. Acta Materiae Compositae Sinica.
Citation: Chaomin GAO, Haihan YU, Yuehan ZHAO, Lina ZHANG, Shenguang GE, Jinghua YU. Controllable construction of ZnO@SnO2 heterojunction composite nanotubes and their photocatalytic properties[J]. Acta Materiae Compositae Sinica.

ZnO@SnO2异质结复合纳米管的可控构筑及其光催化性能

基金项目: 国家自然科学基金项目(22104043),济南市“一事一议”顶尖人才项目,济南市“高校20条”项目 (2018GXRC001)
详细信息
    作者简介:

    葛慎光,博士,教授,博士生导师,研究方向为功能纳米材料的制备与传感应用 E-mail: chm_gesg@163.com

    通讯作者:

    张丽娜,博士,副教授,硕士生导师,研究方向为功能纳米材料可控制备及其光催化应用 E-mail: mse_zhangln@ujn.edu.cn

  • 中图分类号: (O611.4;O643.32,O643.36)

Controllable construction of ZnO@SnO2 heterojunction composite nanotubes and their photocatalytic properties

  • 摘要: 性能优异的功能纳米材料的设计构筑对于光催化应用而言至关重要。基于模板自刻蚀机理,利用两步溶剂热技术,以一维ZnO纳米棒为模板,在无需附加酸刻蚀的条件下成功制备一维圆顶状ZnO@SnO2异质结纳米管复合材料 (Heterojunction domed nanotubes, HDNs)。由于ZnO与SnO2具有匹配的能级结构,在纳米管界面处可形成促进载流子分离的内建电场,赋予该材料优异的光催化与稳定性能。通过控制实验过程中自产生的碱性强弱,实现两性氧化物ZnO的自刻蚀,从而实现ZnO@SnO2 HDNs的管壁厚度可控调控与催化性能的调节。借助SEM、TEM、STEM以及PL等表征手段对材料的微观形貌、元素组成、生长机理与性能进行了考察。以甲基橙、亚甲基蓝、曙红等为污染物模型,光催化污染物降解实验结果表明,获得的ZnO@SnO2 HDNs具有优良的光催化性能,光照60分钟内对亚甲蓝、曙红的降解率可达到95%,表明构筑的纳米管异质结极大地促进了载流子的分离,抑制其复合,提高了光催化性能。同时,循环稳定性能测试说明构建的异质结纳米管催化剂具有良好的稳定性能,在染料降解方面具有广阔的应用前景。

     

  • 图  1  ZnO@SnO2异质结圆顶状纳米管(HDNs)的生长示意图

    Figure  1.  Schematic of preparation processes of ZnO@SnO2 heterojunction domed nanotubes(HDNs)

    图  2  ZnO@SnO2 HDNs样品的SEM(a)、横截面SEM(b)以及元素分布图(c);(a)中的插图为ZnO@SnO2 HDNs的高分辨率SEM图

    Figure  2.  SEM images (a), corresponding cross-sectional SEM (b) and elemental mappings (c) of ZnO@SnO2 HDNs; The inset in (a) is the high-resolution SEM image of ZnO@SnO2 HDNs

    图  3  (a)、(c) ZnO@SnO2 HDNs的低倍TEM图;(d) ZnO@SnO2 HDNs的高倍TEM图;(b) ZnO NRs的低倍TEM图;ZnO NRs (e)和ZnO@SnO2 HDNs (f)的EDS图

    Figure  3.  Low magnification TEM image ((a),(c)) and high-resolution TEM image (d) of ZnO@SnO2 HDNs; (b) Low magnification TEM image of ZnO NRs; EDS of ZnO NRs (e) and ZnO@SnO2 HDNs (f)

    图  4  (a)单根ZnO@SnO2 HDNs的暗场TEM图及沿(a)中所示橙色线的扫描组分线图(b-d)

    Figure  4.  (a) Dark field TEM image of a single ZnO@SnO2 HDNs; (b-d) compositional line scanning profile along the orange line indicated in (a)

    图  5  ZnO NRs在溶剂热生长SnO2壳前后的SEM图:当SnO2前驱体浓度为0 mmol/L、2 mmol/L, 7 mmol/L和15 mmol/L (a-d)时样品的SEM图以及相应的断面SEM图(e-h)

    Figure  5.  SEM images of ZnO NRs before and after SnO2 shell coating with hydrothermal method: The SnO2 precursors concentration are set at 0 mmol/L (as-prepared ZnO NRs), 2 mmol/L, 7 mmol/L, 15 mmol/L, and the plane SEM images are shown in (a-d) and (e)-(h) present the corresponding cross-sectional SEM, respectively

    图  6  ZnO@SnO2 HDNs 随时间变化的生长过程。ZnO@SnO2 HDNs在反应时间为10分钟(a)、20分钟(b)、40分钟(c)和80分钟(d)时的TEM图

    Figure  6.  Time-dependent growth process of ZnO@SnO2 HDNs. Typical TEM images of the ZnO@SnO2 HDNs grown under the different reaction time: (a) 10 min, (b) 20 min, (c) 40 min, (d) 80 min

    图  7  ZnO (a)、SnO2 (b)和ZnO@SnO2 HDNs (c)的稳态PL和光电流响应曲线

    Figure  7.  Steady state PL and photocurrent responses of ZnO@SnO2 HDNs (a), ZnO (b) and SnO2 (c)

    图  8  ZnO@SnO2 HDNs的带隙结构图及其电子-空穴分离示意图

    Figure  8.  Schematic diagram showing band configuration and electron-hole separation at interface of ZnO@SnO2 HDNs under UV irradiation

    图  9  ZnO@SnO2 HDNs对曙红(a)、甲基橙(b)和亚甲蓝(c)的降解效果;(d)上述三种有机染料的光催化降解速率图

    Figure  9.  UV-vis absorption spectra of eosin red (a), methyl orange (b) and methylene blue (c) in the presence of ZnO@SnO2 HDNs; (d) the photocatalysis degradation rate of the three organic dyes

    C—Real-time concentration of organic dyes; C0—Initial concentration of an organic dye

    图  10  ZnO纳米棒对曙红(a)、亚甲蓝(b)和甲基橙(c)的降解效果

    Figure  10.  Variations of adsorption spectra of organic dye solutions in the presence of the ZnO irradiated by a mercury lamp for varying times: (a) eosin red, (b) methylene blue, (c) methyl orange

    图  11  ZnO@SnO2 HDNs对亚甲蓝光催化降解的循环稳定性能

    Figure  11.  The cycling tests of photocatalytic activity of the ZnO@SnO2 HDNs for methylene blue degradation

    表  1  本工作中ZnO@SnO2 HDNs与以往报道复合光催化剂对甲基橙光催化降解性能的比较

    Table  1.   Comparison of photocatalytic performance of ZnO@SnO2 HDNs toward methyl orange in this work with previously reported composite photocatalysts.

    SampleLight sourceExperimental conditionDegradation timeRefs.
    ZnO/SnO2 nanocomposites300 W Hg lamp200 mg; 100 mL, 20 ppm100 min/56%31
    SnO2 aerogel/rGO
    nanocomposite
    40 W UV lamp
    (370 nm)
    100 mg L−1; 1×10−5 mol/L60 min/84%32
    SnO2-CNT
    nanocomposites
    9 W eight UV-vis
    lamps (365 nm)
    200 mg; 100 mL, 10 ppm180 min/79%33
    Chitosan-SnO28 W mercury lamp100 mg; 5×10−5 mol/L100 min/92%34
    Cu-doped SnO2 QDs200 W xenon lamp100 mg; 100 mL, 20 ppm180 min/99%35
    ZnO@SnO2 HDNs500 W xenon lamp50 mg;80 min/95%This work
    Notes: rGO—reduced graphene oxide; CNT—carbon nanotube; QDs—quantum dot.
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  • 收稿日期:  2021-10-08
  • 录用日期:  2021-11-06
  • 修回日期:  2021-10-26
  • 网络出版日期:  2021-12-01

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