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金属有机凝胶限域CdS QDs异质结光催化剂协同降解诺氟沙星和还原Cr(VI)

计海峰 刘书亭 石洪飞 潘高峰

计海峰, 刘书亭, 石洪飞, 等. 金属有机凝胶限域CdS QDs异质结光催化剂协同降解诺氟沙星和还原Cr(VI)[J]. 复合材料学报, 2023, 40(5): 2847-2858. doi: 10.13801/j.cnki.fhclxb.20220826.001
引用本文: 计海峰, 刘书亭, 石洪飞, 等. 金属有机凝胶限域CdS QDs异质结光催化剂协同降解诺氟沙星和还原Cr(VI)[J]. 复合材料学报, 2023, 40(5): 2847-2858. doi: 10.13801/j.cnki.fhclxb.20220826.001
JI Haifeng, LIU Shuting, SHI Hongfei, et al. Synergistic degradation of norfloxacin and reduction of Cr(VI) by CdS QDs encapsulated in metal-organic gel heterojunction photocatalyst[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2847-2858. doi: 10.13801/j.cnki.fhclxb.20220826.001
Citation: JI Haifeng, LIU Shuting, SHI Hongfei, et al. Synergistic degradation of norfloxacin and reduction of Cr(VI) by CdS QDs encapsulated in metal-organic gel heterojunction photocatalyst[J]. Acta Materiae Compositae Sinica, 2023, 40(5): 2847-2858. doi: 10.13801/j.cnki.fhclxb.20220826.001

金属有机凝胶限域CdS QDs异质结光催化剂协同降解诺氟沙星和还原Cr(VI)

doi: 10.13801/j.cnki.fhclxb.20220826.001
基金项目: 吉林省科技厅优秀青年人才基金(20190103117JH);吉林省教育厅项目(JJKH20190827KJ)
详细信息
    通讯作者:

    潘高峰,博士,教授,硕士生导师,研究方向为污染物处理与资源化 E-mail:pangaofeng@hotmail.com

  • 中图分类号: X703;TB333

Synergistic degradation of norfloxacin and reduction of Cr(VI) by CdS QDs encapsulated in metal-organic gel heterojunction photocatalyst

Funds: Outstanding Young Talents Fund Project of Jilin Provincial Department of Science and Technology (20190103117JH); Project of Jilin Provincial Department of Education (JJKH20190827KJ)
  • 摘要: 构建具有高效电荷转移途径的异质结材料是光催化降解水体复合污染物的关键。采用凝胶限域法将CdS量子点(CdS QDs)分散在金属有机凝胶MOX(Al)中,制备出CdS QDs@MOX(Al)异质结光催化剂。通过 XRD、TEM、XPS、N2吸附-脱附等温曲线、UV-Vis DRS、瞬态光电流(TPC)响应和电化学阻抗谱(EIS)等手段对样品的组成结构和界面电荷传输效率进行了表征及分析,并探讨了在可见光下协同降解诺氟沙星(NF)和还原Cr(VI)的催化活性和机制。结果表明:1.0-CdS QDs@MOX(Al)对NF/Cr(VI)复合污染物体系表现出优异的光催化活性,降解过程符合伪一级动力学模型,表观速率常数k分别是纯MOX(Al)和CdS的6.1(8.5)倍和5.3(3.5)倍。与单一污染物体系相比,CdS QDs@MOX(Al)对NF/Cr(VI)复合污染物体系的光催化效率显著提高。活性物种捕获实验证实h+和•O2为主要活性物种,光催化活性的增强主要归因于MOX(Al)和CdS QDs间形成的Type-II型异质结构,加速了光生电荷在异质结构界面处的有效分离和转移。

     

  • 图  1  MOX(Al)和CdS QDs@MOX(Al)的XRD图谱

    Figure  1.  XRD patterns of MOX(Al) and CdS QDs@MOX(Al)

    图  2  1.0-CdS QDs@MOX(Al)的TEM图像 ((a), (b)) 和HRTEM图像 ((c), (d)) (图2(b)中插图为粒径分布图)

    Daverage—Average size

    Figure  2.  TEM images ((a), (b)) and HRTEM images ((c), (d)) of 1.0-CdS QDs@MOX(Al) (Inset in Fig.2(b) is particle size distribution)

    图  3  MOX(Al)和1.0-CdS QDs@MOX(Al)的XPS图谱

    Figure  3.  XPS spectra of MOX(Al) and 1.0-CdS QDs@MOX(Al)

    图  4  MOX(Al)和CdS QDs@MOX(Al)的N2吸附-脱附等温线和孔径分布曲线(插图)

    V—Pore volume; D—Pore diameter; STP—In standard state; p—N2 partial pressure; p0—At the temperature of liquid nitrogen, the saturated vapor pressure of N2

    Figure  4.  N2 adsorption-desorption isotherms and pore size distribution curves (illustration) of MOX(Al) and CdS QDs@MOX(Al)

    图  5  MOX(Al)、CdS和CdS QDs@MOX(Al)的紫外-可见光吸收图谱和禁带宽度(插图)

    α—Absorption coefficient; h—Planck constant; ν—Incident light frequency; Eg—Band gap width

    Figure  5.  UV-Vis DRS spectra and band gaps (illustration) of MOX(Al), CdS and CdS QDs@MOX(Al)

    图  6  协同降解诺氟沙星(NF) (a) 和还原Cr(VI) (b) 的光催化活性

    C0—Initial absorbance; Ct—Absorbance at light time t

    Figure  6.  Synergistic photocatalytic activity for norfloxacin (NF) degradation (a) and Cr(VI) reduction (b)

    图  7  光催化协同降解NF (a) 和还原Cr(VI) (b) 的伪一级动力学拟合曲线

    Figure  7.  First-kinetic curves of photocatalytic synergistic degradation of NF (a) and reduced Cr(VI) (b)

    图  8  NF和Cr(VI)在单独及协同作用时的降解率

    Figure  8.  Degradation rate of NF, Cr(VI) and NF-Cr(VI) mixture

    图  9  1.0-CdS QDs@MOX(Al)光催化降解NF和还原Cr(VI)的重复使用性

    Figure  9.  Reusability of 1.0-CdS QDs@MOX(Al) for the synergistic degradation of NF and reduction of Cr(VI)

    图  10  催化剂1.0-CdS QDs@MOX(Al)循环使用前后的XRD图谱

    Figure  10.  XRD patterns of the 1.0-CdS QDs@MOX(Al) catalyst before and after recycling

    图  11  不同捕获剂对光催化性能的影响

    TEMPO—4-hydroxy-2, 2, 6, 6-tetramethylpiperidine-1-oxyl; TEOA—Triethanolamine; IPA—Isopropanol

    Figure  11.  Effects of different capture agents on photocatalytic performance

    图  12  MOX(Al)、CdS和1.0-CdS QDs@MOX(Al)的电化学阻抗谱图 (a)、电流响应曲线 (b)、莫特-肖特基曲线 (c) 和能带结构示意图 (d)

    VB—Valence band; CB—Conduction band; NHE—Normal hydrogen electrode

    Figure  12.  EIS Nyquist plots (a), transient photocurrent response curves (b), Mott-Schottky curves (c) and schematic diagram of energy band structure (d) for MOX(Al), CdS and 1.0-CdS QDs@MOX(Al)

    图  13  CdS QDs@MOX(Al)催化剂光催化降解机制

    Figure  13.  Photocatalytic degradation mechanism of CdS QDs@MOX(Al) catalyst

    表  1  CdS量子点@金属有机凝胶(CdS QDs@MOX(Al))复合材料的命名

    Table  1.   Naming of CdS quantum dots@metal-organic gel (CdS QDs@MOX(Al)) composite

    SampleMole ratio of Cd2+ : MOX(Al)
    0.5-CdS QDs@MOX(Al)0.50
    0.75-CdS QDs@MOX(Al)0.75
    1.0-CdS QDs@MOX(Al)1.00
    1.25-CdS QDs@MOX(Al)1.25
    下载: 导出CSV

    表  2  MOX(Al)和CdS QDs@MOX(Al)的比表面积、孔体积和孔径

    Table  2.   Brunauer-Emmett-Teller surface areas, pore volume and pore diameter of MOX(Al) and CdS QDs@MOX(Al)

    SampleSurface aeraa/(m2·g−1)Pore volumeb/(cm3·g−1)Pore diameterc/nm
    MOX(Al)1302.721.43454.79
    0.5-CdS QDs@MOX(Al)1288.561.36144.74
    0.75-CdS QDs@MOX(Al)1198.521.26174.35
    1.0-CdS QDs@MOX(Al)1052.801.24854.23
    1.25-CdS QDs@MOX(Al)1021.231.21113.97
    Notes: a—BET multi-point method specific surface; b—BJH method desorption (Cylindrical pore model, 2.0-49.6 nm) pore volume; c—BJH method desorption (Cylindrical hole model) average hole diameter.
    下载: 导出CSV

    表  3  不同催化剂光催化性能的比较

    Table  3.   Comparison of photocatalytic properties of different catalysts

    Photocatalyst/Amount(mg)Pollutants/V(mL)/C0(mg·L−1)Light sourceTime/hEfficiency/%Ref.
    GTSA/25Cr(VI)/35/50UV mercury light3.079[6]
    3%CdS QDs/BiOI/Bi2MoO6/20NF/20/20Xe lamp1.093[9]
    15%Co9S8/g-C3N4/20Cr(VI)/50/10500 W Xe lamp3.087[34]
    Bi2S3/Bi2WO6/20Cr(VI)/20/10500 W Xe lamp1.088[35]
    ZnO/Cu2ONF/20/10Light intensity 50 mW/cm24.086[36]
    1.0-CdS QDs@MOX(Al)/40Cr(VI)/60/40300 W Xe lamp1.579.5This work
    1.0-CdS QDs@MOX(Al)/40NF/60/100300 W Xe lamp1.580.1This work
    Notes: GTSA—Thiourea/sodium alginate; V—Volume.
    下载: 导出CSV
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  • 收稿日期:  2022-05-31
  • 修回日期:  2022-08-06
  • 录用日期:  2022-08-11
  • 网络出版日期:  2022-08-26
  • 刊出日期:  2023-05-15

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