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Cu2O-PVA/纳米纤维素复合材料的制备与吸附-光催化性能

王艳飞 靳泽远 李卓林 王鹤然 邢鹏宇 罗琳龙 胡英成

王艳飞, 靳泽远, 李卓林, 等. Cu2O-PVA/纳米纤维素复合材料的制备与吸附-光催化性能[J]. 复合材料学报, 2023, 40(1): 180-191. doi: 10.13801/j.cnki.fhclxb.20220117.004
引用本文: 王艳飞, 靳泽远, 李卓林, 等. Cu2O-PVA/纳米纤维素复合材料的制备与吸附-光催化性能[J]. 复合材料学报, 2023, 40(1): 180-191. doi: 10.13801/j.cnki.fhclxb.20220117.004
WANG Yanfei, JIN Zeyuan, LI Zhuolin, et al. Preparation and adsorption-photocatalytic properties of Cu2O-PVA/nanocellulose composite[J]. Acta Materiae Compositae Sinica, 2023, 40(1): 180-191. doi: 10.13801/j.cnki.fhclxb.20220117.004
Citation: WANG Yanfei, JIN Zeyuan, LI Zhuolin, et al. Preparation and adsorption-photocatalytic properties of Cu2O-PVA/nanocellulose composite[J]. Acta Materiae Compositae Sinica, 2023, 40(1): 180-191. doi: 10.13801/j.cnki.fhclxb.20220117.004

Cu2O-PVA/纳米纤维素复合材料的制备与吸附-光催化性能

doi: 10.13801/j.cnki.fhclxb.20220117.004
基金项目: 国家自然科学基金项目(32171692);中央高校基本科研业务费专项资金项目(2572020DR13);东北林业大学院级大学生训练创新项目(CL06)
详细信息
    通讯作者:

    胡英成,博士,教授,博士生导师,研究方向为生物质复合材料性能评价 E-mail: yingchenghu@163.com

  • 中图分类号: TB332

Preparation and adsorption-photocatalytic properties of Cu2O-PVA/nanocellulose composite

Funds: National Natural Science Fundation of China (32171692); Fundamental Research Funds for the Central Universities (2572020DR13); College Students' Innovative Entrepreneurial Training Plan Program of Northeast Forestry University (CL06)
  • 摘要: 为了改善氧化亚铜(Cu2O)的光催化性能,将Cu2O颗粒和聚乙烯醇(PVA)同时加入纳米纤维素(CNF)中,成功制备了具有三维(3D)多孔结构和丰富活性位点的功能化纤维素基气凝胶(Cu2O-PVA/CNF)。采用扫描电子显微镜、傅里叶变换红外光谱、X射线衍射仪、全自动比表面积、压缩测试对气凝胶样品进行了表征。以降解亚甲基蓝(MB)为模型污染物,评价了Cu2O-PVA/CNF复合催化剂的光催化性能,考察了6wt%Cu2O-PVA/CNF在不同初始浓度、不同催化剂用量及不同溶液pH条件下对MB光降解效率的影响。结果表明,三维多孔的纤维素气凝胶的使用提高了对MB的吸附能力,延长了对可见光的吸收。特别是在纤维素基体中掺杂的Cu2O在光照下激发出电子-空穴,增加了活性位点,从而提高了催化能力。6wt%Cu2O-PVA/CNF复合催化剂对MB的光降解率达到95.6%,远高于纯Cu2O的79.6%。Cu2O-PVA/CNF复合催化剂的光降解过程遵循表观准一级动力学模型。此外,与纯CNF气凝胶相比,PVA的加入使其压缩强度提高了4.4倍。该催化剂经5次光催化循环后再利用,对MB的可见光催化降解率仍能达到71.06%。这种Cu2O-PVA/CNF复合材料有利于用太阳辐射处理染料废水。

     

  • 图  1  Cu2O-PVA/CNF复合气凝胶的制备流程图

    Figure  1.  Flow chart of preparation of Cu2O-PVA/CNF composite aerogel

    图  2  CNF、PVA/CNF和Cu2O-PVA/CNF气凝胶的SEM图像

    Figure  2.  SEM images of CNF, PVA/CNF and Cu2O-PVA/CNF aerogel

    图  3  CNF、PVA、Cu2O-PVA和Cu2O-PVA/CNF的红外图谱

    Figure  3.  FTIR spectra of CNF, PVA, Cu2O-PVA and Cu2O-PVA/CNF

    图  4  CNF、Cu2O和Cu2O-PVA/CNF的XRD图谱

    Figure  4.  XRD patterns of CNF, Cu2O and Cu2O-PVA/CNF

    图  5  CNF和Cu2O-PVA/CNF的N2等温吸附曲线(a)和孔径分布图(b)

    Figure  5.  Nitrogen adsorption/desorption isotherms (a) and pore size distribution (b) of CNF and Cu2O-PVA/CNF

    V—Pore volume; D—Diameter

    图  6  CNF和Cu2O-PVA/CNF的压缩应力-应变曲线

    Figure  6.  Compression stress-strain curves of CNF and Cu2O-PVA/CNF

    图  7  CNF和Cu2O-PVA/CNF 的UV-vis DRS图谱

    Figure  7.  UV-vis DRS spectra of CNF and Cu2O-PVA/CNF

    图  8  纯Cu2O和Cu2O-PVA/CNF复合气凝胶的吸附-光催化效率对比(a)和一级动力学模型(b)

    Figure  8.  Comparison of adsorption-photocatalytic efficiency of pure Cu2O and Cu2O-PVA/CNF composite aerogels (a) and first order dynamics model (b)

    C—Instantaneous concentration of MB; C0—Initial concentration of MB

    图  9  6wt%Cu2O-PVA/CNF在不同初始浓度下对催化效率的影响(a)和一级动力学模型(b)

    Figure  9.  Effect of 6wt%Cu2O-PVA/CNF on catalytic efficiency at different initial concentrations (a) and first order dynamics model (b)

    图  10  6wt%Cu2O-PVA/CNF催化剂不同用量对催化效率的影响(a)和一级动力学模型(b)

    Figure  10.  Effect of different amount of 6wt%Cu2O-PVA/CNF catalyst on catalytic efficiency (a) and first order dynamics model (b)

    图  11  6wt%Cu2O-PVA/CNF在不同溶液pH下对光催化效率的影响(a)和一级动力学模型(b)

    Figure  11.  Effect of 6wt%Cu2O-PVA/CNF on photocatalytic efficiency at different solution pH (a) and first order dynamics model (b)

    图  12  活性物质捕获剂对MB降解率的影响(a); 6wt%Cu2O-PVA/CNF (DMPO作为自由基捕获剂)的ESR光谱:在可见光照射下检测DMPO-•O2 (b)和DMPO-•OH (c)

    Figure  12.  Effect of active substance capture agent on MB degradation rate (a); ESR spectra of 6wt%Cu2O-PVA/CNF (DMPO as radical trapper): Detecting DMPO-•O2 (b) and DMPO-•OH (c) under visible light irradiation

    BQ—Benzoquinone; IPA—Isopropyl alcohol; DMPO—Dimethyl pyridine-N-oxide

    图  13  6wt%Cu2O-PVA/CNF重复使用次数对MB降解率的影响(a)和使用前后的XRD图谱(b)

    Figure  13.  Effect of repeated use of 6wt%Cu2O-PVA/CNF on MB degradation rate (a) and XRD patterns before and after use (b)

    表  1  Cu2O-聚乙烯醇(PVA)/纳米纤维素(CNF)气凝胶的用量

    Table  1.   Amount of Cu2O-polyvinyl alcohol (PVA)/nanocellulose (CNF) aerogel

    Sample CNF/g PVA/g Cu2O/g
    2wt%Cu2O-PVA/CNF 5 5 0.1
    4wt%Cu2O-PVA/CNF 5 5 0.2
    6wt%Cu2O-PVA/CNF 5 5 0.3
    8wt%Cu2O-PVA/CNF 5 5 0.4
    下载: 导出CSV

    表  2  CNF和Cu2O-PVA/CNF的比表面积和孔径结构参数

    Table  2.   Surface area and pore size structural parameters of CNF and Cu2O-PVA/CNF

    SamplesSpecific
    surface
    area/(m2·g−1)
    Pore size/nmTotal pore
    volume/
    (cm3·g−1)
    CNF 4.00 2.52 0.00250
    2wt%Cu2O-PVA/CNF 14.00 6.23 0.02200
    4wt%Cu2O-PVA/CNF 10.40 5.89 0.01500
    6wt%Cu2O-PVA/CNF 6.91 5.44 0.00940
    8wt%Cu2O-PVA/CNF 2.67 4.33 0.00380
    下载: 导出CSV

    表  3  Cu2O 和 Cu2O-PVA/CNF的去除率、速率常数和拟合系数r2

    Table  3.   Removal rate, rate constant and correlation coefficient afterfitting r2 of Cu2O and Cu2O-PVA/CNF

    SamplesAdsorption removal
    rate/%
    Catalytic removal
    rate/%
    Total removal
    rate/%
    Κ/min−1r2
    Cu2O10.169.579.60.01850.996
    2wt%Cu2O-PVA/CNF40.850.791.50.02430.983
    4wt%Cu2O-PVA/CNF45.047.092.00.02410.986
    6wt%Cu2O-PVA/CNF46.948.795.60.03110.991
    8wt%Cu2O-PVA/CNF40.742.483.20.02230.991
    Notes: K—Catalytic efficiency; r2—Correlation coefficient after fitting.
    下载: 导出CSV

    表  4  不同溶液pH对亚甲基蓝(MB)脱色动力学模型的数据

    Table  4.   Data of the kinetic model of the decolonization of methylene blue (MB) in different solutions pH

    pHR/(mg·L−1·min−1)r2
    3 0.00347 0.993
    5 0.02350 0.984
    7 0.02860 0.988
    9 0.02880 0.985
    11 0.03760 0.962
    Note: R—Rate constant.
    下载: 导出CSV
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  • 收稿日期:  2021-11-11
  • 修回日期:  2022-01-05
  • 录用日期:  2022-01-07
  • 网络出版日期:  2022-01-18
  • 刊出日期:  2023-01-15

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