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富Bi型Bi4O5Br2/TiO2复合纤维的高效光催化CO2还原

李跃军 曹铁平 孙大伟

李跃军, 曹铁平, 孙大伟. 富Bi型Bi4O5Br2/TiO2复合纤维的高效光催化CO2还原[J]. 复合材料学报, 2023, 40(11): 6251-6259. doi: 10.13801/j.cnki.fhclxb.20230222.004
引用本文: 李跃军, 曹铁平, 孙大伟. 富Bi型Bi4O5Br2/TiO2复合纤维的高效光催化CO2还原[J]. 复合材料学报, 2023, 40(11): 6251-6259. doi: 10.13801/j.cnki.fhclxb.20230222.004
LI Yuejun, CAO Tieping, SUN Dawei. A bismuth-rich Bi4O5Br2/TiO2 composites fibers photocatalyst enables dramatic CO2 reduction activity[J]. Acta Materiae Compositae Sinica, 2023, 40(11): 6251-6259. doi: 10.13801/j.cnki.fhclxb.20230222.004
Citation: LI Yuejun, CAO Tieping, SUN Dawei. A bismuth-rich Bi4O5Br2/TiO2 composites fibers photocatalyst enables dramatic CO2 reduction activity[J]. Acta Materiae Compositae Sinica, 2023, 40(11): 6251-6259. doi: 10.13801/j.cnki.fhclxb.20230222.004

富Bi型Bi4O5Br2/TiO2复合纤维的高效光催化CO2还原

doi: 10.13801/j.cnki.fhclxb.20230222.004
基金项目: 国家自然科学基金项目(21573003);吉林省自然科学基金项目(20140101118JC)
详细信息
    通讯作者:

    曹铁平,博士,教授,硕士生导师,研究方向为功能纳米材料 E-mail: bcctp2008@163.com

  • 中图分类号: O614.32;TB33

A bismuth-rich Bi4O5Br2/TiO2 composites fibers photocatalyst enables dramatic CO2 reduction activity

Funds: National Natural Science Foundation of China (21573003); Natural Science Foundation of Jilin Province (20140101118JC)
  • 摘要: 光催化CO2还原技术既能实现节能减排,又能缓解能源短缺,符合当今绿色可持续发展的理念。本工作以静电纺丝技术制备的TiO2纳米纤维为基质,结合水热还原法制备Bi@Bi4O5Br2/TiO2复合纤维。利用XRD、SEM、HRTEM、XPS、UV-Vis和碳吸附等方法对其微观结构、形貌和光学性能进行表征。结果表明:TiO2 纳米纤维经Bi4O5Br2复合后,光谱响应范围拓展到可见光区,光生电子还原能力增强,可以将CO2还原成CH4和CO;金属Bi的富集不仅能提高催化剂对酸性CO2分子的吸附能力,增强CO2转化效率,而且能改变光催化反应路径,并有醇类物质(CH3OH)的生成。模拟太阳光照射3 h,Bi@Bi4O5Br2/TiO2光催化CO2还原生成CH4、CO和CH3OH的速率分别达到3.87、1.06和0.32 μmol·h−1·g−1。本文为探索高效二氧化碳光还原催化剂提供了新的机会。

     

  • 图  1  样品TiO2、Bi4O5Br2、Bi4O5Br2/TiO2和Bi@Bi4O5Br2/TiO2的XRD图谱 (a) 和局部放大XRD图谱 (b)

    Figure  1.  XRD patterns (a) and the expanded view of XRD patterns (b) of TiO2, Bi4O5Br2, Bi4O5Br2/TiO2 and Bi@Bi4O5Br2/TiO2 samples

    图  2  样品TiO2 (a)、Bi4O5Br2 (b)、Bi4O5Br2/TiO2 (c)Bi@Bi4O5Br2/TiO2 (d)的SEM图像和Bi@Bi4O5Br2/TiO2 ((e), (f)) 的HRTEM图像

    Figure  2.  SEM images of samples TiO2 (a), Bi4O5Br2 (b), Bi4O5Br2/TiO2 (c), Bi@Bi4O5Br2/TiO2 (d) and HRTEM images of Bi@Bi4O5Br2/TiO2 ((e), (f))

    图  3  不同样品的N2吸附-脱附等温线和孔径分布曲线

    dV/dD—Differential pore volume versus diameter

    Figure  3.  N2 adsorption-desorption isotherms and pore-size of different samples

    图  4  不同样品的CO2吸附等温线 (a) 和CO2程序升温脱附 (b)

    Figure  4.  CO2 adsorption isotherms (a) and temperature programmed desorption spectrum of CO2 (b) for the different samples

    图  5  样品Bi@Bi4O5Br2/TiO2的XPS图谱:(a) 全谱;(b) Ti2p;(c) Bi4f;(d) Br3d;(e) O1s

    Figure  5.  XPS spectra of the Bi@Bi4O5Br2/TiO2 sample: (a) Full spectrum; (b) Ti2p; (c) Bi4f; (d) Br3d; (e) O1s

    图  6  样品TiO2、Bi4O5Br2、Bi4O5Br2/TiO2和Bi@Bi4O5Br2/TiO2:(a) 紫外-可见漫反射;(b) 光致发光;(c) 瞬态光电流;(d) Bi4O5Br2/TiO2和Bi@Bi4O5Br2/TiO2的瞬态荧光衰减寿命;(e) TiO2和Bi4O5Br2的莫特肖特基曲线

    τ—Fitting life; A—Corresponding proportion; C—Capacitance

    Figure  6.  TiO2, Bi4O5Br2, Bi4O5Br2/TiO2 and Bi@Bi4O5Br2/TiO2 samples: (a) UV-Vis DRS; (b) PL spectra; (c) Transient photocurrent responses; (d) Transient fluorescence decay lifetime of Bi4O5Br2/TiO2 and Bi@Bi4O5Br2/TiO2 samples; (e) Mott-Schottky curves of TiO2 and Bi4O5Br2 samples

    图  7  样品TiO2、Bi4O5Br2、Bi4O5Br2/TiO2和Bi@Bi4O5Br2/TiO2光催化CO2还原3 h后CH4、CO和CH3OH的生成速率 (a) 及样品Bi@Bi4O5Br2/TiO2光催化产物的生成量随时间变化 (b)

    Figure  7.  Yields of CH4, CO and CH3OH for photocatalytic CO2 reduction over TiO2, Bi4O5Br2, Bi4O5Br2/TiO2 and Bi@Bi4O5Br2/TiO2 samples after 3 hours irradiation (a) and time course of the products in the photocatalytic conversion of CO2 over Bi@Bi4O5Br2/TiO2 sample (b)

    图  8  Bi@Bi4O5Br2/TiO2光催化CO2还原反应机制示意图

    CB—Conduction band; VB—Valence band; Eg—Band gap; E—Energy

    Figure  8.  Schematic mechanism of photocatalytic CO2 reduction of Bi@Bi4O5Br2/TiO2 sample

    表  1  不同样品的比表面积、孔径和孔容大小

    Table  1.   Specific surface area, pore size, pore volume size of different samples

    SampleSpecific
    surface area/
    (m2·g−1)
    Average pore
    diameter/nm
    Total pore
    volume/
    (cm2·g−1)
    TiO2 3014.60.15
    Bi4O5Br212820.40.24
    Bi4O5Br2/TiO214424.90.26
    Bi@Bi4O5Br2/TiO213221.60.25
    下载: 导出CSV

    表  2  CO2光催化还原产物生成速率比较

    Table  2.   Comparison of products generation rate for CO2 photocatalytic reduction

    PhotocatalystIllumination
    period/h
    Reaction
    condition
    ProductYield/
    (μmol·g−1·h−1)
    Reference
    Pt/D-TiO2–x 5 300 W Xe lamp
    120℃, water
    CH4 0.34
    [29]
    Fe-TiO2 12 Visible light
    (λ>400 nm)
    CH4 7.73
    [30]
    TiO2-G 5 300 W Xe lamp
    NaHCO3+H2SO4
    CO
    CH4
    5.20
    26.70

    [31]
    Fe/TiO2/rGO 5 300 W Xe lamp
    (λ>420 nm)
    CH4
    O2
    4.08
    4.32

    [32]
    Bi2Al4O9/β-Bi2O3 10 300 W Xe lamp
    H2O
    CO 13.50
    [33]
    Bi/Bi4O5Br2 2 300 W high pressure Xenon lamp CO
    CH4
    3.16
    0.50

    [18]
    g-C3N4/α-Fe2O3 300 W Xenon lamp CH3OH 5.63
    [34]
    TiO2/Ni(OH)2 3 300 W Xe lamp
    40 mW·cm−2
    CO
    CH4
    CH3OH
    CH3CH2OH
    0.71
    2.20
    0.58
    0.37

    [8]
    Notes: D—Diameter; G—Graphene; rGO—Reduced graphene oxide; λ—Wavelength.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-12-13
  • 修回日期:  2023-02-06
  • 录用日期:  2023-02-10
  • 网络出版日期:  2023-02-22
  • 刊出日期:  2023-11-01

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