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Fe(III)Ox/ZnO催化剂的制备及其光催化CH4氧化性能

郝英东 刘双 孙楠楠 魏伟

郝英东, 刘双, 孙楠楠, 魏伟. Fe(III)Ox/ZnO催化剂的制备及其光催化CH4氧化性能[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60016-1
引用本文: 郝英东, 刘双, 孙楠楠, 魏伟. Fe(III)Ox/ZnO催化剂的制备及其光催化CH4氧化性能[J]. 燃料化学学报. doi: 10.1016/S1872-5813(22)60016-1
HAO Ying-dong, LIU Shuang, SUN Nan-nan, Wei Wei. Photocatalytic oxidation of CH4 to oxygenates on Fe(III)Ox/ZnO[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60016-1
Citation: HAO Ying-dong, LIU Shuang, SUN Nan-nan, Wei Wei. Photocatalytic oxidation of CH4 to oxygenates on Fe(III)Ox/ZnO[J]. Journal of Fuel Chemistry and Technology. doi: 10.1016/S1872-5813(22)60016-1

Fe(III)Ox/ZnO催化剂的制备及其光催化CH4氧化性能

doi: 10.1016/S1872-5813(22)60016-1
基金项目: 上海市科学技术委员会(19YF1452800, 19ZR1463500)资助
详细信息
    通讯作者:

    E-mail:sunnn@sari.ac.cn

    weiwei@sari.ac.cn

  • 中图分类号: O643.36

Photocatalytic oxidation of CH4 to oxygenates on Fe(III)Ox/ZnO

Funds: The project was supported by Shanghai Science and Technology Committee (19YF1452800, 19ZR1463500)
  • 摘要: 基于浸渍法制备了不同Fe含量的nFe(III)Ox/ZnO光催化剂,并对所得样品进行了XRD、N2吸附-脱附、TEM、XPS、UV-vis以及PL表征。结果发现,通过改变浸渍液中Fe物种的浓度,能够实现最终样品中Fe含量的调控,在实验涉及的范围内,Fe的负载没有造成ZnO载体在晶相、形貌和孔道结构等方面的显著变化,但却改变了催化剂表面的电子状态,从而引入了更多的O空位。此外,Fe的修饰增加了光生载流子的分离效率,显著提升了样品的CH4光催化性能。通过对溶剂体积,H2O2浓度以及反应时间等参数的优化,0.1Fe(III)Ox/ZnO样品表现出了最佳的性能,其液相氧化产物(CH3OH、CH3OOH、HCHO)的产率和选择性分别达到了5443 μmol/(gcat·h)和99%。基于自由基捕获实验,发现H2O2在光生载流子的作用下形成的${{\rm{O}}_2^-} $自由基是CH4活化为CH3的关键。
  • 图  1  ZnO和nFe(III)Ox/ZnO样品的(a)XRD谱图,(b)N2吸附-脱附等温曲线

    Figure  1  (a) XRD patterns and (b) nitrogen adsorption-desorption isotherms of ZnO and nFe(III )Ox /ZnO

    图  2  (a),(b),(c)0.1Fe(III)Ox/ZnO样品的TEM照片,(d)0.1Fe(III)Ox/ZnO样品的不同元素分布

    Figure  2  (a), (b) and (c) TEM images of 0.1Fe(III)Ox/ZnO, (d) EDS mapping images for various elements

    图  3  ZnO和nFe(III)Ox/ZnO的XPS谱图(a)Zn 2p,(b)Fe 2p,(c)O 1s

    Figure  3  XPS profiles of ZnO and nFe(III)Ox/ZnO (a) Zn 2p, (b) Fe 2p, (c) O 1s

    图  4  ZnO和0.1Fe(III)Ox/ZnO的(a)UV-vis吸收谱图,(b)PL谱图

    Figure  4  (a) Ultraviolet-visible diffusive reflectance spectra, (b) PL spectra of ZnO and 0.1Fe(III)Ox/ZnO

    图  5  ZnO和nFe(III)Ox/ZnO催化剂上的光催化CH4氧化液相产物产率及选择性

    (A)不同Fe负载量,(B)不同H2O体积,(C)不同H2O2浓度,(D)不同反应时间

    Figure  5  Product yields and selectivity by ZnO and nFe(III)Ox/ZnO with (a) different amounts of Fe, (b) varying water amount, (c) varying H2O2 amount, (d) different reaction time

    图  6  (a)加入不同自由基捕获剂的光催化CH4氧化液相产物产率及选择性,(b)反应路径

    Figure  6  (a) Product yields and selectivity over ZnO and nFe(III)Ox/ZnO with different quenchers, (b) Sketch of the proposed reaction mechanism for photocatalytic CH4 oxidation to CH3OOH, CH3OH, and HCHO on 0.1Fe(III)Ox/ZnO

    表  1  ZnO和nFe(III)Ox/ZnO催化剂的孔结构特性

    Table  1  Pore structure characteristics of ZnO and nFe(III)Ox/ZnO catalysts

    SampleFe loading w/%Surface area/(m2·g−1)
    ZnO16
    0.1Fe(III)Ox/ZnO0.0819
    0.5Fe(III)Ox/ZnO0.5015
    1.0Fe(III)Ox/ZnO0.9916
    2.0Fe(III)Ox/ZnO1.5512
    下载: 导出CSV

    表  2  不同催化剂的CH4光催化活性对比

    Table  2  Comparison of catalytic activity in oxidation of methane to liquid oxygenates

    EntryCatalystConditionProductsReference
    10.1Fe(III)Ox/ZnO5 mg catalyst, 90 mL H2O, 5 mmol/L H2O2,
    3 MPa CH4, 3 h, RT,
    300 W Xe lamp, 320−780 nm
    liquid products: CH3OOH + CH3OH + HCHO,
    total productivity: 5.44 mmol/(gcat·h)
    this work
    2q-BiVO410 mg catalyst, 10 mL H2O, 1 MPa O2,
    1 MPa CH4, RT, 7 h,
    Hg lamp, 300−400 nm
    liquid products: CH3OH + C2H5OH + HCHO,
    total productivity: 2.16 mmol/(gcat·h)
    [13]
    3Au-CoOx/TiO210 mg catalyst, 100 mL H2O, 0.1 MPa O2,
    2 MPa CH4, 2 h, 25 ℃,
    Xe lamp, 300−500 nm
    liquid product: CH3OOH + CH3OH + HCHO,
    total productivity: 2.5 mmol/(gcat·h)
    [12]
    4ZnO nanosheets4 mg catalyst, 10 mL H2O, 5 mmol/L H2O2,
    0.1 MPa CH4, 1h, 50 ℃, 300 W Xe lamp
    liquid products: CH3OOH +
    CH3OH + HOCH2OOH + HCOOH,
    total productivity: 2.21 mmol/(gcat·h)
    [23]
    下载: 导出CSV
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出版历程
  • 收稿日期:  2022-02-09
  • 录用日期:  2022-04-12
  • 修回日期:  2022-03-15
  • 网络出版日期:  2022-04-28

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