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Sr掺杂羟基磷灰石负载Co3O4催化N2O分解

刘晓丽 王永钊 赵永祥

刘晓丽, 王永钊, 赵永祥. Sr掺杂羟基磷灰石负载Co3O4催化N2O分解[J]. 燃料化学学报(中英文), 2021, 49(8): 1190-1200. doi: 10.19906/j.cnki.JFCT.2021047
引用本文: 刘晓丽, 王永钊, 赵永祥. Sr掺杂羟基磷灰石负载Co3O4催化N2O分解[J]. 燃料化学学报(中英文), 2021, 49(8): 1190-1200. doi: 10.19906/j.cnki.JFCT.2021047
LIU Xiao-li, WANG Yong-zhao, ZHAO Yong-xiang. Co3O4 supported on Sr doped hydroxyapatite as catalysts for N2O catalytic decomposition[J]. Journal of Fuel Chemistry and Technology, 2021, 49(8): 1190-1200. doi: 10.19906/j.cnki.JFCT.2021047
Citation: LIU Xiao-li, WANG Yong-zhao, ZHAO Yong-xiang. Co3O4 supported on Sr doped hydroxyapatite as catalysts for N2O catalytic decomposition[J]. Journal of Fuel Chemistry and Technology, 2021, 49(8): 1190-1200. doi: 10.19906/j.cnki.JFCT.2021047

Sr掺杂羟基磷灰石负载Co3O4催化N2O分解

doi: 10.19906/j.cnki.JFCT.2021047
基金项目: 国家自然科学基金(U1710221)和山西省自然科学基金(201801D121043)资助
详细信息
    通讯作者:

    E-mail:catalyst@sxu.edu.cn. Tel:0351-7010588

  • 中图分类号: O643

Co3O4 supported on Sr doped hydroxyapatite as catalysts for N2O catalytic decomposition

Funds: The project was supported by the National Natural Science Foundation of China (U1710221) and Natural Science Foundation of Shanxi Province (201801D121043)
  • 摘要: 通过共沉淀法合成了羟基磷灰石(HAP)和一系列Sr掺杂羟基磷灰石载体(Ca9Sr1、Ca8Sr2和Ca7Sr3),以浸渍法制备负载型Co3O4催化剂。采用XRD、N2-physisorption、Raman、FT-IR、H2-TPR、XPS、O2-TPD和CO2-TPD对所制备的样品进行表征,使用连续流动微反应装置研究了其N2O分解性能。实验结果表明,催化活性顺序为Co/Ca8Sr2 > Co/Ca9Sr1 > Co/HAP > Co/Ca7Sr3。当Sr/Ca比为1∶9和2∶8时较好地保持了HAP载体的结构,适量Sr的掺杂不仅促进了Co3O4分散,增加了催化剂中Co2+和表面氧空位的数量,同时提高了催化剂的表面碱量和碱性位密度,从而更加有利于N2O活化和O2脱附。
  • FIG. 846.  FIG. 846.

    FIG. 846.  FIG. 846.

    图  1  载体(a)和催化剂(b)的XRD谱图

    Figure  1  XRD patterns of supports (a) and catalysts (b)

    图  2  载体(a)和催化剂(b)的N2物理吸附-脱附曲线和孔径分布

    Figure  2  N2-physisorption isotherms and pore size distribution of supports (a) and catalysts (b)

    图  3  催化剂的拉曼光谱谱图

    Figure  3  Raman spectra of catalysts

    图  4  载体和催化剂的红外光谱谱图

    Figure  4  FT-IR spectra of supports and catalysts

    图  5  载体和催化剂的TEM照片

    Figure  5  TEM images of supports and catalysts

    图  6  催化剂的XPS谱图

    Figure  6  XPS spectra of catalysts

    图  7  载体和催化剂的H2-TPR谱图

    Figure  7  H2-TPR profiles of supports and catalysts

    图  8  催化剂的O2-TPD谱图

    Figure  8  O2-TPD profiles of catalysts

    图  9  催化剂的CO2-TPD谱图

    Figure  9  CO2-TPD profiles of catalysts

    图  10  载体和催化剂的N2O催化分解性能

    Figure  10  N2O conversion over the supports and catalysts

    feed gas: 1× 10−3 N2O/Ar, GHSV = 10000 h−1

    表  1  载体和催化剂的织构性质以及Co3O4的晶体尺寸

    Table  1  Textural properties of the supports and catalysts as well as crystal size of Co3O4

    SampleBET
    surface
    area/
    (m2·g−1)
    Total
    pore
    volume/
    (cm3·g−1)
    Average
    pore
    diameter/
    nm
    Crystal
    size of
    Co3O4/nm
    HAP440.2018
    Ca9Sr1330.1012
    Ca8Sr2270.1116
    Ca7Sr370.0213
    Co/HAP340.182219.6
    Co/Ca9Sr1220.091616.9
    Co/Ca8Sr2260.101614.7
    Co/Ca7Sr350.021219.8
    下载: 导出CSV

    表  2  催化剂的XPS表征

    Table  2  XPS results of catalysts

    CatalystBinding energy/eV
    Co3+Co2+Ex Co2+satelliteCo2+/Co3+Oα1Oα2Oα3Oα2/(Oα1+Oα2+Oα3)
    Co/HAP779.5782.4781.1787.61.25530.4531.4532.90.31
    Co/Ca9Sr1779.4782.4781.1787.21.40530.4531.2532.50.34
    Co/Ca8Sr2779.3782.4781.1787.21.69530.3531.1532.40.45
    Co/Ca7Sr3779.7782.4781.2787.20.96530.3531.4532.30.28
    下载: 导出CSV

    表  3  催化剂的H2-TPR表征

    Table  3  H2-TPR results of catalysts

    CatalystPeak temperature/℃H2 uptake/(μmol·g−1)
    Co3+
    1)
    Co2+
    2)
    Ex Co2+
    (β)
    Co3+
    1)
    Co2+
    2)
    Ex Co2+
    (β)
    Co/HAP33644261783.5227.098.1
    Co/Ca9Sr135541863462.4186.699.0
    Co/Ca8Sr233345063280.0232.3106.2
    Co/Ca7Sr335630057719.080.09.1
    下载: 导出CSV

    表  4  催化剂表面上不同碱性位点的数量和碱性位点密度

    Table  4  Amount of different basic sites and basic site density on the catalyst surface

    SampleWeak basic
    sites/(μmol·g−1)
    Strong basic
    sites/(μmol·g−1)
    Basic site density
    /(μmol·m−2)
    Co/HAP122.110.90.39
    Co/Ca9Sr185.47.00.42
    Co/Ca8Sr2131.09.20.54
    Co/Ca7Sr313.21.10.29
    下载: 导出CSV
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  • 收稿日期:  2021-01-22
  • 修回日期:  2021-02-20
  • 网络出版日期:  2021-03-16
  • 刊出日期:  2021-08-31

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