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负载型CuMn2O4催化剂同时去除甲苯与NOx性能及机理研究

刘旭 黄妍 赵令葵 李思密 陶泓帆 饶思敏 朱洪

刘旭, 黄妍, 赵令葵, 李思密, 陶泓帆, 饶思敏, 朱洪. 负载型CuMn2O4催化剂同时去除甲苯与NOx性能及机理研究[J]. 燃料化学学报(中英文), 2023, 51(12): 1856-1865. doi: 10.19906/j.cnki.JFCT.2023024
引用本文: 刘旭, 黄妍, 赵令葵, 李思密, 陶泓帆, 饶思敏, 朱洪. 负载型CuMn2O4催化剂同时去除甲苯与NOx性能及机理研究[J]. 燃料化学学报(中英文), 2023, 51(12): 1856-1865. doi: 10.19906/j.cnki.JFCT.2023024
LIU Xu, HUANG Yan, ZHAO Ling-kui, LI Si-mi, TAO Hong-fan, RAO Si-min, ZHU Hong. Study on performance and mechanism of CuMn2O4 supported catalyst for simultaneous removal of toluene and NOx[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1856-1865. doi: 10.19906/j.cnki.JFCT.2023024
Citation: LIU Xu, HUANG Yan, ZHAO Ling-kui, LI Si-mi, TAO Hong-fan, RAO Si-min, ZHU Hong. Study on performance and mechanism of CuMn2O4 supported catalyst for simultaneous removal of toluene and NOx[J]. Journal of Fuel Chemistry and Technology, 2023, 51(12): 1856-1865. doi: 10.19906/j.cnki.JFCT.2023024

负载型CuMn2O4催化剂同时去除甲苯与NOx性能及机理研究

doi: 10.19906/j.cnki.JFCT.2023024
基金项目: 湖南省教育厅科研项目(22A0129)和国家自然科学基金(52270107)资助
详细信息
    通讯作者:

    E-mail: xtuhy@163.com

  • 中图分类号: X701

Study on performance and mechanism of CuMn2O4 supported catalyst for simultaneous removal of toluene and NOx

Funds: The project was supported by Hunan Provincial Department of Education funded research projects (22A0129), Supported by the National Natural Science Foundation of China (52270107)
  • 摘要: 本研究使用低温溶胶凝胶自燃法制备了不同载体负载的CuMn2O4/MO2 (M=Mn、Ti、Ce)催化剂,并对其同时去除甲苯和NOx的性能进行了评价。结果表明,CeO2载体的加入可显著缓解CuMn2O4上甲苯氧化与NH3-SCR的相互抑制,因此,CuMn2O4/CeO2催化剂表现出最优异的甲苯与NOx同时去除效率。通过BET、XRD、NH3-TPD、O2-TPD及结合XPS与in-situ DRIFTs对催化剂的物化性质及CuMn2O4同时去除甲苯与NOx的反应机理进行了分析。结果表明,CeO2的引入提高了催化剂中Mn4 + /Mnn + 的占比,促使CuMn2O4/CeO2催化剂形成表面丰富的酸性位点和氧空位。此外,Cu、Mn和Ce之间的强相互作用加速电子转移,增强了Cu + + Ce4 + ↔Cu2 + + Ce3 + 、Mn4 + + Ce3 + ↔Mn3 + + Ce4 + 的氧化还原循环。In-situ DRIFTs证实了CuMn2O4催化剂上NH3-SCR反应遵循Langmuir-Hinshelwood机制,甲苯的氧化遵循Mars-van Krevelen机制。因此,CeO2作为载体的CuMn2O4/CeO2催化剂优异的氧化还原能力促使甲苯的完全氧化,表现出优异的甲苯与NOx同时去除能力。本工作可为同时消除甲苯和NOx的催化剂开发提供指导。
  • FIG. 2812.  FIG. 2812.

    FIG. 2812.  FIG. 2812.

    图  1  实验装置示意图

    Figure  1  Schematic diagram of experimental apparatus

    图  2  CuMn2O4/MO2(M=Mn、Ce、Ti)催化剂NH3-SCR还原NO(a), 单独氧化甲苯(b)

    Figure  2  CuMn2O4/MO2 (M=Mn, Ce, Ti) catalyst NH3-SCR reduction of NO (a), alone oxidized toluene (b)

    图  3  CuMn2O4/MO2(M=Mn、Ce、Ti)催化剂协同处理NO(a), 协同处理甲苯(b)

    Figure  3  CuMn2O4/MO2 (M=Mn, Ce, Ti) catalyst synergistic treatment of NO (a), synergistic treatment of toluene (b)

    图  4  CuMn2O4/CeO2的稳定性测试

    Figure  4  Stability test of CuMn2O4/CeO2

    图  5  催化剂吸附等温线

    Figure  5  Catalyst adsorption isotherms

    图  6  负载前后尖晶石的XRD谱图

    Figure  6  Spinel XRD before and after loading

    图  7  不同载体负载尖晶石催化剂的NH3-TPD谱图

    Figure  7  NH3-TPD spectra of spinel catalysts supported by different carriers

    图  8  不同载体负载尖晶石催化剂的O2-TPD谱图

    Figure  8  O2-TPD spectra of spinel catalysts supported by different carriers

    图  9  不同载体催化剂的XPS谱图

    Figure  9  XPS spectra of different supported catalysts

    图  10  CuMn2O4在300 ℃吸附时间原位光谱研究

    Figure  10  In-situ spectroscopic study of CuMn2O4 adsorption time at 300 ℃ (a): Adsorption of toluene and NO after toluene adsorption; (b): Toluene is oxidized into toluene; (c): Toluene is oxidized into NH3-SCR

    图  11  甲苯与NO的同时去除示意图

    Figure  11  Diagram of simultaneous removal of toluene and NO

    表  1  催化剂的比表面积以及孔容孔径

    Table  1  Catalyst specific surface area

    SpeciesSurface area
    /(m2·g−1
    Pore volume
    /(cm3·g−1
    Mean pore
    size /nm
    CuMn2O41.610.002495.99
    CuMn2O4/MnO218.520.041657.89
    CuMn2O4/TiO219.240.047598.32
    CuMn2O4/CeO223.760.052478.84
    下载: 导出CSV

    表  2  催化剂的XPS表面元素比值

    Table  2  XPS of surface element ratio

    SpeciesO Atomic/% Binding energy/eV Cu + /Cu2 + Mn4 + /Mn3 + Atomic /%
    OadsOlattOads/OlatOadsOlatCuMnOM
    CuMn2O452.5447.461.10 531.7530.1 0.57 0.47 7.1626.2966.55
    CuMn2O4/MnO247.8552.150.91531.8530.40.820.506.0126.8167.17
    CuMn2O4/TiO242.2057.800.73532.4530.90.220.226.5623.0665.245.14
    CuMn2O4/CeO235.1164.890.54531.0529.60.280.785.5123.6665.755.08
    下载: 导出CSV
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  • 收稿日期:  2023-03-08
  • 修回日期:  2023-03-22
  • 录用日期:  2023-03-24
  • 网络出版日期:  2023-04-06
  • 刊出日期:  2023-12-05

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