负载型CuMn2O4催化剂同时去除甲苯与NOx性能及机理研究

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

  • 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。

     

    Abstract: In this study, CuMn2O4/MO2 (M=Mn, Ti, Ce) catalysts with different support loads were prepared by sol-gel spontaneous combustion at low temperature, and the removal performance of toluene and NOx was evaluated. The results showed that the addition of CeO2 carrier could significantly alleviate the mutual inhibition of toluene oxidation and NH3-SCR over CuMn2O4. Therefore, CuMn2O4/CeO2 catalyst showed the best removal efficiency of toluene and NOx simultaneously. The physicochemical properties of the catalyst and the reaction mechanism of CuMn2O4 were analyzed by BET, XRD, NH3-TPD, O2-TPD and combined XPS and in-situ DRIFTs. The results showed that the introduction of CeO2 increased the proportion of Mn4 + /Mnn + in the catalyst, and promoted the formation of rich acid sites and oxygen vacancies on the surface of CuMn2O4/CeO2 catalyst. In addition, the strong interaction between Cu, Mn and Ce accelerated electron transfer and enhance the redox cycle for Cu + + Ce4 + ↔Cu2 + + Ce3 + 、Mn4 + + Ce3 + ↔Mn3 + + Ce4 + . It has been confirmed by in-situ DRIFTs that NH3-SCR reaction on CuMn2O4 catalyst follows Langmuir-Hinshelwood mechanism and oxidation of toluene follows Mars-van Krevelen mechanism. Therefore, CuMn2O4/CeO2 catalyst with CeO2 as the support has excellent reoxidation ability to promote the complete oxidation of toluene, so it shows excellent removal ability of toluene and NOx simultaneously. This work can provide guidance for the development of catalysts for simultaneous removal of toluene and NOx.

     

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