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基于Cu基催化剂的低温NH3-SCR脱硝机制

Denitrification mechanism of low temperature NH3-SCR based on Cu-based catalysts

  • 摘要: Cu-菱沸石(Cu-CHA)内的NH3-溶剂化Cu位点的动态运动是连接异质催化和均质催化的独特现象,也是柴油机尾气后处理中氨辅助选择性催化还原氮氧化物(NH3-SCR)技术最有前途和最先进的催化剂。首先总结了低温铜动力学理论认知的最新进展,重点列举分子动力学(AIMD)或动力学模拟所提供的笼内和笼间铜原子运动的证据。随后展示同步辐射X射线光谱学,包括振动光谱和光学光谱学(漫反射红外傅立叶变换光谱学(DRIFTS)和漫反射紫外可见光谱学(DRS)、电子顺磁谱学(EPR)、阻抗光谱学(IS)等方法的互补耦合,用以跟踪低温NH3-SCR过程中Cu配位环境和局部结构的演变。进一步阐述铜动力学在调控低温铜的氧化还原性能、固态离子交换方法制备高分散Cu-CHA催化剂及直接监测NH3储存和转化中的重要作用。简要讨论利用铜动力学提升低温NH3-SCR效率的新视角,并延伸讨论其对金属离子交换沸石催化的其他重要反应。

     

    Abstract: The dynamic movement of the NH3-solvated Cu site in Cu-CHA zeolite is a unique phenomenon connecting heterogeneous catalysis and homogeneous catalysis,and is the most promising and advanced catalyst for ammonium-assisted selective reduction of nitrogen oxides(NH3-SCR) technology in diesel exhaust post-treatment. Firstly,recent theoretical advances in low-temperature copper dynamics were summarized,and the evidence for the movement of copper atoms in and between cages resulting from molecular dynamics(AIMD) or kinetic simulations was highlighted. Synchrotron X-ray spectroscopy,vibrational and optical techniques,including diffuse infrared Fourier Transform spectroscopy(DRIFTS) and diffuse ultraviolet-visible spectroscopy(DRS),electron paramagnetic spectroscopy(EPR) and impedance spectroscopy(IS)were combined to track evolution of Cu coordination and local structure during low-temperature NH3-SCR. The role of copper dynamics in tuning redox properties,preparing highly dispersed Cu-CHA via solid-state ion exchange and in situ monitoring of NH3 storage and conversion was elucidated. Mechanistic insights provide new strategies for enhancing low-temperature NH3-SCR efficiency and extend to other metal-exchanged-zeolite reactions.

     

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