Ce/Cu掺杂Fe-ZSM-5催化剂NH_(3)选择性催化还原NO_(x)的活性位点演化机理

Evolution mechanism of active sites for selective catalytic reduction of NO_(x) with NH_(3) over Fe-ZSM-5 catalysts doped by Ce/Cu

通过水溶液离子交换法和初湿浸渍法制备Cu和Ce改性的Fe-ZSM-5催化剂,研究其在NH_(3)选择性催化还原NO_(x)中的作用。通过表征技术(NH_(3)-SCO,BET,XRD,XPS,UV-Vis,NH_(3)-TPD,H_(2)-TPR)探讨了催化剂活性位、酸性位和孔结构的变化,发现活性Cu物种和Fe物种的分散情况是影响整个催化过程中催化活性的重要因素。Fe-ZSM-5催化剂中Cu的掺杂带来了新的活性物种,孤立Cu离子和CuO颗粒,从而改善了低温催化活性。然而,催化剂的氨氧化作用也随之加强,催化剂中的部分Fe^(3+)活性位和Brønsted酸性位被Cu物种取代,这导致了高温活性的降低。进一步掺杂Ce后,高温活性得到恢复,可以归因于Ce促进了活性Cu物种和Fe物种的高度分散。这些发现为多金属掺杂调节铁基SCR催化剂的活性窗口提供了理论支持。

Fe-ZSM-5 catalysts modified by Cu and Ce by aqueous solution ion-exchange and incipient wetness impregnation methods were tested in the selective catalytic reduction of NO_(x) with NH_(3).A variety of characterization techniques(NH_(3)-SCO,BET,XRD,XPS,UV-Vis,NH_(3)-TPD,H_(2)-TPR)were used to explore the changes of the active sites,acid sites and pore structure of the catalyst.It was found that the dispersion of active Cu species and Fe species had great influences on the catalytic activity in the whole catalytic process.The Cu doping into the Fe-ZSM-5 catalyst produced new active species,isolated Cu ions and CuO particles,resulting in the improved low-temperature catalytic activity.However,the NH_(3) oxidation was enhanced,and part of the Fe^(3+)active sites and more Brønsted acidic sites in the catalyst were occupied by Cu species,which causes the decrease of the high-temperature activity.The recovery of hightemperature activity could be attributed to the recovery of active Cu species and Fe species promoted by Ce and the promotion of active species dispersion.The results provide theoretical support for adjusting the active window of Febased SCR catalyst by multi-metal doping.