State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, PR China.
State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, PR China.
J Hazard Mater. 2016 Nov 15;318:615-622. doi: 10.1016/j.jhazmat.2016.07.058. Epub 2016 Jul 25.
Arsenic resistance on MoO3 doped CeO2/TiO2 catalysts for selective catalytic reduction of NOx with NH3 (NH3-SCR) is investigated. It is found that the activity loss of CeO2-MoO3/TiO2 caused by As oxide is obvious less than that of CeO2/TiO2 catalysts. The fresh and poisoned catalysts are compared and analyzed using XRD, Raman, XPS, H2-TPR and in situ DRIFTS. The results manifest that the introduction of arsenic oxide to CeO2/TiO2 catalyst not only weakens BET surface area, surface acid sites and adsorbed NOx species, but also destroy the redox circle of Ce(4+) to Ce(3+) because of interaction between Ce and As. When MoO3 is added into CeO2/TiO2 system, the main SCR reaction path are found to be changed from the reaction between coordinated NH3 and ad-NOx species to that between an amide and gaseous NO. Additionally, for CeO2-MoO3/TiO2 catalyst, As toxic effect on active sites CeO2 can be released because of stronger As-Mo interaction. Moreover, not only are the reactable Brønsted and Lewis acid sites partly restored, but the cycle of Ce(4+) to Ce(3+) can also be free to some extent.
研究了 MoO3 掺杂的 CeO2/TiO2 催化剂上的砷抗药性在 NH3(NH3-SCR)选择性催化还原 NOx 中的作用。结果发现,CeO2-MoO3/TiO2 催化剂上氧化砷引起的活性损失明显小于 CeO2/TiO2 催化剂。通过 XRD、Raman、XPS、H2-TPR 和原位 DRIFTS 对新鲜和中毒催化剂进行了比较和分析。结果表明,砷氧化物的引入不仅削弱了 CeO2/TiO2 催化剂的 BET 表面积、表面酸位和吸附的 NOx 物种,还由于 Ce 和 As 之间的相互作用破坏了 Ce(4+)到 Ce(3+)的氧化还原循环。当 MoO3 被引入 CeO2/TiO2 体系时,主要的 SCR 反应途径被发现从配位 NH3 和吸附的 NOx 物种之间的反应转变为酰胺和气相 NO 之间的反应。此外,对于 CeO2-MoO3/TiO2 催化剂,由于较强的 As-Mo 相互作用,CeO2 上的砷毒性可以得到释放。此外,不仅部分恢复了可反应的 Brønsted 和 Lewis 酸位,而且 Ce(4+)到 Ce(3+)的循环也可以在一定程度上自由进行。