摘要
The NO oxidation processes on CrO_2(110) was investigated by virtue of DFT + U calculation together with microkinetic analysis, aiming to uncover the reaction mechanism and activity-limiting factors for CrO_2 catalyst. It was found that NO oxidation on CrO_2(110) has to be triggered with the lattice Obri involved(Mars-van Krevelen mechanism) rather than the Langmuir-Hinshelwood path occurring at the Cr_(5 c) sites alone. Specifically, the optimal reaction path was identified. Quantitatively, the microkinetic analysis showed that CrO_2(110) can exhibit a high turnover rate of 0.978 s^(-1) for NO oxidation at room temperature.Such an activity could originate from the bifunctional synergetic catalytic mechanism, in which the Cr_(5c)sites can exclusively adsorb NO and the Obri is very reactive and provides oxidative species. However, it is worth noting that, as the reactive Obri tightly binds NO_2, the nitrate species was found to be difficult removed and constituted the key poisoning species, eventually limiting the overall activity of CrO_2. This work demonstrated the considerable catalytic ability of CrO_2 for NO oxidation at room temperature, and the understanding may facilitate the further design of more active Cr-based catalyst.
The NO oxidation processes on CrO_2(110) was investigated by virtue of DFT + U calculation together with microkinetic analysis, aiming to uncover the reaction mechanism and activity-limiting factors for CrO_2 catalyst. It was found that NO oxidation on CrO_2(110) has to be triggered with the lattice Obri involved(Mars-van Krevelen mechanism) rather than the Langmuir-Hinshelwood path occurring at the Cr_(5 c) sites alone. Specifically, the optimal reaction path was identified. Quantitatively, the microkinetic analysis showed that CrO_2(110) can exhibit a high turnover rate of 0.978 s^(-1) for NO oxidation at room temperature.Such an activity could originate from the bifunctional synergetic catalytic mechanism, in which the Cr_(5c)sites can exclusively adsorb NO and the Obri is very reactive and provides oxidative species. However, it is worth noting that, as the reactive Obri tightly binds NO_2, the nitrate species was found to be difficult removed and constituted the key poisoning species, eventually limiting the overall activity of CrO_2. This work demonstrated the considerable catalytic ability of CrO_2 for NO oxidation at room temperature, and the understanding may facilitate the further design of more active Cr-based catalyst.
基金
supported by the National Natural Science Foundation of China(NSFC,Nos.21333003,21622305)
National Ten Thousand Talent Program for Young Top-notch Talents in China
The Shanghai Shuguang Scholar Program(No.17SG30)
