文献类型：期刊文献

中文题名：Insight into room-temperature catalytic oxidation of NO by CrO_2(110):A DFT study

英文题名：Insight into room-temperature catalytic oxidation of NO by CrO_2(110):A DFT study

作者：Jiamin Jin[1];Jianfu Chen[1];Haifeng Wang[1];Peijun Hu[1,2]

机构：[1]Key Laboratories for Advanced Materials, Centre for Computational Chemistry and Research Institute of Industrial Catalysis, School of Chemistry and Molecular Engineering, East China University of Science and Technology;[2]School of Chemistry and Chemical Engineering, The Queen's University of Belfast

年份：2019

卷号：30

期号：3

起止页码：618

中文期刊名：Chinese Chemical Letters

外文期刊名：中国化学快报（英文版）

收录：CSTPCD;;Scopus;CSCD:【CSCD2019_2020】；PubMed;

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)

语种：英文

中文关键词：Density;functional;theory;Chromium;dioxides;NO;oxidation;Room;temperature;Catalytic;mechanism

外文关键词：Density functional theory;Chromium dioxides;NO oxidation;Room temperature;Catalytic mechanism

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.