Insight into the promotional mechanism of Cu modification towards wide-temperature NH3-SCR performance of NbCe catalyst

doi:10.1016/j.cjche.2022.05.028

中国化学工程学报 ›› 2022, Vol. 50 ›› Issue (10): 301-309.DOI: 10.1016/j.cjche.2022.05.028

• Catalysis, Kinetics and Reaction Engineering • 上一篇下一篇

Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst

Dongqi An¹, Yuyao Yang², Weixin Zou³, Yandi Cai³, Qing Tong⁴, Jingfang Sun⁴, Lin Dong⁵

1 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Vehicle Emissions Control, Nanjing University, Nanjing 210093, China;
2 Center for Nanochemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China;
3 Jiangsu Key Laboratory of Vehicle Emissions Control, School of Environment, Nanjing University, Nanjing 210093, China;
4 Jiangsu Key Laboratory of Vehicle Emissions Control, Center of Modern Analysis, Nanjing University, Nanjing 210093, China;
5 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Vehicle Emissions Control, School of Environment, Center of Modern Analysis, Nanjing University, Nanjing 210093, China

收稿日期:2022-03-20 修回日期:2022-05-19 出版日期:2022-10-28 发布日期:2023-01-04
通讯作者: Jingfang Sun,E-mail:sunjf@nju.edu.cn;Lin Dong,E-mail:donglin@nju.edu.cn
基金资助:
Financial support from the National Natural Science Foundation of China, China (Nos. 21972062, 21976081, 21976111) is gratefully acknowledged.

Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst

Dongqi An¹, Yuyao Yang², Weixin Zou³, Yandi Cai³, Qing Tong⁴, Jingfang Sun⁴, Lin Dong⁵

1 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Vehicle Emissions Control, Nanjing University, Nanjing 210093, China;
2 Center for Nanochemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China;
3 Jiangsu Key Laboratory of Vehicle Emissions Control, School of Environment, Nanjing University, Nanjing 210093, China;
4 Jiangsu Key Laboratory of Vehicle Emissions Control, Center of Modern Analysis, Nanjing University, Nanjing 210093, China;
5 Key Laboratory of Mesoscopic Chemistry of MOE, School of Chemistry and Chemical Engineering and Jiangsu Key Laboratory of Vehicle Emissions Control, School of Environment, Center of Modern Analysis, Nanjing University, Nanjing 210093, China

Received:2022-03-20 Revised:2022-05-19 Online:2022-10-28 Published:2023-01-04
Contact: Jingfang Sun,E-mail:sunjf@nju.edu.cn;Lin Dong,E-mail:donglin@nju.edu.cn
Supported by:
Financial support from the National Natural Science Foundation of China, China (Nos. 21972062, 21976081, 21976111) is gratefully acknowledged.

摘要/Abstract

摘要： A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst. The best catalyst Cu_0.010/Nb₁Ce₃ presented over 90% NO conversion in a wide temperature range of 200-400 ℃ and exhibited an excellent H₂O or/and SO₂ resistance at 275 ℃. To understand the promotional mechanism of Cu modification, the correlation among the “activity-structure-property” were tried to establish systematically. Cu species highly dispersed on NbCe catalyst to serve as the active component. The strong interaction among Cu, Nb and Ce promoted the emergence of NbO₄ and induced more Brønsted acid sites. And Cu modification obviously enhanced the redox behavior of the NbCe catalyst. Besides, EPR probed the Cu species exited in the form of monomeric and dimeric Cu²⁺, the isolated Cu²⁺ acted as catalytic active sites to promote the reaction: Cu²⁺-NO₃^-+NO(g) → Cu²⁺-NO₂^-+NO₂(g). Then the generated NO₂ would accelerate the fast-SCR reaction process and thus facilitated the low-temperature deNO efficiency. Moreover, surface nitrates became unstable and easy to decompose after Cu modification, thus providing additional adsorption and activation sites for NH₃, and ensuring the improvement of catalytic activity at high temperature. Since the NH₃-SCR reaction followed by E-R reaction pathway efficaciously over Cu_0.010/Nb₁Ce₃ catalyst, the excellent H₂O and SO₂ resistance was as expected.

关键词: NH₃-SCR, NbCe catalyst, Cu modification, NO₂ promoting effect, Fast-SCR, Flue gas

Abstract: A simple strategy of Cu modification was proposed to broaden the operation temperature window for NbCe catalyst. The best catalyst Cu_0.010/Nb₁Ce₃ presented over 90% NO conversion in a wide temperature range of 200-400 ℃ and exhibited an excellent H₂O or/and SO₂ resistance at 275 ℃. To understand the promotional mechanism of Cu modification, the correlation among the “activity-structure-property” were tried to establish systematically. Cu species highly dispersed on NbCe catalyst to serve as the active component. The strong interaction among Cu, Nb and Ce promoted the emergence of NbO₄ and induced more Brønsted acid sites. And Cu modification obviously enhanced the redox behavior of the NbCe catalyst. Besides, EPR probed the Cu species exited in the form of monomeric and dimeric Cu²⁺, the isolated Cu²⁺ acted as catalytic active sites to promote the reaction: Cu²⁺-NO₃^-+NO(g) → Cu²⁺-NO₂^-+NO₂(g). Then the generated NO₂ would accelerate the fast-SCR reaction process and thus facilitated the low-temperature deNO efficiency. Moreover, surface nitrates became unstable and easy to decompose after Cu modification, thus providing additional adsorption and activation sites for NH₃, and ensuring the improvement of catalytic activity at high temperature. Since the NH₃-SCR reaction followed by E-R reaction pathway efficaciously over Cu_0.010/Nb₁Ce₃ catalyst, the excellent H₂O and SO₂ resistance was as expected.

Key words: NH₃-SCR, NbCe catalyst, Cu modification, NO₂ promoting effect, Fast-SCR, Flue gas

Dongqi An, Yuyao Yang, Weixin Zou, Yandi Cai, Qing Tong, Jingfang Sun, Lin Dong. Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst[J]. 中国化学工程学报, 2022, 50(10): 301-309.

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Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst

Insight into the promotional mechanism of Cu modification towards wide-temperature NH₃-SCR performance of NbCe catalyst

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