An unexpected reversal: The smart performance of hydrogen chloride on SbCe catalysts for NH3-SCR reaction

doi:10.1016/S1872-2067(24)60155-5

Abstract

Abstract:

Understanding the influence of HCl on the NH₃-selective catalytic reduction reaction mechanism is crucial for designing highly efficient denitrification catalysts. The formation of chlorate species on the surface of the synthesized SbCeO_x catalyst, induced by HCl, significantly enhances low-temperature activity, as evidenced by a 30% increase in NO conversion at 155 °C. Furthermore, it improves N₂ selectivity at high temperatures, with a notable 17% increase observed at 405 °C. Both experimental results and density functional theory calculations confirm that chlorate species form at Ce sites. This formation facilitates the creation of oxygen vacancies, boosting the oxygen exchange capacity. It also increases NH₃ adsorption at the Ce sites, promotes the formation of Sb-OH, and reduces competitive OH adsorption on these sites. Notably, compared with the reaction mechanism without HCl, the presence of chlorate species enhances NH₃ adsorption and activation, which is vital for subsequent catalytic reactions.

Key words: NH₃-selective catalytic reduction, Chlorate species, SbCeO_x catalyst, Density functional theory, HCl

Caixia Liu, Chaojun Huang, Baiyu Fan, Yan Zhang, Lijing Fang, Yuhe Wang, Qingling Liu, Weichao Wang, Yanguo Chen, Yawei Zhang, Jiancheng Liu, Fang Dong, Ziyin Zhang. An unexpected reversal: The smart performance of hydrogen chloride on SbCe catalysts for NH₃-SCR reaction[J]. Chinese Journal of Catalysis, 2025, 68: 376-385.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60155-5

https://www.cjcatal.com/EN/Y2025/V68/I1/376

Figures/Tables 9

Fig. 1. SCR performance of the SbCe catalyst before and after HCl treatment. SCR activity (a) and N2 selectivity (b) of catalysts with different Sb:Ce ratios. SCR activity (c) and N2 selectivity (d) of Sb:Ce = 1.3:1 catalyst after HCl treatment.

Fig. 2. (a) XRD patterns of the SbCe catalyst at three distinct temperatures(180, 280, and 380 °C) before and after HCl treatment. (b) SbCe-280 element mappings. SbCe-ori (c-e) and SbCe-280 (f-h) TEM pictures.

Table 1 The porosity results of SbCe catalysts with or without HCl treatment.

Sample	BET specific surface area (m²/g)	Pore volume (cm³/g)	Average pore size (nm)
SbCe-ori	49.8	0.05	5.10
SbCe-180	55.6	0.07	4.92
SbCe-280	51.4	0.05	4.11
SbCe-380	52.2	0.09	6.33

Fig. 3. XPS spectrum of SbCe catalyst before and after HCl treatment at different temperatures: Cl 2p (a), O 1s (b), Ce 3d (c), and Sb 3d (d).

Fig. 4. NH3-TPD profiles (a) and H2-TPR profiles (b) of the SbCe catalyst before and after HCl treatment at different temperatures.

Fig. 5. DRIFTS experimental results of the NH3-SCR reaction at different temperatures for SbCe-ori and SbCe-280 catalysts. (a) SbCe-ori catalyst. (b) SbCe-280 catalyst. Reaction gas flow rate: 100 mL/min; Reaction conditions: [NO] = [NH3] = 500 ppm, [O2] = 10%, N2 balance. GHSV: 60000 h-1.

Fig. 6. The optimized configurations of CeO2 and SbCe catalysts and the PDOS diagram of O 2p orbitals. (a) Optimized model structure of the CeO2 catalyst. (b) Optimized model structure of the SbCe catalyst. (c) Structure of CeO2 catalyst after forming oxygen vacancies. (d) Structure of the SbCe catalyst after forming oxygen vacancies. (e) Structure of the SbCe catalyst after adsorbing HCl. (f) Structure of the SbCe catalyst with oxygen vacancies formed after HCl adsorption. (g) Structure of the SbCe catalyst after adsorbing ClO3-. (h) Structure of the SbCe catalysts with oxygen vacancies formed after ClO?- adsorption. (i) PDOS diagram of O 2p orbitals.

Fig. 7. Adsorption configuration of NH3 and OH on the SbCe catalyst. (a) Structure of the SbCe catalyst adsorbing NH3 at the Ce site. (b) Structure of the SbCe catalyst adsorbing NH3 at the Sb site. (c) Structure of the SbCe-ClO3 catalyst adsorbing NH3 at Ce site. (d) Structure of the SbCe-ClO3 catalyst adsorbing NH? at the Sb site. (e) Structure of the SbCe catalyst adsorbing OH at the Ce site. (f) Structure of the SbCe catalyst adsorbing OH at the Sb site. (g) Structure of the SbCe-ClO3 catalyst adsorbing OH at the Ce site. (h) Structure of the SbCe-ClO3 catalyst of adsorbing OH at the Sb site.

Scheme 1. Schematic illustration of activity and selectivity promoted over the SbCe catalyst.

References

[1]	N. R. Jaegers, J. K. Lai, Y. He, E. Walter, D. A. Dixon, M. Vasiliu, Y. Chen, C. Wang, M. Y. Hu, K. T. Mueller, I. E. Wachs, Y. Wang, J. Z. Hu, Angew. Chem. Int. Ed., 2019, 58, 12609-12616.
[2]	F. Göltl, P. Sautet, I. Hermans, Angew. Chem. Int. Ed., 2015, 54, 7799-7804.
[3]	X. Mou, B. Zhang, Y. Li, L. Yao, X. Wei, D. S. Su, W. Shen, Angew. Chem. Int. Ed., 2012, 51, 2989-2993.
[4]	P. G. Smirniotis, D. A. Peña, B. S. Uphade, Angew. Chem. Int. Ed., 2001, 40, 2479-2482.
[5]	P. Forzatti, I. Nova, E. Tronconi, Angew. Chem. Int. Ed., 2009, 48, 8366-8368.
[6]	Y. Jiang, M. Lu, S. Liu, C. Bao, G. Liang, C. Lai, W. Shi, S. Ma, RSC Adv., 2018, 8, 17677-17684.
[7]	N. Yang, R. Guo, W. Pan, Q. Chen, Q. Wang, C. Lu, S. Wang, Appl. Surf. Sci., 2016, 378, 513-518.
[8]	A. Lanza, L. Zheng, R. Matarrese, L. Lietti, J. D. Grunwaldt, S. A. Clave, J. Collier, A. Beretta, Chem. Eng. J., 2021, 416, 128933.
[9]	H. Chang, J. Li, W. Su, Y. Shao, J. Hao, Chem. Commun., 2014, 50, 10031-10034.
[10]	L. Lisi, G. Lasorella, S. Malloggi, G. Russo, Appl. Catal. B, 2004, 50, 251-258.
[11]	Q. Wang, F. Lin, J. Zhou, J. Zhang, J. Jin, Appl. Catal. A, 2020, 605, 117801.
[12]	F. Gao, X. Tang, H. Yi, S. Zhao, J. Wang, T. Gu, Appl. Surf. Sci., 2019, 466, 411-424.
[13]	S. Martins, J. B. Fernandes, S. C. Mojumdar, J. Therm. Anal. Calori., 2015, 119, 831-835.
[14]	J. Liu, G. Li, Y. Zhang, X. Liu, Y. Wang, Y. Li, Appl. Surf. Sci., 2017, 401, 7-16.
[15]	Y. Hao, Y. Wang, T. Zhang, Y. Liu, Q. Y. Fan, Y. Jiang, Y. Gao, Z. Mao, X. Gu, S. Zeng, Appl. Catal. B, 2024, 340, 123254.
[16]	X. Jia, H. Liu, Y. Zhang, W. Chen, Q. Tong, G. Piao, C. Sun, L. Dong, J. Colloid Interface Sci., 2021, 581, 427-441.
[17]	H. Xu, Y. Wang, Y. Cao, Z. Fang, T. Lin, M. Gong, Y. Chen, Chem. Eng. J., 2014, 240, 62-73.
[18]	L. He, Y. Zhang, Y. Zang, C. Liu, W. Wang, R. Han, N. Ji, S. Zhang, Q. Liu, ACS Catal., 2021, 11, 14224-14236.
[19]	X. Liu, K. Zhou, L. Wang, B. Wang, Y. Li, J. Am. Chem. Soc., 2009, 131, 3140-3141.
[20]	M. S. Maqbool, A. K. Pullur, H. P. Ha, Appl. Catal. B, 2014, 152-153, 28-37.
[21]	H. Wang, Z. Qu, H. Xie, N. Maeda, L. Miao, Z. Wang, J. Catal., 2016, 338, 56-67.
[22]	Z. Hao, Z. Shen, Y. Li, H. Wang, L. Zheng, R. Wang, G. Liu, S. Zhan, Angew. Chem. Int. Ed., 2019, 58, 6351-6356.
[23]	R. Guo, X. Sun, J. Liu, W. Pan, M. Li, S. Liu, P. Sun, S. Liu,, Appl. Catal. A, 2018, 558, 1-8.
[24]	C. Xu, J. Liu, Z. Zhao, F. Yu, K. Cheng, Y. Wei, A. Duan, G. Jiang, J. Environ. Sci., 2015, 31, 74-80.
[25]	A. Marberger, D. Ferri, M. Elsener, O. Kröcher, Angew. Chem. Int. Ed., 2016, 55, 11989-11994.
[26]	Z. Wang, R. Guo, X. Shi, W. Pan, J. Liu, X. Sun, S. Liu, X. Liu, H. Qin, Appl. Surf. Sci., 2019, 475, 334-341.
[27]	Z. Wang, X. Li, R. Shi, React. Kinet. Mech. Catal., 2019, 127, 437-447.
[28]	H. Chitsazi, N. Zhang, L. Li, X. Liu, R. Wu, J. He, L. Song, H. He, J. Rare Earths, 2021, 39, 526-531.
[29]	X. Zhao, S. Ma, Z. Li, F. Yuan, X. Niu, Y. Zhu, Chem. Eng. J., 2020, 392, 123801.

An unexpected reversal: The smart performance of hydrogen chloride on SbCe catalysts for NH₃-SCR reaction

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