CeO2 Modified Mn-Fe-O Composites and their Catalytic Performance for NH3-SCR of NO

doi:10.15541/jim20190266

Abstract

Abstract:

The ammonia selective catalytic reduction (NH₃-SCR) technology is still necessary to further develop denitration catalytic materials which have good catalytic activity, high stability and environmental friendliness at relatively low temperature (<300 ℃). In this work, the Mn-Fe-O catalyst was prepared by oxalate co-precipitation method and modified with different contents of CeO₂ for low temperature NH₃-SCR of NO. The catalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption, X-ray photoelectron spectroscopy (XPS), temperature programmed reduction or desorption (H₂-TPR, NH₃-TPD). The catalytic results show that as compared with pure Mn-Fe-O sample, Mn-Fe-O modified with suitable CeO₂ content shows much better performance for NH₃-SCR with 95% conversion of NO and a high N₂ selectivity at 80 ℃ under the same reaction conditions. CeO₂ modification increases the content of Fe ³⁺, Mn ³⁺ and Mn ⁴⁺, and the number of surface acid sites on the surface of Mn-Fe-O oxide, which contribute to the adsorption of NH₃ and the catalytic reaction. In addition, redox reactions among Fe ²⁺/Fe ³⁺, Mn ²⁺/Mn ³⁺/Mn ⁴⁺ and Ce ³⁺/Ce ⁴⁺ pairs improve the redox ability and stability of the catalyst.

Key words: ceria, modification, Fe-Mn oxide, NO removal

CLC Number:

TB34

HUANG Xiubing, WANG Peng, TAO Jinzhang, XI Zuoshuai. CeO₂ Modified Mn-Fe-O Composites and their Catalytic Performance for NH₃-SCR of NO[J]. Journal of Inorganic Materials, 2020, 35(5): 573-580.

Figures/Tables 10

Fig. 1 XRD patterns of the composites

Fig. 2 SEM images of Ce(x)/Mn-Fe-O

Fig. 3 N2 adsorption-desorption curves of catalysts

Table 1 Structure properties of Ce(x)/Mn-Fe-O

Sample	Surface area /(m²·g^-1)	Pore volume /(cm³·g^-1)	Average pore size/nm
Mn-Fe-O	148.08	0.302	8.92
Ce(0.01)/Mn-Fe-O	145.42	0.290	7.82
Ce(0.05)/Mn-Fe-O	142.39	0.265	7.45
Ce(0.1)/Mn-Fe-O	142.31	0.262	7.36
Ce(0.3)/Mn-Fe-O	142.71	0.255	7.14

Fig. 4 Raman spectra of samples Mn-Fe-O and Ce(0.1)/Mn-Fe-O

Fig. 5 XPS spectra of samples Mn-Fe-O and Ce(0.1)/Mn-Fe-O (a) Full spectrum; (b) Ce3d; (c) Mn2p; (d) Fe2p

Table 2 Surface atomic content of Ce(x)/Mn-Fe-O composites

Sample	Ce : Mn : Fe molar ratio	Surface atomic content/%
Sample	Ce : Mn : Fe molar ratio	Fe²⁺	Fe³⁺	Mn²⁺	Mn³⁺	Mn⁴⁺	Ce³⁺	Ce⁴⁺
Mn-Fe-O	0 : 1.00 : 2.02	39	61	24	41	35	-	-
Ce(0.01)/Mn-Fe-O	0.01 : 1 : 2.02	35	65	20	42	38	19	81
Ce(0.05)/Mn-Fe-O	0.08 : 1 : 2.02	29	71	20	45	35	18	82
Ce(0.1)/Mn-Fe-O	0.17 : 1 : 2.02	30	70	17	45	38	19	81
Ce(0.3)/Mn-Fe-O	0.43 : 1 : 2.02	32	68	26	43	31	17	83

Fig. 6 (a) H2-TPR and (b) NH3-TPD curves of Mn-Fe-O and Ce(0.1)/Mn-Fe-O

Fig. 7 Catalytic activity toward NH3-SCR of NO over different catalysts (a) Conversion of NO; (b) Selectivity of N2

Fig. 8 SO2 and H2O step response experiments for Ce(0.1)/ Mn-Fe-O

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CeO₂ Modified Mn-Fe-O Composites and their Catalytic Performance for NH₃-SCR of NO

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