CeO2对MnOx催化剂低温脱硝性能的影响及其机理研究

doi:10.15541/jim20250044

无机材料学报 ›› 2026, Vol. 41 ›› Issue (1): 87-95.DOI: 10.15541/jim20250044 CSTR: 32189.14.jim20250044

CeO₂对MnO_x催化剂低温脱硝性能的影响及其机理研究

邬博宇¹(), 张深根¹^,²(), 张生杨¹, 刘波¹, 张柏林¹^,²()

1.北京科技大学新材料技术研究院, 北京 100083
2.南昌大学物理与材料学院, 南昌 330031

收稿日期:2025-02-05 修回日期:2025-04-13 出版日期:2026-01-20 网络出版日期:2025-06-05
通讯作者: 张深根, 教授. E-mail: zhangshengen@ncu.edu.cn;
张柏林, 副研究员. E-mail: zhangbolin@ncu.edu.cn
作者简介:邬博宇(1997-), 男, 博士研究生. E-mail: wuboyu@aol.com
基金资助:
国家自然科学基金(52204414);国家节能低碳材料生产应用示范平台项目(TC220H06N)

Effect of CeO₂ on Low-temperature Denitrification Performance of MnO_x Catalysts and Its Mechanism

WU Boyu¹(), ZHANG Shengen¹^,²(), ZHANG Shengyang¹, LIU Bo¹, ZHANG Bolin¹^,²()

1. Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China
2. School of Physics and Materials Science, Nanchang University, Nanchang 330031, China

Received:2025-02-05 Revised:2025-04-13 Published:2026-01-20 Online:2025-06-05
Contact: ZHANG Genshen, professor. E-mail: zhangshengen@ncu.edu.cn;
ZHANG Bolin, associate professor. E-mail: zhangbolin@ncu.edu.cn
About author:WU Boyu (1997-), male, PhD candidate. E-mail: wuboyu@aol.com
Supported by:
National Natural Science Foundation of China(52204414);Low-Carbon Materials Production and Application Demonstration Platform Program(TC220H06N)

摘要/Abstract

摘要： 氮氧化物(NO_x)作为我国主要的大气污染物, 通常采用氨气选择性催化还原(NH₃-SCR)技术实现其超低排放。低温NH₃-SCR具有能耗低、成本低等优势, 但在120 ℃条件下, MnO_x基催化剂普遍存在稳定性不足和SO₂、H₂O中毒的问题。为提高MnO_x基催化剂在低温、稀薄烟气条件下的脱硝性能, 本研究采用沉淀-焙烧分解法制备了CeO₂/MnO_x催化剂。通过一系列表征手段, 系统研究了CeO₂对催化剂结构、表面性质及低温NH₃-SCR性能的影响。结合第一性原理计算, 从微观层面揭示了CeO₂对催化机理的影响及其反应活化能降低的内在原因。结果表明, 添加CeO₂细化了催化剂微观颗粒尺寸, 降低了主晶相MnO₂的占比, 显著提升了催化剂的弱酸位点浓度, 提高了Mn³⁺/Mn和O_α/O比值, 改善了催化剂的表面酸性和氧化还原性能。其中, Mn10Ce3和Mn10Ce5催化剂中Mn : Ce物质的量比为10 : 3和10 : 5, 两者均在120 ℃获得了98%以上的NO转化率和较好的稳定性, 且添加CeO₂使团聚态的MnO_x得到分散和Mn⁴⁺分布浓度降低, 这在一定程度上阻碍了高价态Mn⁴⁺对NH₃和NO的过度氧化, 从而抑制了N₂O的形成, 提升了催化剂的N₂选择性。第一性原理计算进一步证实, 添加CeO₂可降低反应路径中各中间态的活化能, 从而降低反应温度并提高低温NH₃-SCR效率。

关键词: 低温氨气选择性催化还原, CeO₂/MnO_x催化剂, 反应机理

Abstract:

Nitrogen oxides (NO_x), as main atmospheric pollutants in China, are usually removed through ammonia selective catalytic reduction (NH₃-SCR) technology to achieve ultra-low emissions. Low-temperature NH₃-SCR has gained much attention due to its low energy consumption and cost. However, MnO_x-based catalysts generally suffer from insufficient stability and are susceptible to SO₂ and H₂O poisoning at 120 ℃. To improve the denitrification performance of MnO_x-based catalysts under low temperature and lean flue gas conditions, CeO₂/MnO_x catalysts were prepared by precipitation-calcination decomposition method in this study. Influence of CeO₂ modification on structure, surface properties and low-temperature NH₃-SCR performance of catalyst was systematically studied. Combining first principles calculations, influence of CeO₂ modification on catalytic mechanism for reducing activation energy of the reaction was revealed at microscopic level. The results showed that addition of CeO₂ refined micro particle size of catalyst, reduced proportion of main crystalline phase MnO₂, significantly increased concentration of weak acid sites in the catalyst, augmented proportion of Mn³⁺/Mn and O_α/O, and improved surface acidity and redox performance of the catalyst. The prepared Mn10Ce3 and Mn10Ce5 catalysts achieved a NO conversion rate of over 98%, maintaining stability even at 120 ℃. Addition of CeO₂ dispersed the aggregated MnO_x and reduced concentration of Mn⁴⁺ distribution, which to some extent hindered excessive oxidation of NH₃ and NO by high valence Mn⁴⁺, thereby suppressing N₂O formation and improving N₂ selectivity of the catalyst. First principles calculations further confirmed that CeO₂ modification reduced the activation energy of various intermediate states in reaction pathway, lowering the reaction temperature and improving the low-temperature NH₃-SCR efficiency.

Key words: low-temperature ammonia selective catalytic reduction, CeO₂/MnO_x catalyst, reaction mechanism

中图分类号:

X701

邬博宇, 张深根, 张生杨, 刘波, 张柏林. CeO₂对MnO_x催化剂低温脱硝性能的影响及其机理研究[J]. 无机材料学报, 2026, 41(1): 87-95.

WU Boyu, ZHANG Shengen, ZHANG Shengyang, LIU Bo, ZHANG Bolin. Effect of CeO₂ on Low-temperature Denitrification Performance of MnO_x Catalysts and Its Mechanism[J]. Journal of Inorganic Materials, 2026, 41(1): 87-95.

图/表 17

图1 催化剂样品的XRD图谱

Fig. 1 XRD patterns of the prepared catalysts

图2 催化剂样品的Raman光谱图

Fig. 2 Raman spectra of the prepared catalysts

图3 (a) Mn10、(b) Mn10Ce1、(c) Mn10Ce3和(d) Mn10Ce5催化剂样品的SEM照片

Fig. 3 SEM images of (a) Mn10, (b) Mn10Ce1, (c) Mn10Ce3, and (d) Mn10Ce5 catalysts

图4 催化剂样品的(a) NH3-TPD和(b) NO-TPD曲线

Fig. 4 (a) NH3-TPD and (b) NO-TPD profiles of the prepared catalysts

图5 催化剂样品的(a) Mn2p、(b) Ce3d和(c) O1s高分辨XPS图谱

Fig. 5 High-resolution XPS spectra of (a) Mn2p, (b) Ce3d and (c) O1s of the prepared catalysts

图6 催化剂样品的H2-TPR曲线

Fig. 6 H2-TPR profiles of the prepared catalysts

图7 催化剂在90~150 ℃的(a) NO转化率和(b) N2选择性

Fig. 7 (a) NO conversion and (b) N2 selectivity of the prepared catalysts in the range of 90-150 ℃

图8 催化剂在120 ℃的抗SO2和H2O性能

Fig. 8 SO2 and H2O resistance of the prepared catalysts at 120 ℃

表1 NH3在CeO2/MnO2表面不同吸附位点的吸附能

Table 1 NH3 adsorption energies at different sites on CeO2/MnO2 surface

Site	NH₃@O_l	NH₃@O_α
1	-1.28 eV	-1.61 eV
2	-1.53 eV	-1.97 eV
3	-1.60 eV	-2.06 eV
4	-1.10 eV	-1.84 eV

图9 MnO2和CeO2/MnO2的表面NH3-SCR路径

Fig. 9 NH3-SCR pathways on the surface of MnO2 and CeO2/MnO2

图S1 催化剂样品的(a) N2吸附-脱附等温线和(b) BJH孔径分布曲线

Fig. S1 (a) N2 adsorption-desorption isotherms and (b) corresponding BJH pore diameter distributions of the prepared catalysts

图S2 (a) CeO2二聚体在MnO2表面的最佳构型和(b) CeO2/MnO2催化剂表面模型形成能

Fig. S2 (a) Optimal configuration of CeO2 dimer on MnO2 surface and (b) formation energy of CeO2/MnO2 model

表S1 催化剂样品的比表面积、孔容和平均孔径

Table S1 Speciﬁc surface area, pore volume and average pore size of the prepared catalysts

Catalyst	S_BET/(m²·g⁻¹)	Pore volume/ (cm³·g⁻¹)	Average pore size/nm
Mn10	34.7	0.078	7.9
Mn10Ce1	35.4	0.067	6.8
Mn10Ce3	37.3	0.074	7.2
Mn10Ce5	38.3	0.079	7.5

表S2 催化剂样品的NH3和NO吸附量(μmol·g−1)

Table S2 Adsorption capacity for NH3 and NO of the prepared catalysts (μmol·g−1)

Catalyst	NH₃-TPD			NO-TPD
Catalyst	Peak I	Peak II	Total	Peak I	Peak II	Total
Mn10	64.4	35.3	99.7	1.9	0.4	2.3
Mn10Ce1	66.1	17.9	84.0	1.9	1.0	2.9
Mn10Ce3	72.6	45.0	117.6	2.3	1.9	4.2
Mn10Ce5	100.6	30.5	131.1	2.1	1.0	3.1

表S3 催化剂样品表面元素分析(%, 原子分数)

Table S3 Surface elements analysis of the prepared catalysts (%, atom fraction)

Catalyst	Mn	Ce	O	Mn³⁺/Mn	Ce³⁺/Ce	O_α/O
Mn10	36.4	-	63.6	19.4	-	26.4
Mn10Ce1	30.1	4.4	65.5	21.3	5.7	29.0
Mn10Ce3	21.9	11.9	66.2	22.4	7.9	35.9
Mn10Ce5	19.6	15.6	64.8	23.2	6.4	29.3

表S4 催化剂样品H2-TPR测试的H2消耗量相对值

Table S4 H2 relative consumption of the prepared catalysts by H2-TPR test

Catalyst	Peak I	Peak II	Total
Mn10	3.3	16.4	19.7
Mn10Ce1	3.2	16.9	20.1
Mn10Ce3	4.4	15.2	19.6
Mn10Ce5	4.1	14.2	18.3

表S5 本研究制备催化剂的NH3-SCR性能与文献数据对比

Table S5 Comparison of NH3-SCR performance of the samples prepared in this study with existing literature

Catalyst	NO conversion @120 ℃/%	T₉₀/℃	NO inlet/ppm
Mn10Ce3	99.1	110	100
Mn10Ce5	98.2	110	100
MnO_x-CeO₂^[S4]	-	120	400
NbmCeO_x^[S5]	-	200	1000
Mn-Ce/Al₂O₃^[S6]	~98	100	500
MnO_x-CeO₂-TiO₂^[S7]	~28	220	3000
CeO₂/Mn-Fe-O^[S8]	~98	-	500

参考文献 30

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CeO₂对MnO_x催化剂低温脱硝性能的影响及其机理研究

Effect of CeO₂ on Low-temperature Denitrification Performance of MnO_x Catalysts and Its Mechanism

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