CeO2修饰Mn-Fe-O复合材料及其NH3-SCR脱硝催化性能

doi:10.15541/jim20190266

无机材料学报 ›› 2020, Vol. 35 ›› Issue (5): 573-580.DOI: 10.15541/jim20190266

所属专题：环境与催化材料论文精选；【虚拟专辑】化学反应催化剂(2020~2021)

CeO₂修饰Mn-Fe-O复合材料及其NH₃-SCR脱硝催化性能

黄秀兵¹,王鹏¹,陶进长²,席作帅¹

1.北京科技大学材料科学与工程学院, 北京 100083
2.广东省稀土开发及应用研究重点实验室, 广州 510310

收稿日期:2019-05-31 修回日期:2019-07-25 出版日期:2020-05-20 网络出版日期:2019-09-04
作者简介:黄秀兵(1985-), 男, 副教授. E-mail: xiubinghuang@ustb.edu.cn<br/>HUANG Xiubing (1985-), male, assoate professor. E-mail: xiubinghuang@ustb.edu.cn
基金资助:
国家重点研发计划项目(2018YFB0605900);国家自然科学基金青年基金(51802015);广东省稀土开发及应用研究重点实验室开放基金(XTKY-201803)

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

HUANG Xiubing¹,WANG Peng¹,TAO Jinzhang²,XI Zuoshuai¹

1.School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
2.Guangdong Provincial Key Laboratory of Rare Earth Development and Application, Guangzhou 510310, China

Received:2019-05-31 Revised:2019-07-25 Published:2020-05-20 Online:2019-09-04
Supported by:
Fund:National Key Research and Development Progran of China(2018YFB0605900);National Natural Science Fundation of China(51802015);Open Fund of Guangdong Provincial Key Laboratory of Rare Earth Development and Application(XTKY-201803)

摘要/Abstract

摘要：

氨选择性催化还原(NH₃-SCR)技术需要进一步研发在相对较低温度(<300 ℃)下具有良好催化活性、高稳定性及环境友好的脱硝催化材料。本工作采用草酸共沉淀法制备Mn-Fe-O催化材料, 并对其进行不同含量CeO₂修饰, 用于低温NH₃-SCR脱硝催化反应。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、氮气吸附-脱附、X射线光电子能谱(XPS)、程序升温还原或脱附(H₂-TPR、NH₃-TPD)等手段对催化剂进行了表征。催化结果表明, 在相同反应条件下适量CeO₂修饰后的Mn-Fe-O样品比纯Mn-Fe-O表现出更优异的NH₃-SCR脱硝催化性能, 在80 ℃时NO转化率在95%以上, 且具有较高的N₂选择性。CeO₂修饰提高了Mn-Fe-O氧化物表面的Fe ³⁺、Mn ³⁺和Mn ⁴⁺含量及表面酸性位点数量, 从而有助于NH₃的吸附及催化反应的进行, 并且Fe ²⁺/Fe ³⁺、Mn ²⁺/Mn ³⁺/Mn ⁴⁺以及Ce ³⁺/Ce ⁴⁺电子对之间的相互氧化还原反应提高了催化剂的氧化还原能力及稳定性。

关键词: 二氧化铈, 修饰, 铁锰氧化物, 脱硝

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

中图分类号:

TB34

黄秀兵, 王鹏, 陶进长, 席作帅. CeO₂修饰Mn-Fe-O复合材料及其NH₃-SCR脱硝催化性能[J]. 无机材料学报, 2020, 35(5): 573-580.

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.

图/表 10

图1 复合氧化物的XRD图谱

Fig. 1 XRD patterns of the composites

图2 Ce(x)/Mn-Fe-O的SEM照片

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

图3 催化材料的N2吸脱附曲线

Fig. 3 N2 adsorption-desorption curves of catalysts

表1 Ce(x)/Mn-Fe-O的结构属性

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

图4 Mn-Fe-O和Ce(0.1)/Mn-FeO样品的Raman图谱

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

图5 Mn-Fe-O及Ce(0.1)/Mn-Fe-O样品的XPS谱图

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

表2 Ce(x)/Mn-Fe-O复合材料表面离子含量

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

图6 Mn-Fe-O和Ce(0.1)/Mn-Fe-O的(a) H2-TPR和(a) NH3-TPD曲线

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

图7 不同催化材料的NH3还原NO的催化性能

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

图8 Ce(0.1)/Mn-Fe-O的SO2和H2O阶跃应答实验

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

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CeO₂修饰Mn-Fe-O复合材料及其NH₃-SCR脱硝催化性能

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

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