Fe对Mn/CeO2-TiO2催化剂低温NH3选择性催化还原NO的影响

doi:10.3724/SP.J.1077.2012.00495

无机材料学报 ›› 2012, Vol. 27 ›› Issue (5): 495-500.DOI: 10.3724/SP.J.1077.2012.00495 CSTR: 32189.14.SP.J.1077.2012.00495

Fe对Mn/CeO₂-TiO₂催化剂低温NH₃选择性催化还原NO的影响

吴大旺^1,2, 张秋林², 林涛², 龚茂初², 陈耀强²

(1. 黔南民族师范学院化学与化工系, 都匀 558000; 2. 四川大学绿色化学与技术教育部重点实验室, 成都 610064)

收稿日期:2011-05-30 修回日期:2011-07-27 出版日期:2012-05-10 网络出版日期:2012-03-31
作者简介:吴大旺(1965-), 男, 副教授. E-mail: wudawang123@126.com
基金资助:
贵州省教育厅自然科学基金(2005221);国家自然科学基金(20773090)

Effect of Fe on the Selective Catalytic Reduction of NO by NH₃ at Low Temperature over Mn/CeO₂-TiO₂ Catalyst

WU Da-Wang^1,2, ZHANG Qiu-Lin², LIN Tao², GONG Mao-Chu², CHEN Yao-Qiang²

(1. Chemistry and Chemical Engineering Department, Qiannan Normal University, Duyun 558000, China; 2. The Key Laboratory of Green Chemistry & Technology (Sichuan University), Ministry of Education, Chengdu 610064, China)

Received:2011-05-30 Revised:2011-07-27 Published:2012-05-10 Online:2012-03-31
About author:WU Da-Wang. E-mail: wudawang123@126.com
Supported by:
Natural Science Foundation of Guizhou Province of China (2005221);National Natural Science Foundation of China (20773090)

摘要/Abstract

摘要：

以锰氧化物为活性组分, CeO₂-TiO₂为载体制备了Mn/CeO₂-TiO₂催化剂. 考察了Fe的加入对Mn/CeO₂-TiO₂的低温NH₃-SCR活性的影响. 并采用BET比表面积, H₂程序升温还原(H₂-TPR)和X射线光电子能谱(XPS)等手段对催化剂进行了表征. 活性结果表明, Fe的引入显著改善了Mn/CeO₂-TiO₂的NH₃-SCR活性, 催化剂在113’250℃之间表现出良好的NO去除效率. 表征结果表明, Fe的引入促进了锰物种在CeO₂-TiO₂表面的分散, 降低了Mn-Fe/CeO₂-TiO₂中锰物种的还原温度. XPS分析指出Mn-Fe/CeO₂-TiO₂表面Mn以+4价存在, 而Fe主要以+3价的Fe₂O₃存在, 且Fe与载体表面间存在强相互作用.

关键词: 铁, 选择性催化还原(SCR), 氮氧化物, 锰

Abstract:

The Mn/CeO₂-TiO₂ catalyst was prepared using manganese oxide as active component, CeO₂-TiO₂ as support. Effect of the addition of Fe on the performance of NH₃-SCR over Mn/CeO₂-TiO₂ at low temperature was investigated. These catalysts were characterized by BET surface area, H₂ temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscope (XPS). The activity result shows that the SCR performance of Mn/CeO₂-TiO₂ is obviously enhanced by the introduction of Fe. The Mn-Fe/CeO₂-TiO₂ catalyst shows high NO conversion within a wide temperature range of 113-250℃. The characterization results show that the introduction of Fe promotes the dispersion of manganese species on the surface of CeO₂-TiO₂, and the reduction temperature of manganese species shifts to lower temperature. The XPS analysis indicates that the valence of surface Mn on Mn-Fe/CeO₂-TiO₂ is +4, while the Fe mainly exists as +3 of Fe₂O₃, and the strong interaction happens between the Fe and the support.

Key words: iron, selective catalytic reduction (SCR), nitrogen oxides, manganese

中图分类号:

O643

吴大旺, 张秋林, 林涛, 龚茂初, 陈耀强. Fe对Mn/CeO₂-TiO₂催化剂低温NH₃选择性催化还原NO的影响[J]. 无机材料学报, 2012, 27(5): 495-500.

WU Da-Wang, ZHANG Qiu-Lin, LIN Tao, GONG Mao-Chu, CHEN Yao-Qiang. Effect of Fe on the Selective Catalytic Reduction of NO by NH₃ at Low Temperature over Mn/CeO₂-TiO₂ Catalyst[J]. Journal of Inorganic Materials, 2012, 27(5): 495-500.

图/表 7

图1 不同催化剂的NH3-SCR活性曲线

Fig. 1 Catalytic activities of different catalysts in NH3-SCR reaction

图2 不同催化剂的XRD图谱

Fig. 2 XRD patterns of different catalysts

图3 表1 不同催化剂的TPR结果

Fig. 3 H2-TPR profile of different catalysts

Table 1 TPR results of different catalysts

Catalyst	Temperature and areas of every peak					Total areas
Catalyst	T-1	T-2	T-3	T-4	T-5	Total areas
Mn-CT	331℃	445℃	487℃	-	-	7589
Mn-CT	888	4116	2595	-	-	7589
Fe-CT	-	450℃	-	609℃	641℃	7046
Fe-CT	-	1825	-	3361	1860	7046
Mn-Fe-CT	308℃	418℃	476℃	508℃	623℃	9006
Mn-Fe-CT	559	3156	2777	1759	755	9006

Table 2 Binding energy of different catalysts

Sample	Mn2p_3/2 /eV	Fe2p_3/2/eV	Ce3d_5/2/eV
Mn-CT	642.3±0.1	-	882.6±0.1
Fe-CT	-	711.6±0.1	882.8±0.1
Mn-Fe-CT	642.4±0.1	711.5±0.1	882.4±0.1

图4 不同催化剂的Mn2p(a), Fe2p(b)和Ce3d(c)XPS图谱 (a) Mn2p; (b) Fe2p; (c) Ce3d

Fig. 4 XPS spectra of two different catalysts

Table 3 Specific surface area, pore volume and of Mn content for different samples

Sample	Specific surface area /(m²·g^-1)	Pore volume /(mL·g^-1)	Mn content /mol%
CT	116	0.29	-
Mn-CT	35.2	0.09	4.9
Fe-CT	56.7	0.11	-
Mn-Fe-CT	36.7	0.08	4.7

参考文献 20

[1]	Garcia-Bordeje E, Calvillo L, Lazaro M J, et al. Vanadium supported on carbon-coated monoliths for the SCR of NO at low temperature: effect of pore structure. Appl. Catal. B: Environ., 2004, 50(4): 235-242.
[2]	Tang F S, Xu B L, Shi H H, et al. The poisoning effect of Na+ and Ca2+ ions doped on the V2O5/TiO2 catalysts for selective catalytic reduction of NO by NH3. Appl. Catal. B: Environ., 2010, 94(1/2): 71-76.
[3]	Huang J H, Tong Z Q, Huang Y, et al. Selective catalytic reduction of NO with NH3 at low temperatures over iron and manganese oxides supported on mesoporous silica. Appl. Catal. B: Environ., 2008, 78(3/4): 309-314.
[4]	Qi G S, Yang R T, Chang R. MnOx-CeO2 mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH3 at low temperatures. Appl. Catal. B: Environ., 2004, 51(2): 93-106.
[5]	Qi G S, Yang R T. Low-temperature selective catalytic reduction of NO with NH3 over iron and manganese oxides supported on titania. Appl. Catal. B: Environ., 2003, 44(3): 217-225.
[6]	Qi G S, Yang R T. Performance and kinetics study for low-temperature SCR of NO with NH3 over MnOx-CeO2 catalyst. J. Catal., 2003, 217(2): 434-441.
[7]	林涛, 徐海迪, 李伟, 等(LIN Tao, et al). 整体式Mn-Fe／ZrO2-TiO2催化剂的制备及在低温NH3-SCR反应中的性能. 高等学校化学学报(Chem. J. Chinese Universities), 2009, 30(11): 2240-2246.
[8]	侯亚芹, 黄张根, 马建蓉, 等(HOU Ya-Qin, et al). V2O5／ACF催化剂低温下选择性催化还原NO的机理. 催化学报(Chinese J. Catal), 2009, 30(10): 1007-1011.
[9]	吴大旺, 张秋林, 林涛, 等(WU Da-Wang, et al). CexTi1-xO2负载锰基催化剂的制备及其低温NH3选择性催化还原NO. 无机化学学报(Chin. J. Inorg. Chem.), 2011, 27(1): 53-60.
[10]	Pena D A, Uphade B S, Smirniotis P G. TiO2-supported metal oxide catalysts for low-temperature selective catalytic reduction of NO with NH3: I. evaluation and characterization of first row transition metals. J. Catal., 2004, 221(2): 421-431.
[11]	Huang H Y, Yang R T. Removal of NO by reversible adsorption on Fe-Mn based transition metal oxides. Langmuir, 2001, 17(16): 4997-5003.
[12]	Ettireddy P R, Ettireddy N, Mamedov S, et al. Surface characterization studies of TiO2 supported manganese oxide catalysts for low temperature SCR of NO with NH3. Appl. Catal. B: Environ, 2007, 76(1/2): 123-134.
[13]	Li N, Wang A Q, Liu Z M, et al. On the catalytic nature of Mn/sulfated zirconia for selective reduction of NO with methane. Appl. Catal. B: Environ., 2006, 62(3/4): 292-298.
[14]	Wu X D, Liang Q, Weng D, et al. Synthesis of CeO2–MnOx mixed oxides and catalytic performance under oxygen-rich condition. Catal. Today, 2007, 126(3/4): 430-435.
[15]	Reddya A. S, Chen C Y, Chen C C, et al. Synthesis and characterization of Fe/CeO2 catalysts: epoxidation of cyclohexene. J. Mol. Catal. A, Chemical, 2010, 318(1/2): 60-67.
[16]	Zieliński J, Zglinicka I, Znak L, et al. Reduction of Fe2O3 with hydrogen. Appl. Catal. A: General, 2010, 381(1/2): 191-196.
[17]	Hayashi H, Chen L Z, Tago T, et al. Catalytic properties of Fe/SiO2 catalysts prepared using microemulsion for CO hydrogenation. Appl. Catal. A :General, 2002, 231(1/2): 81-89.
[18]	Wagner C D, Riggs W M, Davis L E, et al. Handbook of X-Ray Photoelectron Spectroscopy. Eden Prairie: Perking-Elmer Corp, 1979: 78.
[19]	Larachi F, Pierre J, Adnot A, et al. Ce3d XPS study of composite CexMn1-xO2-y wet oxidation catalysts. Appl Surface Science, 2002, 195(1-4): 236-250.
[20]	Qi G S, Yang R T. Characterization and FTIR studies of MnOx-CeO2 catalyst for low-temperature selective catalytic reduction of NO with NH3. J. Phys. Chem. B, 2004, 108(40): 15738-15747.

Fe对Mn/CeO₂-TiO₂催化剂低温NH₃选择性催化还原NO的影响

Effect of Fe on the Selective Catalytic Reduction of NO by NH₃ at Low Temperature over Mn/CeO₂-TiO₂ Catalyst

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 20

相关文章 15

编辑推荐

Metrics

本文评价

[1]	沈浩, 陈倩倩, 周渤翔, 唐晓东, 张媛媛. A位La/Sr共掺杂PbZrO₃薄膜的制备及储能特性优化[J]. 无机材料学报, 2024, 39(9): 1022-1028.
[2]	蔡和庆, 韩璐, 杨松松, 薛新玉, 张扣, 孙志成, 刘儒平, 胡堃, 危岩. 小粒径Fe₃O₄-DMSA-PEI磁性纳米颗粒的制备及其基因负载能力研究[J]. 无机材料学报, 2024, 39(5): 517-524.
[3]	石睿健, 雷俊伟, 张祎, 谢爱文, 左如忠. 具有优异储能性能与充放电特性的类线性NaNbO₃基无铅弛豫反铁电陶瓷[J]. 无机材料学报, 2024, 39(4): 423-431.
[4]	程节, 周月, 罗薪涛, 高美婷, 骆思妃, 蔡丹敏, 吴雪垠, 朱立才, 袁中直. 蛋黄壳结构FeF₃·0.33H₂O@N掺杂碳纳米笼正极材料的构筑及其电化学性能[J]. 无机材料学报, 2024, 39(3): 299-305.
[5]	李承瑜, 丁自友, 韩颖超. 锰掺杂纳米羟基磷灰石的体外抗菌-促成骨性能研究[J]. 无机材料学报, 2024, 39(3): 313-320.
[6]	刘松, 张发强, 罗进, 刘志甫. 0.9BaTiO₃-0.1Bi(Mg_1/2Ti_1/2)O₃铁电薄膜制备及储能特性[J]. 无机材料学报, 2024, 39(3): 291-298.
[7]	厉佥元, 李纪伟, 张钰涵, 刘焱康, 孟阳, 储余, 朱一佳, 徐诺言, 朱亮, 张传香, 陶海军. PbTiO₃修饰和极化处理提升钙钛矿太阳能电池性能[J]. 无机材料学报, 2024, 39(11): 1205-1211.
[8]	戴乐, 刘洋, 高轩, 王书豪, 宋雅婷, 唐明猛, 刘丽莎, 汪尧进. 浓度梯度掺杂实现BiFeO₃薄膜自极化[J]. 无机材料学报, 2024, 39(1): 99-106.
[9]	陈海燕, 唐志鹏, 尹良君, 张林博, 徐鑫. CIPs@Mn_0.8Zn_0.2Fe₂O₄-CNTs复合材料低频吸波性能研究[J]. 无机材料学报, 2024, 39(1): 71-80.
[10]	王艳莉, 钱心怡, 沈春银, 詹亮. 石墨烯基介孔锰铈氧化物催化剂: 制备和低温催化还原NO[J]. 无机材料学报, 2024, 39(1): 81-89.
[11]	孟波, 肖刚, 王秀丽, 涂江平, 谷长栋. 离子热合成锰基氧化物及其可逆储热性能[J]. 无机材料学报, 2023, 38(7): 793-799.
[12]	王雪瑶, 王武港, 李应卫, 彭奇, 梁瑞虹. PZT陶瓷本构行为与断裂性能的相关性研究[J]. 无机材料学报, 2023, 38(7): 839-844.
[13]	林俊良, 王占杰. 铁电超晶格的研究进展[J]. 无机材料学报, 2023, 38(6): 606-618.
[14]	杜剑宇, 葛琛. 光电人工突触研究进展[J]. 无机材料学报, 2023, 38(4): 378-386.
[15]	王彤宇, 冉皓丰, 周广东. 氧化铁忆阻器中缺陷态诱导的模拟型阻变及突触双脉冲易化特性[J]. 无机材料学报, 2023, 38(4): 437-444.