Fe掺杂对La0.9Sr0.1Co1-xFexO3催化剂同时净化NO和碳烟活性规律研究

doi:10.11949/0438-1157.20190851

摘要/Abstract

摘要：

采用柠檬酸-EDTA络合法制备了纳米钙钛矿催化剂La_0.9Sr_0.1Co_1-_xFe_xO₃，催化剂具有较好的同时去除NO和碳烟(soot)催化活性，其中La_0.9Sr_0.1Co_0.7Fe_0.3O₃展现出最佳的催化活性，其在380.0℃时NO转化率为32.5%，soot最大燃烧速率温度(T_m)为368.5℃。H₂-程序升温还原(H₂-TPR)和NO-程序升温脱附(NO-TPD)结果表明， Fe掺杂能显著提高催化剂低温还原性能、表面氧物种活性及NO吸附性能，这有利于其改善催化活性。X射线光电子能谱(XPS)结果表明，Fe掺杂能增加催化剂表面吸附氧浓度和高价离子(Co⁴⁺)，这对提高催化氧化能力至关重要。采用颗粒物捕集器(DPF)作为载体涂覆CeO₂涂层用于负载La_0.9Sr_0.1Co_0.7Fe_0.3O₃催化剂进行柴油机台架实验，结果表明该催化剂具有较好的同时去除NO_x和soot催化活性，最大NO转化率为23.0%，T_m为341.0℃，表明Fe掺杂对提高催化活性至关重要。

关键词: 催化, 多相反应, Fe掺杂, 氧化, NO, 碳烟, 台架实验

Abstract:

The nano-perovskite catalyst La_0.9Sr_0.1Co_1-_xFe_xO₃ was prepared by citric acid-EDTA complex method. The catalysts exhibit excellent catalytic activities for the simultaneous removal of NO and soot. Among them, the La_0.9Sr_0.1Co_0.7Fe_0.3O₃ exhibits the best catalytic activity and wide activity window. The maximum NO conversion is 32.5% at 380.0℃, and the maximum soot combustion rate (T_m) is 368.5℃. The results of H₂-TPR and NO-TPD indicate that the Fe-doping can significantly improve the reduction performance at the low temperature, surface oxygen species activity and NO adsorption performance of catalyst, leading to the enhancement of the catalytic activity. The XPS results show a strong interaction between Co and Fe. With increasing of Fe-doping, the surface adsorbed oxygen concentration and (Co⁴⁺) content could increase on the surface catalyst, it is essential to improve the catalytic oxidation ability. Based on the previous works, the commercial DPF carrier is used to coating the CeO₂ coat, and the La_0.9Sr_0.1Co_0.7Fe_0.3O₃ catalyst is further loaded to carry out the actual diesel engine bench test. The results show that the catalyst has good catalytic activity for simultaneous removal of NO_x and soot. The best NO conversion can reach 23.0%, and the T_m was 341.0℃, indicating that the Fe-doping in the nano-perovskite catalysts can effectively improve the catalytic activity. It is expected that this study will provide strong theoretical support for the design and development of future four-way exhaust catalysts.

Key words: catalysis, multiphase reaction, Fe-doping, oxidation, NO, soot, bench test

中图分类号:

TQ 132.3⁺3

魏炜, 乔智威, 李树华, 苗梦涵, 梁红, 彭峰. Fe掺杂对La_0.9Sr_0.1Co_1-_xFe_xO₃催化剂同时净化NO和碳烟活性规律研究[J]. 化工学报, 2019, 70(12): 4654-4663.

Wei WEI, Zhiwei QIAO, Shuhua LI, Menghan MIAO, Hong LIANG, Feng PENG. Study on simultaneous removal of NO and soot by Fe-doped La_0.9Sr_0.1Co_1-_xFe_xO₃ catalyst[J]. CIESC Journal, 2019, 70(12): 4654-4663.

图/表 8

图1 La0.9Sr0.1Co1-xFexO3 (x= 0、0.1、0.2、0.3、0.4) 催化剂同时去除NO和soot活性曲线

Fig.1 La0.9Sr0.1Co1-xFexO3 (x=0,0.1,0.2,0.3,0.4) catalyst simultaneously removes NO and soot activity curves

图2 La0.9Sr0.1Co1-xFexO3 (x= 0、0.1、0.2、0.3、0.4) 催化剂XRD谱图

Fig.2 XRD patterns of La0.9Sr0.1Co1-xFexO3 (x= 0,0.1,0.2,0.3,0.4) catalysts

图3 La0.9Sr0.1Co1-xFexO3 (x= 0、0.1、0.2、0.3、0.4) 催化剂FT-IR谱图

Fig.3 FT-IR spectra of La0.9Sr0.1Co1-xFexO3 (x= 0,0.1,0.2,0.3,0.4) catalysts

图4 La0.9Sr0.1Co1-xFexO3 (x= 0、0.1、0.2、0.3、0.4) 催化剂的SEM照片

Fig.4 SEM photographs of La0.9Sr0.1Co1-xFexO3 (x= 0,0.1,0.2,0.3,0.4) catalysts

图5 La0.9Sr0.1Co1-xFexO3 (x = 0、0.1、0.2、0.3、0.4) 催化剂H2-TPR和NO-TPD谱图

Fig.5 H2-TPR and NO-TPD profiles of La0.9Sr0.1Co1-xFexO3(x = 0,0.1,0.2,0.3,0.4) catalysts

图6 La0.9Sr0.1Co1-xFexO3催化剂La 3d、Co 2p、Fe 2p及O 1s的XPS谱图

Fig.6 XPS spectra of La 3d, Co 2p, Fe 2p and O 1s core level for La0.9Sr0.1Co1-xFexO3 catalysts

表1 催化剂La 3d、Co 2p和O 1s的XPS结合能及表面吸附氧、Fe2+的相对含量

Table 1 Binding energy of catalyst La 3d, Co 2p and O 1s and relative content of surface adsorption oxygen and Fe2+

Sample	Binding energy/eV			Fe²⁺/(Fe²⁺+ Fe³⁺)	O_α/(O_α+O_β)	O/%(at)
Sample	La 3d_3/2	Co 2p_3/2	O 1s	Fe²⁺/(Fe²⁺+ Fe³⁺)	O_α/(O_α+O_β)	O/%(at)
LaCoO₃	833.80	780.10	529.05	—	52.3	18.81
La_0.9Sr_0.1CoO₃	833.75	780.20	528.90	—	53.5	18.09
La_0.9Sr_0.1Co_0.9Fe_0.1O₃	833.40	779.95	528.70	26.1	53.1	45.72
La_0.9Sr_0.1Co_0.8Fe_0.2O₃	833.65	779.85	528.90	26.5	54.0	45.84
La_0.9Sr_0.1Co_0.7Fe_0.3O₃	833.45	779.85	528.85	57.5	55.1	46.05
La_0.9Sr_0.1Co_0.6Fe_0.4O₃	833.50	779.90	528.80	54.0	45.7	45.17

图7 催化剂La0.9Sr0.1Co0.7Fe0.3O3同时去除柴油机中NOx和soot台架实验

Fig.7 Simultaneous removal of NOx and soot in diesel engine by catalyst La0.9Sr0.1Co0.7Fe0.3O3

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Fe掺杂对La_0.9Sr_0.1Co_1-_xFe_xO₃催化剂同时净化NO和碳烟活性规律研究

Study on simultaneous removal of NO and soot by Fe-doped La_0.9Sr_0.1Co_1-_xFe_xO₃ catalyst

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