用于高性能单Pd三效催化剂的复合组分CexZr1-xO2材料的制备

doi:10.15541/jim20170387

无机材料学报 ›› 2018, Vol. 33 ›› Issue (7): 798-804.DOI: 10.15541/jim20170387 CSTR: 32189.14.10.15541/jim20170387

用于高性能单Pd三效催化剂的复合组分Ce_xZr_1-_xO₂材料的制备

李红梅¹, 兰丽¹, 陈山虎², 刘达玉¹, 王卫¹, 陈耀强³

1. 成都大学药学与生物工程学院, 成都 610106;
2. 中自环保科技股份有限公司, 成都 611731;
3. 四川大学化学学院, 绿色化学与技术教育部重点实验室, 成都 610064

收稿日期:2017-08-09 出版日期:2018-07-10 网络出版日期:2018-06-19
作者简介:李红梅. E-mail: lihongmeihappy@126.com

Preparation of Ce_xZr_1-_xO₂ with Combined Composition for Improved Pd-only Three-way Catalyst

LI Hong-Mei¹, LAN Li¹, CHEN Shan-Hu², LIU Da-Yu¹, WANG Wei¹, CHEN Yao-Qiang³

1. College of Pharmacy and Biological Engineering, Chengdu University, Chengdu 610106, China;
2. Sinocat Environmental Technology Co., Ltd., Chengdu 611731, China;
3. Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China;

Received:2017-08-09 Published:2018-07-10 Online:2018-06-19
About author:LI Hong-Mei(1980–), female, PhD. E-mail: lihongmeihappy@126.com
Supported by:
National Hi-tech Research and Development Program of China (863 Program, 2015AA034603);Opening Project of Key Laboratory of Sichuan Institutes of Higher Education(15-S07, 16-R04)

摘要/Abstract

摘要：

用简单的顺序沉淀法制备了两种具有混合组分的CeO₂-ZrO₂材料。用X射线衍射(XRD), 拉曼光谱(Raman), X射线光电子能谱(XPS), 氮气吸附-脱附, 氢气程序升温还原(H₂-TPR)和储氧量(OSC)研究了不同组合形式对负载的单Pd催化剂性能的影响。结果表明, 两个混和组分的催化剂结构和织构性能都得到了改善。由于贵金属和载体材料之间以及载体材料内部各组分之间的强相互作用, 组合的结构促进了Ce³⁺和晶格缺陷的形成, 提高了氧的移动性, 并且相应的催化剂老化前后对于CO、C₃H₈和NO的转化都具有较宽的窗口范围, 说明这种具有混合组分的载体材料在汽油车尾气净化方面具有良好的应用前景。

关键词: 复合组分结构, 顺序沉淀法, 单Pd三效催化剂, 催化性能

Abstract:

Two special CeO₂-ZrO₂ composites with combined compositions were prepared by a simple sequential precipitation method. The effect of the combination styles on properties of the supported Pd-only three-way catalysts was investigated by means of X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption, H₂-temperature programmed reduction (H₂-TPR), and oxygen storage capacity measurement (OSC). The results reveal that the structural and textural properties are modified for the two catalysts with compositional heterogeneity. Combined configuration facilitates the formation of Ce³⁺ and lattice defects, resulting in improved oxygen mobility, due to strong interaction between the noble metal and the support as well as the synergistic function inside the support. Consequently, the corresponding catalysts show amplified operation windows for the conversions of CO, C₃H₈ and NO before and after aging, indicating promising application in purification of automobile exhaust gases.

Key words: combined composition, sequential precipitation, Pd-only three-way catalyst, catalytic performance

中图分类号:

TQ174

李红梅, 兰丽, 陈山虎, 刘达玉, 王卫, 陈耀强. 用于高性能单Pd三效催化剂的复合组分Ce_xZr_1-_xO₂材料的制备[J]. 无机材料学报, 2018, 33(7): 798-804.

LI Hong-Mei, LAN Li, CHEN Shan-Hu, LIU Da-Yu, WANG Wei, CHEN Yao-Qiang. Preparation of Ce_xZr_1-_xO₂ with Combined Composition for Improved Pd-only Three-way Catalyst[J]. Journal of Inorganic Materials, 2018, 33(7): 798-804.

图/表 9

Fig. 1 XRD patterns of (a) fresh and (b) aged catalysts

Fig. 2 Raman spectra of (a) fresh and (b) aged catalysts

Table 1 Textural properties of fresh and aged catalysts

Sample	Surface area /(m²•g^-1)		Pore volume /(ml•g^-1)		Average pore radius/nm
Sample	fresh	aged	fresh	aged	fresh	aged
Pd/Ce65i	125	26	0.29	0.15	4.6	11.2
Pd/Ce35i	122	25	0.26	0.14	4.3	11.0
Pd/Ce65	131	23	0.24	0.12	3.6	10.9
Pd/Ce35	117	17	0.25	0.11	4.0	13.9

Fig. 3 Pore size distributions of the fresh catalysts.

Table 2 XPS results of fresh and aged catalysts

Samples	Atomic concentration/%				Ce/Zr	(Ce³⁺/Ce) /%
Samples	Ce3d	Zr3d	Pd3d	O1s	Ce/Zr	(Ce³⁺/Ce) /%
Pd/Ce65i-F	7.5	13.7	1.2	77.6	0.5	21.2
Pd/Ce35i-F	8.5	13.9	1.2	76.4	0.6	19.0
Pd/Ce65-F	11.3	9.2	1.7	77.8	1.2	18.9
Pd/Ce35-F	5.8	16.3	1.4	76.5	0.4	18.7
Pd/Ce65i-A	7.0	13.4	1.2	78.4	0.5	20.7
Pd/Ce35i-A	6.9	13.9	1.1	78.1	0.5	18.9
Pd/Ce65-A	8.4	9.9	1.4	80.3	0.8	18.2
Pd/Ce35-A	6.0	15.8	0.8	77.4	0.4	17.7

Fig. 4 TPR profiles of (a) fresh and (b) aged catalysts

Fig. 5 OSC values of fresh and aged catalysts

Fig. 6 Conversion curves of CO, C3H8 and NO as a function of air/fuel ratio (λ) of fresh and aged catalysts

Fig. 7 Schematics of the combination modes of Pd/CeO2-ZrO2 catalysts prepared from sequential precipitation route

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用于高性能单Pd三效催化剂的复合组分Ce_xZr_1-_xO₂材料的制备

Preparation of Ce_xZr_1-_xO₂ with Combined Composition for Improved Pd-only Three-way Catalyst

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