花状结构Mn/CuO-CeO2的合成及对CO氧化反应的催化性能

doi:10.7503/cjcu20190382

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (12): 2549.doi: 10.7503/cjcu20190382

花状结构Mn/CuO-CeO₂的合成及对CO氧化反应的催化性能

田龙^1,⁴,龙艳^1,^2,^*(),宋术岩¹,王成^1,^3,^*()

^1. 中国科学院长春应用化学研究所, 稀土资源利用国家重点实验室, 长春 130022
^2. 四川师范大学化学与材料科学学院, 成都 610068
^3. 天津理工大学新能源材料与低碳技术研究院, 天津 300384
^4. 中国科学院大学, 北京 100049

收稿日期:2019-07-10 出版日期:2019-12-04 发布日期:2019-12-04
通讯作者: 龙艳,王成 E-mail:longyan@sicnu.edu.cn;cwang@tjut.edu.cn
基金资助:
国家重点研发计划项目(2017YFA0700104);国家自然科学基金(21571170);天津市自然科学基金(17JCZDJC000)

Synthesis of Flower-like Structured Mn/CuO-CeO₂ and the Catalytic Performance for CO Oxide Reaction ^†

Long TIAN^1,⁴,Yan LONG^1,^2,^*(),Shuyan SONG¹,Cheng WANG^1,^3,^*()

^1. State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Science, Changchun 130022, China
^2. College of Chemistry and Materials Science, Sichuan Normal University, Chengdu 610068, China
^3. Institute for New Energy Materials & Low-Carbon Technologies, Tianjin University of Technology, Tianjin 300384, China;
^4. University of Chinese Academy of Sciences, Beijing 100049, China

Received:2019-07-10 Online:2019-12-04 Published:2019-12-04
Contact: Yan LONG,Cheng WANG E-mail:longyan@sicnu.edu.cn;cwang@tjut.edu.cn
Supported by:
? Supported by the National Key Research and Development Project of China(2017YFA0700104);the National Natural Science Foundation of China(21571170);the Natural Science Foundation of Tianjin, China(17JCZDJC000)

摘要/Abstract

摘要：

通过构建CeO₂与过渡金属氧化物的复合材料提高了CeO₂的高温热稳定性并改善其催化活性. 利用溶剂热法合成了不同组成的三维花状结构Mn/CuO-CeO₂多元复合纳米材料. XRD分析结果表明, 复合材料是以萤石相CeO₂结构为主体的固溶体; SEM照片显示花状结构微球由无数纳米片组装而成, 而每个纳米片的结构单元为尺寸约10 nm的纳米颗粒. 复合材料中CuO和MnO_x的高分散性使各组分之间产生强的相互作用, 所以催化剂的催化活性按照CeO₂<CuO-CeO₂<xMn/CuO-CeO₂的顺序依次升高. 随着Mn掺杂量的增加, 复合材料的催化活性先升高后降低, 在n_Ce∶n_Cu∶n_Mn=25∶5∶2时催化剂表现出最佳催化性能: 在CO氧化反应中, 173 ℃时即能实现CO的完全转化, 并且具有很好的催化稳定性.

关键词: CeO₂, CuO, 复合纳米材料, CO氧化, 协同作用

Abstract:

The unique properties make CeO₂ play important roles in many catalytic reactions. However, CeO₂ alone as a catalyst is fairly unfavorable due to its low catalytic activity and poor stability for high-temperature reactions. Therefore, in this work, we constructed the composite of CeO₂ and transition metal oxides for the purpose of increasing the stability and improving the catalytic performance of CeO₂. We synthesized the Mn/CuO-CeO₂ composite nanomaterials with different components and three-dimensional flower-like structures via solvent thermal method. The XRD patterns confirmed that the synthesis formed solid solutions affording the single phase of fluorite-type CeO₂. And the SEM images showed the composites have flower-like structures which were assembled by numerous nanocrystals and the structural unit of each nanocrystal was nanoparticles with a size of about 10 nm. The catalytic activity of the catalyst increases successively in the order of CeO₂<CuO-CeO₂<xMn/CuO-CeO₂ mainly associated with the strong interaction between constituents owing to the highly dispersed copper and manganese species. And with the increase of Mn doping, the catalytic activity of the composite increases first and then decreases. When n_Ce∶n_Cu∶n_Mn=25∶5∶2, the catalyst exhibited the best catalytic performance: the complete transformation of CO can be achieved at 173 ℃ in CO oxidation test, and it showed good stability.

Key words: CeO₂, CuO, Composite nanomaterial, Oxidation of CO, Synergy

中图分类号:

O643

TrendMD:

田龙,龙艳,宋术岩,王成. 花状结构Mn/CuO-CeO₂的合成及对CO氧化反应的催化性能. 高等学校化学学报, 2019, 40(12): 2549.

Long TIAN,Yan LONG,Shuyan SONG,Cheng WANG. Synthesis of Flower-like Structured Mn/CuO-CeO₂ and the Catalytic Performance for CO Oxide Reaction ^†. Chem. J. Chinese Universities, 2019, 40(12): 2549.

图/表 8

Scheme 1 Synthetic process of xMn/CuO-CeO2

Fig.1 XRD pattern(A), mean particle size distribution(B) and SEM images(C, D) of 0.08Mn/CuO-CeO2 Image (D) is enlarged part of image (C).

Fig.2 SEM images of samples obtained at different reaction time Reaction time/h: (A) 1; (B) 3; (C) 5; (D) 7.

Fig.3 SEM images of samples synthesized with different dosages of NaOH NaOH dosage/mL:(A) 0; (B) 1; (C) 2; (D) 3; (E) 4; (F) 5.

Table 1 Molar ratio of Ce, Cu and Mn in the precursors and the products

Sample	Molar ratio of Ce/Cu/Mn		Sample	Molar ratio of Ce/Cu/Mn
Sample	In precursor	In product	Sample	In precursor	In product
CeO₂	25:0:0	25:0:0	0.08Mn/CuO-CeO₂	25:5:2	25:5.18:1.73
CuO-CeO₂	25:5:0	25:5.09:0	0.20Mn/CuO-CeO₂	25:5:5	25:5.37:5.10
0.04Mn/CuO-CeO₂	25:5:1	25:4.89:0.87

Fig.4 XRD patterns(A, B) and SEM images(C—G) of CeO2, CuO-CeO2 and xMn/CuO-CeO2 a. CeO2; b. CuO-CeO2; c. 0.04Mn/CuO-CeO2; d. 0.08Mn/CuO-CeO2; e. 0.20Mn/CuO-CeO2; (C) CeO2; (D) CuO-CeO2; (E) 0.04Mn/CuO-CeO2; (F) 0.08Mn/CuO-CeO2; (G) 0.20Mn/CuO-CeO2.

Fig.5 Catalytic activity of asprepared catalysts for CO oxide a. CeO2; b. CuO-CeO2; c. 0.04Mn/CuO-CeO2;d. 0.20Mn/CuO-CeO2; e. 0.08Mn/CuO-CeO2.

Fig.6 Stability test of 0.08Mn/CuO-CeO2 at 175 ℃(a) and 100 ℃(b)

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花状结构Mn/CuO-CeO₂的合成及对CO氧化反应的催化性能

Synthesis of Flower-like Structured Mn/CuO-CeO₂ and the Catalytic Performance for CO Oxide Reaction ^†

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