草酸盐热分解法制备CeO2负载CuO催化剂用于CO优先氧化反应

doi:10.7503/cjcu20170181

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (12): 2296.doi: 10.7503/cjcu20170181

草酸盐热分解法制备CeO₂负载CuO催化剂用于CO优先氧化反应

王成¹, 郭丽红^1,², 李新刚¹(), 马奎¹, 丁彤¹(), 王新雷¹, 程庆鹏¹, 田野¹

1. 天津化学化工协同创新中心, 天津市应用催化科学与工程重点实验室,天津大学化工学院, 天津 300354
2. 河南工业大学化学化工学院, 郑州 450001

收稿日期:2017-03-27 出版日期:2017-12-10 发布日期:2017-11-13
作者简介:联系人简介: 李新刚, 男, 博士, 教授, 主要从事多相催化方面的研究. E-mail: xingang_li@tju.edu.cn.丁彤, 女, 博士, 副教授, 主要从事环境催化方面的研究. E-mail: d_tong@tju.edu.cn
基金资助:
国家自然科学基金(批准号: 21476159, 21476160)和天津市自然科学基金(批准号: 15JCYBJC23000)资助

CuO Catalyst Supported on CeO₂ Prepared by Oxalate Thermal Decomposition Method for Preferential Oxidation of CO^†

WANG Cheng¹, GUO Lihong^1,², LI Xingang^1,^*(), MA Kui¹, DING Tong^1,^*(), WANG Xinlei¹, CHENG Qingpeng¹, TIAN Ye¹

1. Collaborative Innovation Center of Chemical Science and Engineering(Tianjin),Tianjin Key Laboratory of Applied Catalysis Science and Engineering,School of Chemical Engineering & Technology, Tianjin University, Tianjin 300354, China
2. School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou 450001, China

Received:2017-03-27 Online:2017-12-10 Published:2017-11-13
Contact: LI Xingang,DING Tong E-mail:xingang_li@tju.edu.cn;d_tong@tju.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21476159, 21476160) and the Natural Science Foundation of Tianjin, China(No.15JCYBJC23000)

摘要/Abstract

摘要：

采用草酸盐热分解-浸渍法制备了一系列不同CuO负载量的CuO/CeO₂催化剂, 并将其用于CO优先氧化(PROX)研究. 当CuO负载量为10%时催化剂活性最高, 具有温区最宽且温度最低的CO完全转化窗口(96~160 ℃), 并且当反应温度低于131 ℃时, 产物中CO₂选择性始终保持100%. 研究结果表明, 当负载少量CuO时, Cu²⁺离子会进入CeO₂晶格形成固溶体; 进一步提高CuO负载量会导致CuO在CeO₂表面聚集. 对于CuO/CeO₂催化剂, 形成Cu-Ce固溶体会在催化剂表面生成大量的表面氧空位和Ce³⁺; Ce³⁺则与Cu²⁺作用产生更多的表面Cu⁺, 而Cu⁺是CO PROX的活性中心, 因此表面Ce³⁺含量的提高和Cu-Ce之间相互作用的增强是活性提高的主要原因. 与普通沉淀-浸渍法制备的CuO/CeO₂催化剂相比, 草酸盐热分解-浸渍法制备的催化剂更有利于Cu-Ce固溶体的形成, 从而具有更多的表面Ce³⁺和更强的表面Cu-Ce相互作用, 因此具有更高的CO优先氧化活性.

关键词: 草酸盐热分解法, CuO/CeO2催化剂, CO 优先氧化, 强相互作用, 表面Ce3+

Abstract:

A series of CuO/CeO₂ catalysts with different CuO loadings was prepared via oxalate thermal decomposition-impregnation method for the CO preferential oxidation(PROX) reaction. The catalyst with 10% CuO loading has the best activity, with the lowest and the widest CO full conversion temperature window of 96—160 ℃, and 100% selectivity to CO₂ below 131℃. The results indicate that the Cu-Ce solid solution is formed when a small amount of CuO is loaded. However, the increased CuO loading will result in the aggregation of CuO on the surface of CeO₂, which is unfavorable to form the solid solution. For the CuO/CeO₂ catalysts, the formation of Cu-Ce solid solution can inevitably generate surface oxygen vacancy and Ce³⁺, which can react with the Cu²⁺ to produce Cu⁺ through the balance of Ce³⁺+Cu^{2+ $\rightleftharpoons$ ?}Ce⁴⁺+Cu⁺. As the Cu⁺ is the active center for the CO PROX, the increased surface Ce³⁺ content and the strengthened interaction between CuO and CeO₂ can enhance the CO PROX activity of the catalyst. Compared with the CuO/CeO₂ catalysts prepared by precipitation-impregnation method, the catalysts prepared by oxalate thermal decomposition-impregnation method have the higher surface Ce³⁺ content and stronger interaction between Cu and Ce, resulting in the better CO PROX activity.

Key words: Oxalate thermal decomposition method, CuO/CeO2 catalyst, CO preferential oxidation, Strong interaction, Surface Ce3+

中图分类号:

O643

TrendMD:

王成, 郭丽红, 李新刚, 马奎, 丁彤, 王新雷, 程庆鹏, 田野. 草酸盐热分解法制备CeO₂负载CuO催化剂用于CO优先氧化反应. 高等学校化学学报, 2017, 38(12): 2296.

WANG Cheng, GUO Lihong, LI Xingang, MA Kui, DING Tong, WANG Xinlei, CHENG Qingpeng, TIAN Ye. CuO Catalyst Supported on CeO₂ Prepared by Oxalate Thermal Decomposition Method for Preferential Oxidation of CO^†. Chem. J. Chinese Universities, 2017, 38(12): 2296.

图/表 10

Fig.1 CO conversions and CO2 selectivities for CO PROX of the catalysts (A) 5%CuCe; (B) 10%CuCe; (C) 15%CuCe; (D) 20%CuCe; (E) 10%CuCe-P.

Fig.2 TEM(A, C) and HRTEM(B, D) images of the CeO2-CS(A, B) and CeO2-P(C, D) supports

Fig.3 TEM(A, C, E, G, I) and HRTEM(B, D, F, H, J) images of the catalysts(A, B) 10%CuCe-P; (C, D) 5%CuCe; (E, F) 10%CuCe; (G, H) 15%CuCe; (I, J) 20%CuCe.

Fig.4 N2 adsorption-desorption isotherms(A) and pore size distributions(B) of the catalystsa. CeO2-CS; b. CeO2-P; c. 5%CuCe; d. 10%CuCe; e. 15%CuCe; f. 20%CuCe; g. 10%CuCe-P.

Table 1 Physical properties of the samples

Sample	S_BET/(m²·g^-1)	Pore volume/(cm³·g^-1)	Cell parameter of CeO₂/nm	Crystallite size of CeO₂/nm
CeO₂-CS	86	0.105	0.5412	5.0
CeO₂-P	65	0.053	0.5412	9.7
5%CuCe	85	0.218	0.5410	6.6
10%CuCe	79	0.212	0.5404	6.3
15%CuCe	73	0.160	0.5406	6.7
20%CuCe	68	0.150	0.5411	6.9
10%CuCe-P	24	0.069	0.5413	10.3

Fig.5 XRD patterns of the catalystsa. CeO2-CS; b. CeO2-P; c. 5%CuCe; d. 10%CuCe;e. 15%CuCe; f. 20%CuCe; g. 10%CuCe-P.

Fig.6 H2-TPR profiles of the catalystsa. 10%CuCe-P; b. 20%CuCe; c. 15%CuCe; d. 10%CuCe; e. 5%CuCe.

Fig.7 UV-Raman spectra of the catalystsa. 20%CuCe; b. 15%CuCe; c. 10%CuCe;d. 5%CuCe; e. 10%CuCe-P.

Table 2 UV-Raman and XPS results of the catalysts

Catalyst	I₅₈₄/ $I 452 a$	$O latt b$ (%)	C $u + c$ (%)	C $e 3 + d$ (%)
5%CuCe	0.31	60.0	80.0	10.4
10%CuCe	0.44	46.3	82.7	14.7
15%CuCe	0.41	50.5	76.3	11.8
20%CuCe	0.33	67.5	66.5	9.9
10%CuCe-P	0.27	74.2	47.0	8.9

Table 2 UV-Raman and XPS results of the catalysts

Catalyst	I₅₈₄/ $I 452 a$	$O latt b$ (%)	C $u + c$ (%)	C $e 3 + d$ (%)
5%CuCe	0.31	60.0	80.0	10.4
10%CuCe	0.44	46.3	82.7	14.7
15%CuCe	0.41	50.5	76.3	11.8
20%CuCe	0.33	67.5	66.5	9.9
10%CuCe-P	0.27	74.2	47.0	8.9

Fig.8 O1s XPS spectra(A), Cu2p XPS spectra(B), Cu LMM spectra(C) and Ce3d XPS spectra(D) of the catalysts(A) 5%CuCe; (B) 10%CuCe; (C) 15%CuCe; (D) 20%CuCe; (E) 10%CuCe-P.

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草酸盐热分解法制备CeO₂负载CuO催化剂用于CO优先氧化反应

CuO Catalyst Supported on CeO₂ Prepared by Oxalate Thermal Decomposition Method for Preferential Oxidation of CO^†

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