富H2/CO2气氛下CuO-NiO/CeO2催化CO-PROX性能的研究

曹栋梁; 刘姝; 姜雅新; 韩蛟; 张财顺; 王宏浩; 侯晓宁; 张磊; 高志贤

doi:10.19906/j.cnki.JFCT.2023077

富H₂/CO₂气氛下CuO-NiO/CeO₂催化CO-PROX性能的研究

doi: 10.19906/j.cnki.JFCT.2023077

曹栋梁^1,,
刘姝^1,,
姜雅新^{1, 2,},
韩蛟^1,,
张财顺^1,,
王宏浩^1,,
侯晓宁^3,,
张磊^1, ,,
高志贤^1, ,

1.
辽宁石油化工大学石油化工学院, 辽宁抚顺 113001
2.
北京中医药大学东方学院医学检验技术学院, 河北沧州 061108
3.
山西师范大学化学与材料科学学院, 山西太原 030000

基金项目: 国家自然科学基金（22379059），辽宁省应用基础研究计划项目（2023JH2/101300224），辽宁省教育厅服务地方项目（揭榜挂帅）（LJKFZ20220201），辽宁省教育厅面上项目（LJKMZ20220728）和山西省应用基础研究青年基金项目（20210302124338）资助

详细信息

通讯作者:
E-mail: lnpuzhanglei@163.com

gaozx@lnpu.edu.cn

中图分类号: O643
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出版历程
- 收稿日期: 2023-09-02
- 修回日期: 2023-10-26
- 录用日期: 2023-10-29
- 网络出版日期: 2023-11-21
- 刊出日期: 2024-04-03

Study on the catalytic performance of CO-PROX catalyzed by CuO-NiO/CeO₂ in H₂/CO₂ rich atmosphere

CAO Dongliang^1
,,
LIU Shu^1
,,
JIANG Yaxin^{1, 2
,},
HAN Jiao^1
,,
ZHANG Caishun^1
,,
WANG Honghao^1
,,
HOU Xiaoning^3
,,
ZHANG Lei^{1
, ,},
GAO Zhixian^{1
, ,}

1.
College of Petrochemical Engineering, Liaoning Petrochemical University, Fushun 113001, China
2.
Institute of Medical Laboratory Technology, Beijing University of Chinese medicine DongFang College, Cangzhou 061108, China
3.
School of Chemistry and Materials Science, Shanxi Normal University, Taiyuan 030000, China

Funds: The project was supported by National Natural Science Foundation of China (22379059), Applied Basic Research Program Project of Liaoning Province (2023JH2/101300224), Service Local Project of the Education Department of Liaoning Province (Enlisting and Leading) (LJKFZ20220201), General Project of the Educational Department of Liaoning Province (LJKMZ20220728) and Fundamental Research Program (Free Exploration) of Shanxi Province (20210302124338)

More Information

Corresponding author: E-mail: lnpuzhanglei@163.com; gaozx@lnpu.edu.cn

摘要

摘要: 采用分步浸渍法制备CuO-NiO/CeO₂催化剂，通过XRD、BET、H₂-TPR、Raman和XPS手段对催化剂进行表征，探究NiO-CeO₂前驱体焙烧温度对催化剂物化性质及富H₂/CO₂气氛下CO选择性氧化性能的影响。结果表明，前驱体焙烧温度主要影响催化剂的还原性能和氧空位的含量。当焙烧温度为500 ℃时，催化剂中氧空位的含量较高，其催化性能较好。在反应温度为130 ℃，氧过量系数为1.2，空速为20266 mL/(g·h)时，CO转化率为95.9%，CO氧化选择性为86.3%。
- 焙烧温度 /
- CuO-NiO/CeO₂ /
- CO-PROX /
- 氧空位
Abstract: The CuO-NiO/CeO₂ catalyst was prepared by step impregnation method. The catalyst was characterized by XRD, BET, H₂-TPR, Raman and XPS, and the effects of the calcination temperature of NiO-CeO₂ precursor on the physicochemical properties of the catalyst and the selective oxidation of CO in H₂/CO₂ rich atmosphere were investigated. The results showed that the precursor calcination temperature mainly affected the reduction performance and oxygen vacancy content of the catalyst. When the calcination temperature is 500 ℃, the content of oxygen vacancy in the catalyst is higher, and the catalytic performance is better. When the reaction temperature is 130 ℃, the oxygen excess coefficient is 1.2, and the air speed is 20266 mL/(g·h), the CO conversion rate is 95.9%, and the CO oxidation selectivity is 86.3%.
- calcination temperature /
- CuO-NiO/CeO₂ /
- CO-PROX /
- oxygen vacancy

HTML全文

FIG. 3081. FIG. 3081.

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图 1 (a)为CeO₂和CuO-NiO/CeO₂-t催化剂的XRD谱图；(b)为(111)晶面放大图

Figure 1 (a) shows the XRD diffraction pattern of CeO₂ and CuO-NiO/CeO₂-t catalysts； (b) is an enlarged view of the (111) crystal plane

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图 2 CuO-NiO/CeO₂-t催化剂N₂吸附-脱附等温线

Figure 2 N₂ adsorption desorption and desorption isotherms of CuO-NiO/CeO₂-t catalysts

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图 3 CeO₂和CuO-NiO/CeO₂-t催化剂的H₂-TPR谱图

Figure 3 H₂-TPR curves of CeO₂ and CuO-NiO/CeO₂-t catalysts

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图 4 CuO-NiO/CeO₂-t催化剂的拉曼光谱谱图

Figure 4 Raman spectra of CuO-NiO/CeO₂-t catalysts

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图 5 CuO-NiO/CeO₂-t催化剂的A₆₀₀/A₄₆₅值

Figure 5 A₆₀₀/A₄₆₅ values of CuO-NiO/CeO₂-t catalysts

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图 10 CuO-NiO/CeO₂-t催化剂的CO转化率

Figure 10 CO conversion of CuO-NiO/CeO₂-t catalysts

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图 6 CuO-NiO/CeO₂-t催化剂的Ni 2p XPS谱图

Figure 6 Ni 2p XPS spectra of CuO-NiO/CeO₂-t catalysts

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图 7 CuO-NiO/CeO₂-t催化剂的Cu 2p XPS谱图

Figure 7 Cu 2p XPS spectra of CuO-NiO/CeO₂-t catalysts

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图 8 CuO-NiO/CeO₂-t催化剂的O 1s XPS谱图

Figure 8 O 1s XPS spectra of CuO-NiO/CeO₂-t catalysts

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图 9 CuO-NiO/CeO₂-t催化剂的Ce 3d XPS谱图

Figure 9 Ce 3d XPS spectra of CuO-NiO/CeO₂-t catalysts

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图 11 CuO-NiO/CeO₂-t催化剂的CO氧化选择性

Figure 11 CO selectivity of CuO-NiO/CeO₂-t catalysts

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表 1 CeO₂及CuO-NiO/CeO₂-t催化剂的XRD分析

Table 1 XRD analysis of CeO₂ and CuO-NiO/CeO₂-t catalyst

Catalyst	Cell parameter/Å	Crystallite size/nm
CeO₂	5.4094	20.1
CuO-NiO/CeO₂-300	5.4086	20.1
CuO-NiO/CeO₂-400	5.4073	20.1
CuO-NiO/CeO₂-500	5.4063	20.0
CuO-NiO/CeO₂-600	5.4082	20.0

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表 2 CeO₂和CuO-NiO/CeO₂-t催化剂的比表面积、孔体积、平均孔径

Table 2 Specific surface area, pore volume and average pore size of CeO₂ and CuO-NiO/CeO₂-t catalyst

Catalyst	S_BET/ (m²·g⁻¹)	Pore volume/ (mL·g⁻¹)	Average pore size/nm
CeO₂	34.2	0.134	15.67
CuO-NiO/CeO₂-300	31.5	0.131	17.56
CuO-NiO/CeO₂-400	28.5	0.124	17.44
CuO-NiO/CeO₂-500	28.9	0.128	17.69
CuO-NiO/CeO₂-600	28.3	0.122	17.27

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表 3 CuO-NiO/CeO₂-t催化剂的峰位置t_peak及峰面积占比area

Table 3 Peak position t_peak and peak area ratio of CuO-NiO/CeO₂-t catalysts

Catalyst	α		β		γ		η	α/β
Catalyst	t_peak /℃	area /%	t_peak /℃	area /%	t_peak /℃	area /%	area /%	α/β
CuO-NiO/CeO₂-300	135.9	6.9	163.7	14.6	266.2	23.9	55.3	0.47
CuO-NiO/CeO₂-400	140.9	5.6	173.5	10.4	284.1	29.2	54.8	0.54
CuO-NiO/CeO₂-500	132.6	5.3	162.4	7.4	293.5	33.2	54.2	0.72
CuO-NiO/CeO₂-600	141.0	6.9	154.9	14.2	282.7	27.4	50.8	0.49

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表 4 XPS结果分析

Table 4 XPS results analyzed

Catalyst	O_ads/%	Ce³⁺/%
CuO-NiO/CeO₂-300	22.47	11.26
CuO-NiO/CeO₂-400	25.76	13.98
CuO-NiO/CeO₂-500	27.01	15.70
CuO-NiO/CeO₂-600	23.70	13.32

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表 5 CuO-NiO/CeO₂-t催化剂的t₅₀、t_top和x_max

Table 5 t₅₀, t_top and x_max of CuO-NiO/CeO₂-t catalysts

Catalyst	t₅₀/℃	t_top/℃	x_max/%
CuO-NiO/CeO₂-300	93	130	94.6
CuO-NiO/CeO₂-400	91	130	94.8
CuO-NiO/CeO₂-500	87	130	95.9
CuO-NiO/CeO₂-600	91	130	94.5

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表 6 本文及文献中催化剂的活性对比(130 ℃)

Table 6 Comparison of catalyst activity in this article and in the literature (130 ℃)

Catalyst	Cu load /%	The gas content in the reaction gas				GHSV/(mL·g⁻¹·h⁻¹)	Rate/(μmol·g⁻¹·s⁻¹)	Rate/(μmol·g⁻¹·s⁻¹)
Catalyst	Cu load /%	CO	O₂	H₂	CO₂	GHSV/(mL·g⁻¹·h⁻¹)	Rate/(μmol·g⁻¹·s⁻¹)	Rate/(μmol·g⁻¹·s⁻¹)
CuO-NiO/CeO₂-500	1.00	0.9	0.5	68	11	20266	217	76
CuCe500^[14]	7.99	1	1	50	−	12000	19	−
CuO-CeO₂^[15]	1.13	4	2	50	−	600	21	−
Ce₂₀Cu₅Ni_0.4O_x^[22]	8.21	1	1	−	−	18000	27	25
CuNiCeO^[23]	4.79	1	1	60	−	40000	103	24

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