还原-氧化预处理对Co3O4催化分解N2O性能的影响

郑珂; 王永钊; 胡晓波; 武瑞芳; 刘晓丽; 赵永祥

还原-氧化预处理对Co₃O₄催化分解N₂O性能的影响

郑珂^{1, 2},
王永钊^1, ,,
胡晓波^{1, 2},
武瑞芳¹,
刘晓丽^{1, 2},
赵永祥¹

1.
精细化学品教育部工程研究中心, 山西太原 030006
2.
山西大学化学化工学院, 山西太原 030006

基金项目:

国家自然科学基金 U1710221

详细信息

中图分类号: O643
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- PDF下载量: 16
- 被引次数: 0
出版历程
- 收稿日期: 2018-12-21
- 修回日期: 2019-02-25
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-04-10

Effect of reduction-oxidation pretreatment on the catalytic performance of Co₃O₄ catalyst in N₂O decomposition

ZHENG Ke^{1, 2},
WANG Yong-zhao^{1
, ,},
HU Xiao-bo^{1, 2},
WU Rui-fang¹,
LIU Xiao-li^{1, 2},
ZHAO Yong-xiang¹

1.
Engineering Research Center of Ministry of Education for Fine Chemicals, Taiyuan 030006, China
2.
School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China

Funds:

the National Natural Science Foundation of China U1710221

More Information

Corresponding author: WANG Yong-zhao, Tel: 0351-7010588, E-mail: catalyst@sxu.edu.cn

摘要

摘要: 采用液相沉淀法制备了Co₃O₄催化剂，并对其进行还原-氧化预处理制得Co₃O₄-RO。通过XRD、N₂-physisorption、Raman、H₂-TPR、XPS和O₂-TPD等技术对催化剂进行表征，在连续流动微反应装置上考察了催化剂催化分解N₂O性能。结果表明，经过还原-氧化预处理，与Co₃O₄催化剂相比，Co₃O₄-RO结晶度变差，晶粒粒径减小，尤其是尖晶石结构重构过程削弱了Co-O键，增强了催化剂表面的氧物种脱附能力，降低了催化分解N₂O反应的活化能，因而显著提高了催化剂的催化活性。同时，Co₃O₄-RO对原料气中的O₂ 2%（体积分数）和H₂O 2.3%（体积分数）表现出较强的耐受性。
- Co₃O₄ /
- 还原-氧化预处理 /
- 催化分解N₂O
Abstract: In this paper, Co₃O₄ catalysts were prepared by the liquid precipitation method, and further was subjected to reduction-oxidation pretreatment to obtain Co₃O₄-RO. The catalysts were characterized by XRD, N₂-physisorption, Raman, H₂-TPR, XPS and O₂-TPD. Their catalytic activities in N₂O decomposition were tested on a fixed-bed continuous flow microreactor. The results show that both the crystallinity and the crystallite size of Co₃O₄-RO decrease in comparison with Co₃O₄. Especially the structural reconstruction resulted from the reduction-oxidation pretreatment weakens the Co-O bond and enhances the oxygen desorption capacity on the catalyst surface, which endows the Co₃O₄-RO a lower activation energy. Thus the catalytic activity of the Co₃O₄-RO in N₂O decomposition increases significantly. At the same time, Co₃O₄-RO shows strong resistance to O₂ (2% in feed)and H₂O (2.3% in feed).
- Co₃O₄ /
- reduction-oxidation pretreatment /
- catalytic decomposition of N₂O

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图 1 Co₃O₄和Co₃O₄-RO催化剂的XRD谱图

Figure 1 XRD patterns of the Co₃O₄ and Co₃O₄-RO catalysts

a: Co₃O₄; b: Co₃O₄-RO

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图 2 Co₃O₄和Co₃O₄-RO催化剂的Raman谱图

Figure 2 Raman spectra of the Co₃O₄ and Co₃O₄-RO catalysts

a: Co₃O₄; b: Co₃O₄-RO

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图 3 Co₃O₄和Co₃O₄-RO催化剂的H₂-TPR谱图

Figure 3 H₂-TPR profiles of the Co₃O₄ and Co₃O₄-RO catalysts

a: Co₃O₄; b: Co₃O₄-RO

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图 4 Co₃O₄和Co₃O₄-RO催化剂的XPS谱图

Figure 4 XPS spectra of the Co₃O₄ and Co₃O₄-RO catalysts

(a): Co 2p; (b): O 1s a: Co₃O₄; b: Co₃O₄-RO

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图 5 Co₃O₄和Co₃O₄-RO催化剂的O₂-TPD谱图

Figure 5 O₂-TPD profiles of the Co₃O₄ and Co₃O₄-RO catalysts

a: Co₃O₄; b: Co₃O₄-RO

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图 6 Co₃O₄和Co₃O₄-RO催化剂的活性评价

Figure 6 N₂O conversion over the Co₃O₄ and Co₃O₄-RO catalysts

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图 7 Co₃O₄和Co₃O₄-RO催化剂的稳定性评价

Figure 7 N₂O conversion versus time-on-stream at 420 ℃ of the Co₃O₄ and Co₃O₄-RO catalysts

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图 8 Co₃O₄和Co₃O₄-RO催化剂的lnk与1/T关系图

Figure 8 lnk as a function of 1/T for the reaction over the Co₃O₄ and Co₃O₄-RO catalysts

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表 1 Co₃O₄和Co₃O₄-RO催化剂的织构性质和晶粒粒径

Table 1 Textural properties and crystal size of the Co₃O₄ and Co₃O₄-RO catalysts

Sample	BET surface area A/(m²·g^-1)	Total pore volume v/(cm³·g^-1)	Average pore diameter d/nm	Crystal size d/nm	Lattice parameter /nm
Co₃O₄	47.8	0.20	16.1	24.5	0.8084
Co₃O₄-RO	21.1	0.15	27.7	8.1	0.9835

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表 2 Co₃O₄和Co₃O₄-RO催化剂的H₂消耗量

Table 2 H₂ consumption of the Co₃O₄ and Co₃O₄-RO catalysts obtained from H₂-TPR profiles

Sample	H₂ consumption /(mmol·g^-1)		Peak β/ peak α
Sample	peak α	peak β	Peak β/ peak α
Co₃O₄	4.17	12.34	2.96
Co₃O₄-RO	4.31	9.86	2.29

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表 3 Co₃O₄和Co₃O₄-RO催化剂的XPS表征

Table 3 XPS results of the Co₃O₄ and Co₃O₄-RO catalysts

Catalyst	Binding energy of Co 2p/eV		ΔE	Binding energy of O 1s/eV			O_α1 /(O_α1 + O_α2 + O_β)	O_α2 /(O_α1 + O_α2 + O_β)
Catalyst	Co 2p_3/2	Co 2p_1/2	ΔE	O_α1	O_α2	O_β	O_α1 /(O_α1 + O_α2 + O_β)	O_α2 /(O_α1 + O_α2 + O_β)
Co₃O₄	779.4	794.4	15.0	530.7	O_α2	532.5	529.7	0.23	0.13
Co₃O₄-RO	779.2	794.3	15.1	530.8	532.1	529.4	0.34	0.10

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表 4 Co₃O₄和Co₃O₄-RO的动力学参数

Table 4 Kinetic parameters of the reaction over Co₃O₄ and Co₃O₄-RO catalysts

Catalyst	t/℃	r/(μmol·s^-1·g^-1)	k/(m³·s^-1·g^-1)	E_a /(kJ·mol^-1)
Co₃O₄	280	0.028	7.80×10^-7	75.9
	300	0.048	1.48×10^-6
	320	0.070	2.47×10^-6
Co₃O₄-RO	260	0.049	1.52×10^-6	51.6
	280	0.090	3.63×10^-6
	300	0.110	5.37×10^-6

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还原-氧化预处理对Co₃O₄催化分解N₂O性能的影响

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Effect of reduction-oxidation pretreatment on the catalytic performance of Co₃O₄ catalyst in N₂O decomposition

Corresponding author: WANG Yong-zhao, Tel: 0351-7010588, E-mail: catalyst@sxu.edu.cn

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