一步水热合成Y-Co3O4复合氧化物催化剂及催化分解N2O

ZHAO Tian-qi; GAO Qiang; LI He-jian; XU Xiu-feng

一步水热合成Y-Co₃O₄复合氧化物催化剂及催化分解N₂O

烟台大学化学化工学院, 应用催化研究所, 山东烟台 264005

基金项目:

Shandong Natural Science Foundation ZR2017MB020

Graduate Innovation Foundation of Yantai University YDYB1909

详细信息

中图分类号: O643.3
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出版历程
- 收稿日期: 2019-01-08
- 修回日期: 2019-03-03
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-04-10

Catalytic decomposition of N₂O over Y-Co₃O₄ composite oxides prepared by one-step hydrothermal method

Institute of Applied Catalysis, School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China

Funds:

Shandong Natural Science Foundation ZR2017MB020

Graduate Innovation Foundation of Yantai University YDYB1909

More Information

Corresponding author: XU Xiu-feng, E-mail: xxf@ytu.edu.cn

本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).

摘要

摘要: 用一步水热、分步水热、浸渍等方法分别制备Y-Co₃O₄复合氧化物，用于催化分解N₂O的反应，其中，一步水热法制备的催化剂活性较高。再用一步水热法制备了不同Y/Co物质的量比的Y-Co₃O₄复合氧化物，在优化出的催化剂（0.03Y-Co₃O₄）表面浸渍K₂CO₃溶液，制备K改性催化剂（0.02K/0.03Y-Co₃O₄）。用X射线衍射（XRD）、N₂物理吸附、H₂程序升温还原（H₂-TPR）、O₂程序升温脱附（O₂-TPD）、扫描电镜（SEM）、X射线光电子谱（XPS）等技术表征催化剂结构。研究发现，Co₃O₄和Y-Co₃O₄同为尖晶石结构，但Y-Co₃O₄的催化活性显著高于Co₃O₄。K改性增加了催化剂表面的活性位（Co²⁺），还有利于吸附氧的脱除，从而提高了催化剂活性。在无氧无水、有氧无水、有氧有水气氛中，K改性催化剂上的N₂O全分解温度分别为325、350、375 ℃，催化剂活性较高。有氧有水气氛350 ℃连续反应50 h，K改性催化剂上N₂O分解率保持90%以上，稳定性较高。研究发现，Y-Co₃O₄及K改性催化剂上N₂O分解反应的E_a和lnA之间存在动力学补偿效应。
- N₂O催化分解 /
- Y-Co₃O₄复合氧化物催化剂 /
- K改性催化剂 /
- 一步水热合成 /
- 催化活性
Abstract: Y-Co₃O₄ catalysts with Y/Co molar ratio of 0.03 were prepared by several methods, such as one-step hydrothermal, two-step hydrothermal, and impregnation methods, to catalyze the decomposition of N₂O. Among these catalysts, the one prepared by one-step hydrothermal method exhibited the highest activity, and then the Y-Co₃O₄ catalysts with various molar ratios of Y/Co were synthesized by one-step hydrothermal method. Subsequently, the optimized 0.03Y-Co₃O₄ was impregnated by K₂CO₃ solution to prepare K-modified catalyst and named as 0.02K/0.03Y-Co₃O₄. These catalysts were characterized by X-ray diffraction (XRD), nitrogen physisorption, hydrogen temperature-programmed reduction (H₂-TPR), oxygen temperature-programmed desorption (O₂-TPD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques. The results show that both Co₃O₄ and Y-Co₃O₄ exhibit spinel structure, however Y-doped Co₃O₄ catalysts are more active than bare Co₃O₄. After further modified by potassium, the 0.02K/0.03Y-Co₃O₄ reveals higher activity due to the more active sites (Co²⁺) and easier desorption of surface oxygen species than un-modified 0.03Y-Co₃O₄. In detail, the temperatures of N₂O full conversion over 0.02K/0.03Y-Co₃O₄ catalyst are 325, 350, 375℃, under the reaction atmospheres of 1%N₂O+Ar, 1%N₂O+2%O₂+Ar, 1%N₂O+2%O₂+8.2%H₂O+Ar, respectively. In addition, over 90% conversion of N₂O can be maintained at 350℃ after continuous reaction for 50 h in the co-presence of oxygen and steam on K-modified Y-Co₃O₄ catalyst. There is a dynamic compensation effect between apparent activation energy (E_a) and pre-exponential factor (A) in N₂O decomposition over Y-Co₃O₄ and K-modified catalysts.
- catalytic decomposition of N₂O /
- Y-Co₃O₄ composite oxides /
- K-modified catalyst /
- one-step hydrothermal method /
- catalytic activity
本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813).
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Figure 1 XRD patterns of 0.03Y-Co₃O₄ catalysts prepared by different methods

a: one step hydrothermal method; b: two step hydrothermal method; c: impregnation

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Figure 2 N₂O conversions on 0.03Y-Co₃O₄ catalysts prepared by different methods

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Figure 3 H₂-TPR profiles of 0.03Y-Co₃O₄ catalysts prepared by different methods

a: one step hydrothermal method; b: two step hydrothermal method; c: impregnation

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Figure 4 XRD patterns of Y-Co₃O₄ catalysts with various Y/Co molar ratios

a: Y/Co=0 (Co₃O₄); b: Y/Co=0.01; c: Y/Co=0.02; d: Y/Co=0.03; e: Y/Co=0.04; f: Y/Co=0.05

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Figure 5 SEM images of Y-Co₃O₄ catalysts with various Y/Co molar ratios

a: Y/Co=0 (Co₃O₄); b: Y/Co=0.01; c: Y/Co=0.03; d: Y/Co=0.05

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Figure 6 N₂O conversions on Y-Co₃O₄ catalysts with various Y/Co molar ratios

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Figure 7 XPS spectra of Y-Co₃O₄ catalysts with various Y/Co molar ratios

a: Y/Co=0 (Co₃O₄); b: Y/Co=0.01; c: Y/Co=0.03; d: Y/Co=0.05

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Figure 8 H₂-TPR profiles of Y-Co₃O₄ catalysts with various Y/Co molar ratios

a: Y/Co=0 (Co₃O₄); b: Y/Co=0.01; c: Y/Co=0.02; d: Y/Co=0.03; e: Y/Co=0.04; f: Y/Co=0.05

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Figure 9 O₂-TPD profiles of Y-Co₃O₄ catalysts with various Y/Co molar ratios

a: Y/Co=0 (Co₃O₄); b: Y/Co=0.01; c: Y/Co=0.02; d: Y/Co=0.03; e: Y/Co=0.04; f: Y/Co=0.05

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Figure 10 N₂O conversions on 0.03Y-Co₃O₄ and K-modified catalysts under various atmospheres

■: 0.03Y-Co₃O₄; ●: 0.03Y-Co₃O₄ (O₂); ▲: 0.03Y-Co₃O₄ (O₂+H₂O); ▼: 0.02K/0.03Y-Co₃O₄; ◆: 0.02K/0.03Y-Co₃O₄(O₂); ◀: 0.02K/0.03Y-Co₃O₄(O₂+H₂O)

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Figure 11 Catalytic stability of Y-Co₃O₄ and K-modified catalysts for N₂O decomposition in co-presence of oxygen and steam at 350 ℃

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Figure 12 XPS spectra of K-modified and un-modified Y-Co₃O₄ catalysts

a: 0.03Y-Co₃O₄; b: 0.02K/0.03Y-Co₃O₄

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Table 1 Specific surface area of Y-Co₃O₄ catalysts with various Y/Co molar ratios

Y-Co₃O₄ catalyst	Specific surface area A/(m²·g^-1)
Co₃O₄	28.5
Y/Co=0.01	47.7
Y/Co=0.02	61.2
Y/Co=0.03	72.7
Y/Co=0.04	70.8
Y/Co=0.05	80.3

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Table 2 Kinetic data of N₂O decomposition on Y-Co₃O₄ catalysts with various Y/Co molar ratios

Catalyst	k/s^-1					E_a/(kJ·mol^-1)	lnA
Catalyst	275 ℃	300 ℃	325 ℃	350 ℃	375 ℃	E_a/(kJ·mol^-1)	lnA
Co₃O₄	0.26	0.67	1.37	3.02	4.73	86.7	17.7
Y/Co=0.01	0.41	1.18	2.49	4.58	7.29	79.9	16.9
Y/Co=0.02	0.51	1.17	2.50	4.47	7.15	78.5	16.6
Y/Co=0.03	0.50	1.25	2.58	4.57	6.77	77.6	16.4
Y/Co=0.04	0.29	0.90	2.02	3.80	6.28	90.2	18.7
Y/Co=0.05	0.26	0.87	1.82	3.49	5.81	90.7	18.7

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Table 3 Kinetic data of N₂O decomposition over 0.03Y-Co₃O₄ and K-modified catalysts under various reaction atmospheres

Reaction atmospheres	0.03Y-Co₃O₄ catalyst		0.02K/0.03Y-Co₃O₄ catalyst
Reaction atmospheres	E_a /(kJ·mol^-1)	lnA	E_a /(kJ·mol^-1)	lnA
1%N₂O+Ar	77.6	16.4	63.9	15.5
1%N₂O+2%O₂+Ar	91.6	18.7	76.6	18.0
1%N₂O+2%O₂+8.2%H₂O+Ar	110.0	20.6	86.8	19.2

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