水热合成Co3O4的制备参数调变及其催化分解N2O性能

LI He-jian; ZHENG Li; ZHAO Tian-qi; XU Xiu-feng

水热合成Co₃O₄的制备参数调变及其催化分解N₂O性能

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:

the Shandong Provincial Natural Science Foundation ZR2017MB020

Graduate Innovation Foundation of Yantai University YDZD1816

详细信息

中图分类号: O643.3
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- 被引次数: 0
出版历程
- 收稿日期: 2018-02-24
- 修回日期: 2018-05-01
- 网络出版日期: 2021-01-23
- 刊出日期: 2018-06-10

Effect of preparation parameters on the catalytic performance of hydrothermally synthesized Co₃O₄ in the decomposition of N₂O

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

Funds:

the Shandong Provincial Natural Science Foundation ZR2017MB020

Graduate Innovation Foundation of Yantai University YDZD1816

More Information

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

摘要

摘要: 以十六烷基三甲基溴化胺（CTAB）为模板剂，通过调变CTAB浓度水热合成了氧化钴前驱体，焙烧制得棒状形貌的Co₃O₄，在其表面浸渍K₂CO₃溶液制得K改性的Co₃O₄催化剂，用于N₂O分解。用X射线衍射（XRD）、N₂物理吸附（BET）、扫描电镜（SEM）、X射线光电子能谱（XPS）、H₂程序升温还原（H₂-TPR）和O₂程序升温脱附（O₂-TPD）等技术对催化剂进行了表征，考察了CTAB/钴及尿素/钴物质的量比等制备参数对Co₃O₄催化分解N₂O活性的影响。结果表明，CTAB浓度为0.05 mol/L、CTAB/钴离子物质的量比为1、尿素/钴离子物质的量比为4时，所制备的Co₃O₄催化剂具有较高的N₂O分解活性，而K改性可以进一步提升其催化性能。K改性的Co₃O₄在有氧有水气氛中400℃下进行N₂O分解反应，50 h后N₂O转化率仍保持在91%以上。
- Co₃O₄ /
- 水热合成 /
- 制备参数 /
- 催化分解 /
- N₂O
Abstract: With hexadecyl trimethyl ammonium bromide (CTAB) as the template, cobaltosic oxide precursors were hydrothermally synthesized. Co₃O₄ catalysts were then prepared by calcining the cobaltosic oxide precursors, which was further modified by impregnation with K₂CO₃ solution and used in the decomposition of N₂O. The catalysts were characterized by means of X-ray diffraction (XRD), nitrogen physisorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H₂-TPR), and oxygen temperature-programmed desorption (O₂-TPD); the effect of CTAB concentration, CTAB/cobalt molar ratio and urea/cobalt molar ratio on the catalytic activity of Co₃O₄ was investigated. The results indicated that the Co₃O₄ catalyst prepared by using 0.05 mol/L CTAB solution, with a CTAB to cobalt molar ratio of 1 and a urea to cobalt molar ratio of 4, exhibits high activity in N₂O decomposition. The catalytic performance of Co₃O₄ can be further enhanced by modifying with K. Over the 0.02 K/Co₃O₄ catalyst, the N₂O conversion remains over 91% at 400 ℃ after conducting the N₂O decomposition reaction for 50 h in the presence of oxygen and steam.
- Co₃O₄ /
- hydrothermal synthesis /
- preparation parameters /
- catalytic decomposition /
- N₂O

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Figure 1 XRD patterns of various Co₃O₄ catalysts synthesized by changing the CTAB concentrations

a: Co₃O₄(CTAB-0); b: Co₃O₄(CTAB-0.01); c: Co₃O₄(CTAB-0.03); d: Co₃O₄(CTAB-0.05); e: Co₃O₄(CTAB-0.06)

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Figure 2 SEM images of various Co₃O₄ catalysts synthesized by changing the CTAB concentration

(a): Co₃O₄(CTAB-0); (b): Co₃O₄(CTAB-0.01); (c): Co₃O₄(CTAB-0.03); (d): Co₃O₄(CTAB-0.05); (e): Co₃O₄(CTAB-0.06)

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Figure 3 N₂O conversions over various Co₃O₄ catalysts synthesized by changing the CTAB concentration

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Figure 4 XPS spectra of various Co₃O₄ catalysts synthesized by changing the CTAB concentration

a: Co₃O₄(CTAB-0); b: Co₃O₄(CTAB-0.01); c: Co₃O₄(CTAB-0.03); d: Co₃O₄(CTAB-0.05); e: Co₃O₄(CTAB-0.06)

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Figure 5 O₂-TPD profiles of various Co₃O₄ catalysts synthesized by changing the CTAB concentration

a: Co₃O₄(CTAB-0); b: Co₃O₄(CTAB-0.01); c: Co₃O₄(CTAB-0.03); d: Co₃O₄(CTAB-0.05); e: Co₃O₄(CTAB-0.06)

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Figure 6 N₂O conversions over various Co₃O₄ catalysts synthesized by changing the CTAB/cobalt molar ratio

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Figure 7 N₂O conversions over various Co₃O₄ catalysts synthesized by changing urea/cobalt molar ratio

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Figure 8 O₂-TPD profiles of various Co₃O₄ catalysts synthesized by changing the CTAB/cobalt molar ratio

a: Co₃O₄(CTAB/Co-0.83); b: Co₃O₄(CTAB/Co-1); c: Co₃O₄(CTAB/Co-1.1); d: Co₃O₄(CTAB/Co-1.3)

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Figure 9 O₂-TPD profiles of various Co₃O₄ catalysts synthesized by changing urea/cobalt molar ratio

a: Co₃O₄(urea/Co-3); b: Co₃O₄(urea/Co-4); c: Co₃O₄(urea/Co-5)

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Figure 10 Cobalt XPS spectra of the K-free and K-modified Co₃O₄ catalysts a: Co₃O₄; b: 0.02K/Co₃O₄

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Figure 11 H₂-TPR profiles of the K-free and K-modified Co₃O₄ catalysts

a: Co₃O₄; b: 0.02K/Co₃O₄

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Figure 12 Activity of K-modified Co₃O₄ catalyst in N₂O decomposition under different reaction atmospheres

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Figure 13 Stability of the 0.02 K/Co₃O₄ catalyst in N₂O decomposition at 400 ℃ under the atmosphere of 1%N₂O, 2%O₂, 8.2%H₂O, and balanced argon

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Table 1 BET surface area of various Co₃O₄ catalysts synthesized by changing the CTAB concentration

Catalyst	BET surface area A/(m²·g^-1)
Co₃O₄(CTAB-0)	21.1
Co₃O₄(CTAB-0.01)	42.2
Co₃O₄(CTAB-0.03)	47.2
Co₃O₄(CTAB-0.05)	50.3
Co₃O₄(CTAB-0.06)	27.8

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Table 2 Kinetic data for N₂O decomposition over various Co₃O₄ catalysts synthesized by changing the CTAB concentration

Catalyst	k/s^-1					E_a/(kJ·mol^-1)	lnA
Catalyst	300 ℃	325 ℃	350 ℃	375 ℃	400 ℃	E_a/(kJ·mol^-1)	lnA
Co₃O₄(CTAB-0)	-	-	1.96	3.77	6.55	84.2	16.9
Co₃O₄(CTAB-0.01)	0.75	0.91	2.45	4.02	6.55	74.5	15.2
Co₃O₄(CTAB-0.03)	1.01	1.87	3.53	5.70	7.30	65.4	13.8
Co₃O₄(CTAB-0.05)	1.33	2.45	4.40	7.50	11.50	69.8	14.9
Co₃O₄(CTAB-0.06)	0.75	1.42	2.86	5.39	7.71	77.1	15.9

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Table 3 Kinetic data of N₂O decomposition over 0.02K/Co₃O₄ under different reaction atmospheres

Reaction feed	k/s^-1				E_a /(kJ·mol^-1)	lnA
Reaction feed	250 ℃	275 ℃	300 ℃	325 ℃	E_a /(kJ·mol^-1)	lnA
1%N₂O + Ar	2.76	7.50	13.09	20.10	68.2	16.8
1%N₂O + 2%O₂ + Ar	1.78	5.39	9.90	14.04	71.4	17.2
1%N₂O + 2%O₂ + 8.2%H₂O + Ar	0.52	1.42	3.19	6.73	88.5	19.7

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