掺加Nd和K改性对Co3O4催化分解N2O活性的影响

ZHAO Tian-qi; GAO Qiang; LIAO Wei-ping; XU Xiu-feng

掺加Nd和K改性对Co₃O₄催化分解N₂O活性的影响

烟台大学化学化工学院, 山东烟台 264005

基金项目:

the 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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- 被引次数: 0
出版历程
- 收稿日期: 2019-05-06
- 修回日期: 2019-07-10
- 网络出版日期: 2021-01-23
- 刊出日期: 2019-09-10

Effect of Nd-incorporation and K-modification on catalytic performance of Co₃O₄ for N₂O decomposition

School of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China

Funds:

the 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

摘要

摘要: 用水热法和共沉淀法分别制备了Nd-Co₃O₄催化剂，催化分解N₂O。其中，水热法制备的Nd-Co₃O₄催化活性较高。在不同组成的Nd-Co₃O₄中，优化出了较高活性的0.01Nd-Co₃O₄催化剂，在其表面浸渍K₂CO₃溶液制备K改性催化剂（K/Nd-Co₃O₄）。用X射线衍射（XRD）、N₂物理吸附、扫描电镜（SEM）、X射线光电子谱（XPS）、程序升温还原（H₂-TPR）、O₂程序升温脱附（O₂-TPD）等技术表征催化剂结构。结果表明，Nd-Co₃O₄和K改性催化剂均为尖晶石结构；K改性弱化了催化剂表面Co-O键，有利于表面氧的脱除，提高了催化剂活性。有氧有水气氛350 ℃连续反应40 h，K/Nd-Co₃O₄催化剂上的N₂O分解率超过90%，稳定性较好。
- N₂O催化分解 /
- Nd-Co₃O₄ /
- K改性催化剂 /
- 催化活性
Abstract: Nd-Co₃O₄ catalysts were prepared by hydrothermal and co-precipitation methods to catalyze the decomposition of N₂O. The catalysts prepared by hydrothermal method showed higher activity. Among the hydrothermal Nd-Co₃O₄ catalysts, the catalyst with Nd/Co molar ratio of 0.01 had higher activity. 0.01Nd-Co₃O₄ catalyst was then impregnated by K₂CO₃ solution to prepare K-modified catalyst. The catalysts were characterized by means of X-ray diffraction (XRD), nitrogen physisorption, scanning electrons microscopy (SEM), X-ray photoelectron spectroscopy (XPS), hydrogen temperature-programmed reduction (H₂-TPR), and oxygen temperature-programmed desorption (O₂-TPD). The results show that Nd-Co₃O₄ and K-modified catalysts exhibit spinel structure. In contrast to bare Nd-Co₃O₄, the K-modified catalyst with higher activity is due to its weaker strength of Co-O bond and easier desorption of surface oxygen species. In addition, over 90% conversion of N₂O can be reached over 0.02K/0.01Nd-Co₃O₄ at 350 ℃ for 40 h under the co-presence of oxygen and steam in feed gases.
- catalytic decomposition of N₂O /
- Nd-Co₃O₄ catalysts /
- K-modified catalysts /
- catalytic activity

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Figure 1 XRD patterns of 0.01Nd-Co₃O₄ catalysts prepared by hydrothermal and co-precipitation methods

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Figure 2 H₂-TPR profiles of 0.01Nd-Co₃O₄ prepared by hydrothermal and co-precipitation methods

a: hydrothermal synthesis; b: co-precipitation

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Figure 3 N₂O conversions over 0.01Nd-Co₃O₄ catalysts prepared by hydrothermal and co-precipitation methods

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Figure 4 O₂-TPD profiles of 0.01Nd-Co₃O₄ prepared by hydrothermal and co-precipitation methods

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Figure 5 XRD patterns of Nd-Co₃O₄ with various compositions

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Figure 6 SEM images of Nd-Co₃O₄ catalysts with various molar ratios of Nd/Co

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

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Figure 7 N₂O conversions over Nd-Co₃O₄ catalysts with various compositions

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Figure 8 XPS spectra of Co 2p and O 1s on Nd-Co₃O₄ catalysts with various compositions

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Figure 9 H₂-TPR spectra of Nd-Co₃O₄ catalysts with various compositions

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Figure 10 O₂-TPD profiles of Nd-Co₃O₄ catalysts with various compositions

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Figure 11 N₂O conversions over Nd-Co₃O₄ and K-modified catalysts

■: 0.01Nd-Co₃O₄; ●: 0.01Nd-Co₃O₄ (O₂); ▲: 0.01Nd-Co₃O₄ (O₂+H₂O); ▼: 0.02K/0.01Nd-Co₃O₄; ◆: 0.02K/0.01Nd -Co₃O₄(O₂); ◀: 0.02K/0.01Nd -Co₃O₄(O₂+H₂O)

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Figure 12 XPS spectra of Co 2p and O 1s on the Nd-Co₃O₄ and K-modified catalysts

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Figure 13 Catalytic stability of 0.02K/0.01Nd-Co₃O₄ for N₂O decomposition in the co-presence of oxygen and steam

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Table 1 Crystallite size and specific surface area of Nd-Co₃O₄ with various compositions

Catalyst	Crystallite size d/nm	Specific surface area A/(m²·g^-1)
Nd/Co=0 (Co₃O₄)	26.8	28.5
Nd/Co=0.01	19.7	48.0
Nd/Co=0.03	23.4	50.7
Nd/Co=0.05	24.7	47.4

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Table 2 Kinetic data of N₂O decomposition on Nd-Co₃O₄ catalysts with various compositions

Catalyst	k/s^-1				E_a/(kJ·mol^-1)	lnA
Catalyst	300 ℃	325 ℃	350 ℃	375 ℃	E_a/(kJ·mol^-1)	lnA
Nd/Co=0 (Co₃O₄)	0.67	1.37	3.02	4.73	82.4	16.9
Nd/Co=0.01	1.90	3.59	5.97	8.78	63.3	14.0
Nd/Co=0.03	1.23	2.80	4.95	7.83	76.0	16.2
Nd/Co=0.05	1.22	2.65	4.68	7.19	73.0	15.6

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Table 3 XPS data of Nd-Co₃O₄ catalysts with various compositions

Catalyst	Binding energies of Co 2p_3/2 E /eV		Co²⁺/Co³⁺ (molar ratio)
Catalyst	Co²⁺	Co³⁺	Co²⁺/Co³⁺ (molar ratio)
Nd/Co=0 (Co₃O₄)	779.78	781.39	1.48
Nd/Co=0.01	779.72	781.32	1.59
Nd/Co=0.03	779.65	781.26	1.58
Nd/Co=0.05	779.67	781.21	1.45

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Table 4 XPS data of Nd-Co₃O₄ and K-modified catalysts

Catalyst	Binding energies of Co 2p_3/2 E /eV		Co²⁺/Co³⁺ (molar ratio)
Catalyst	Co²⁺	Co³⁺	Co²⁺/Co³⁺ (molar ratio)
0.01Nd-Co₃O₄	779.72	781.32	1.59
0.02K/0.01Nd-Co₃O₄	779.63	781.22	1.59

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