N<sub>2</sub>O在Mg-Co和Mg-Mn-Co复合氧化物上的催化分解

郑丽; 吴藏藏; 徐秀峰

N₂O在Mg-Co和Mg-Mn-Co复合氧化物上的催化分解

烟台大学化学化工学院, 山东烟台 264005

基金项目:

山东省重点研发计划 2016GSF117003

烟台大学研究生科技创新基金 GIFYTU

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: 2016-08-17
- 修回日期: 2016-10-09
- 网络出版日期: 2021-01-23
- 刊出日期: 2016-12-10

Catalytic decomposition of N₂O over Mg-Co and Mg-Mn-Co composite oxides

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

More Information

Corresponding author: Tel: 0535-6902746, xxf@ytu.edu.cn

摘要

摘要: 用溶胶-凝胶法制备了不同组成的Mg-Co和Mg-Mn-Co复合氧化物，用于催化分解N₂O。在较高活性的Mg-Mn-Co表面浸渍K₂CO₃溶液，制备K改性催化剂。用X射线衍射（XRD）、N₂物理吸附（BET）、扫描电镜（SEM）、H₂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，考察了复合氧化物的组成、K负载量等制备参数对催化剂活性的影响。结果表明，加入助剂K显著提高了催化剂活性，其中，0.02 K/MgMn_0.2Co_1.8O₄活性较高，有氧无水、有氧有水气氛400℃连续反应50 h，N₂O转化率分别保持97%和60%。有水-无水气氛交替实验表明，有水反应后再进行无水实验，K改性催化剂的稳定性较好。
- N₂O催化分解 /
- Mg-Co复合氧化物 /
- Mg-Mn-Co复合氧化物 /
- K改性催化剂 /
- 催化性能
Abstract: Mg-Co and Mg-Mn-Co composite oxides with different compositions were prepared by sol-gel method for N₂O catalytic decomposition in the presence of oxygen. Of Mg-Mn-Co catalysts, the one with higher activity was impregnated by K₂CO₃ solution to make K-modified catalyst. These catalysts were characterized by X-ray diffraction(XRD), nitrogen physisorption (BET), scanning electron microscopy(SEM), temperature-programmed reduction of hydrogen(H₂-TPR), and temperature-programmed desorption of oxygen(O₂-TPD). The effect of preparation parameters such as compositions and potassium loadings on their catalytic activity has been investigated. The results show that K-modified catalysts exhibit better activity and higher resistance towards water in contrast to un-modified catalyst due to the weakness of surface metal-oxygen bonds. Among these catalysts, 0.02K/MgMn_0.2Co_1.8O₄ is the most active, over which 97% and 60% conversions of N₂O can be reached at 400℃ after continuous running for 50 h under the atmosphere of oxygen-alone and oxygen-steam together, respectively. When the steam is switched off, the catalytic activity of 0.02K/MgMn_0.2Co_1.8O₄ can be restored to large extent, indicating the good water-resistance of K-modified catalyst.
- catalytic decomposition of N₂O /
- Mg-Co composite oxides /
- Mg-Mn-Co composite oxides /
- K-modified catalysts /
- catalytic performance

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图 1 Mg-Co复合氧化物的XRD谱图

Figure 1 XRD patterns of Mg-Co composite oxides with different compositions

a: Co₃O₄; b: Mg_0.2Co_2.8O₄; c: Mg_0.4Co_2.6O₄; d: Mg_0.6Co_2.4O₄; e: Mg_0.8Co_2.2O₄; f: MgCo₂O₄

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图 2 Mg-Co复合氧化物上的N₂O转化率

Figure 2 N₂O conversions over Mg-Co composite oxides with different compositions

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图 3 Mg-Co复合氧化物的H₂-TPR谱图

Figure 3 H₂-TPR profiles of Mg-Co composite oxides with different compositions

a: Co₃O₄; b: Mg_0.2Co_2.8O₄; c: Mg_0.4Co_2.6O₄; d: Mg_0.6Co_2.4O₄; e: Mg_0.8Co_2.2O₄; f: MgCo₂O₄

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图 4 Mg-Co复合氧化物的O₂-TPD谱图

Figure 4 O₂-TPD profiles of Mg-Co composite oxides with different compositions

a: Mg_0.2Co_2.8O₄; b: Mg_0.4Co_2.6O₄; c: Mg_0.6Co_2.4O₄; d: Mg_0.8Co_2.2O₄; e: MgCo₂O₄

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图 5 Mg-Mn-Co复合氧化物的XRD谱图

Figure 5 XRD patterns of Mg-Mn-Co composite oxides with different compositions

a: MgCo₂O₄; b: MgMn_0.2Co_1.8O₄; c: MgMn_0.4Co_1.6O₄; d: MgMn_0.6Co_1.4O₄; e: MgMn_0.8Co_1.2O₄; f: MgMnCoO₄

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图 6 Mg-Mn-Co复合氧化物的SEM照片

Figure 6 SEM images of Mg-Mn-Co composite oxides with different compositions

(a): MgCo₂O₄; (b): MgMn_0.2Co_1.8O₄; (c): MgMn_0.6Co_1.4O₄; (d): MgMnCoO₄

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图 7 Mg-Mn-Co复合氧化物的催化活性

Figure 7 N₂O conversions over Mg-Mn-Co composite oxides with different compositions

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图 8 Mg-Mn-Co复合氧化物的H₂-TPR谱图

Figure 8 H₂-TPR profiles of Mg-Mn-Co composite oxides with different compositions

a: MgCo₂O₄; b: MgMn_0.2Co_1.8O₄; c: MgMn_0.4Co_1.6O₄; d: MgMn_0.6Co_1.4O₄; e: MgMn_0.8Co_1.2O₄; f: MgMnCoO₄

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图 9 Mg-Mn-Co复合氧化物的O₂-TPD谱图

Figure 9 O₂-TPD profiles of Mg-Mn-Co composite oxides with different compositions

a: MgCo₂O₄; b: MgMn_0.2Co_1.8O₄; c: MgMn_0.4Co_1.6O₄; d: MgMn_0.6Co_1.4O₄; e: MgMn_0.8Co_1.2O₄; f: MgMnCoO₄

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图 10 K/MgMn_0.2Co_1.8O₄催化剂的SEM照片

Figure 10 SEM images of K/MgMn_0.2Co_1.8O₄ catalysts

(a): MgMn_0.2Co_1.8O₄; (b): 0.02K/MgMn_0.2Co_1.8O₄

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图 11 K/MgMn_0.2Co_1.8O₄催化剂的催化活性

Figure 11 N₂O conversions over K/MgMn_0.2Co_1.8O₄ catalysts

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图 12 K/MgMn_0.2Co_1.8O₄催化剂的H₂-TPR谱图

Figure 12 H₂-TPR profiles of K/MgMn_0.2Co_1.8O₄ catalysts

a: MgMn_0.2Co_1.8O₄; b: 0.01K/MgMn_0.2Co_1.8O₄; c: 0.02K/MgMn_0.2Co_1.8O₄; d: 0.03K/MgMn_0.2Co_1.8O₄; e: 0.04K/MgMn_0.2Co_1.8O₄; f: 0.05K/MgMn_0.2Co_1.8O₄

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图 13 不同气氛中0.02K/MgMn_0.2Co_1.8O₄ 催化剂的稳定性

Figure 13 Catalytic stability of 0.02 K/MgMn_0.2Co_1.8O₄ for N₂O decomposition at 400℃ under various atmospheres

■： MgMn_0.2Co_1.8O₄(O₂); ●：MgMn_0.2Co_1.8O₄(O₂+H₂O);▲： 0.02K/MgMn_0.2Co_1.8O₄(O₂); ▼： 0.02K/MgMn_0.2Co_1.8O₄(O₂+H₂O)

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图 14 0.02K/MgMn_0.2Co_1.8O₄催化剂无水-有水交替反应的催化活性

Figure 14 Catalytic activity of 0.02K/MgMn_0.2Co_1.8O₄ for N₂O decomposition at 400℃ under oxygen-only or oxygen-steam atmospheres

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表 1 Mg-Co复合氧化物的晶粒粒径和比表面积

Table 1 Crystallite size and BET surface area of Mg-Co composite oxides

Catalyst	Crystallite size d/nm^a	BET surface area A/(m²·g^-1)
Co₃O₄	113.4	4.0
Mg_0.2Co_2.8O₄	85.0	8.4
Mg_0.4Co_2.6O₄	66.1	13.0
Mg_0.6Co_2.4O₄	104.4	18.8
Mg_0.8Co_2.2O₄	74.1	16.8
MgCo₂O₄	58.8	20.1
^acalculated by Scherrer equation on the basis of (311) crystallographic plane data in XRD patterns

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表 2 Mg-Mn-Co复合氧化物的晶粒粒径和比表面积

Table 2 Crystallite size and BET Surface area of Mg-Mn-Co composite oxides

Catalyst	Crystallite size d/nm^a	BET surface area A/(m²·g^-1)
MgCo₂O₄	58.8	20.1
MgMn_0.2Co_1.8O₄	17.6	75.0
MgMn_0.4Co_1.6O₄	7.8	77.7
MgMn_0.6Co_1.4O₄	8.6	81.0
MgMn_0.8Co_1.2O₄	16.0	72.4
MgMnCoO₄	11.9	73.3
^a calculated by Scherrer equation on the basis of (311) crystallographic plane data in XRD patterns

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表 3 K/MgMn_0.2Co_1.8O₄催化剂的晶粒粒径和比表面积

Table 3 Crystallite size and BET surface area of K/MgMn_0.2Co_1.8O₄ catalysts

Catalyst	Crystallite size d/nm^a	BET surface area A/(m²·g^-1)
MgMn_0.2Co_1.8O₄	17.6	75.0
0.01K/MgMn_0.2Co_1.8O₄	21.2	60.8
0.02K/MgMn_0.2Co_1.8O₄	33.6	54.6
0.03K/MgMn_0.2Co_1.8O₄	25.4	45.7
0.04K/MgMn_0.2Co_1.8O₄	24.7	56.8
0.05K/MgMn_0.2Co_1.8O₄	27.0	44.9
^a calculated by Scherrer equation on the basis of (311) crystallographic plane data in XRD patterns

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