界面效应在锰氧化物修饰的CeO<sub>2</sub>纳米立方甲苯氧化中的作用

叶鹏; 吴启龙; 田茜; 宋华; 甘丽娜

doi:10.19906/j.cnki.JFCT.2024010

界面效应在锰氧化物修饰的CeO₂纳米立方甲苯氧化中的作用

doi: 10.19906/j.cnki.JFCT.2024010

叶鹏^1,,
吴启龙^1,,
田茜^1,,
宋华^2,,
甘丽娜^1, ,

1.
上海理工大学建筑与环境学院, 上海 200093
2.
军事科学院防化研究院, 北京 100191

基金项目: 国家自然科学基金 (22206130)资助

详细信息

通讯作者:
Tel: 021-55275979, Fax: 021-55275979, E-mail: lngan@usst.edu.cn

中图分类号: X551
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出版历程
- 收稿日期: 2024-01-22
- 修回日期: 2024-03-13
- 录用日期: 2024-03-15
- 网络出版日期: 2024-04-23

Role of interfacial effects in the oxidation of toluene by MnO_x-modified CeO₂ nanocubes

YE Peng^1
,,
WU Qilong^1
,,
TIAN Xi^1
,,
SONG Hua^2
,,
GAN Lina^{1
, ,}

1.
School of Environment and Architecture, University of Shanghai for Science and Technology, Shanghai 200093, China
2.
Institute of Chemical Defense, Academy of Military Sciences, Beijing 100191, China

Funds: The project was supported by National Natural Science Foundation of China (22206130).

摘要

摘要: 本研究，通过水热-浸渍两步法成功制备了不同Mn负载量的二元xMn/Ce（xMnO_x/CeO₂）催化剂，并评估了这些催化剂在甲苯催化氧化反应中的性能。研究结果表明，引入MnO_x能显著提高催化剂的甲苯氧化活性。特别是当Mn负载量为10%（10Mn/Ce）时，在气体空速为60000 mL/(g·h)的条件下，t₉₀（甲苯转化率达到90%时的温度）仅为233 ℃，显示出最优的甲苯催化氧化活性。这一结果说明，适量的MnO_x加入能够显著提高催化剂的催化性能。通过X射线衍射（XRD）、拉曼光谱（Raman）、透射电子显微镜（TEM）、程序升温还原（H₂-TPR）和X射线光电子能谱（XPS）等表征手段，发现MnO_x的加入在MnO_x与CeO₂之间形成了界面效应，这显著改变了Mn/Ce催化剂的物理化学性质。由于界面效应的作用，不仅提高了10Mn/Ce催化剂中Ce³⁺、Mn³⁺离子的浓度以及氧空位的浓度，而且还降低了催化剂表面Ce−O键强度，使得表面晶格氧更易于参与甲苯的催化氧化，提升了催化剂的氧化还原性能，从而促进了甲苯的催化氧化。本研究不仅成功制备了具有优异甲苯氧化活性的Mn/Ce催化剂，而且揭示了其背后的界面效应机制，为VOCs高效氧化催化剂设计与制备提供了简单有效的方法与思路。
- 异质纳米结构 /
- 铈基催化剂 /
- 锰氧化物 /
- 界面效应 /
- 甲苯氧化
Abstract: Toluene, a common volatile organic compounds (VOCs), can have adverse effects on the natural environment as well as on human health. Catalytic oxidation technology can remove toluene economically and efficiently, and the key to this technology is the development of efficient catalysts. In order to improve the oxidation efficiency of toluene, it is of great significance to explore and study new efficient catalysts. In this study, binary xMn/Ce (xMnO_x/CeO₂) catalysts with different Mn loadings were successfully prepared by a two-step hydrothermal-impregnation method, and the performance of these catalysts was evaluated in the catalytic oxidation reaction of toluene. The results showed that the introduction of MnO_x significantly increased the toluene oxidation activity of the catalysts. In particular, when the Mn loading was 10% (10Mn/Ce), the t₉₀ (temperature at which toluene conversion reached 90%) was only 233 ℃ at gas hourly space velocity of 60000 mL/(g·h), showing optimal toluene catalytic oxidation activity. This result suggests that the addition of moderate amount of MnO_x can significantly improve the catalytic performance of the catalysts. By characterization means such as X-ray diffraction (XRD), Raman, transmission electron microscopy (TEM), programmed temperature-raising reduction (H₂-TPR), and X-ray photoelectron spectroscopy (XPS), we found that the incorporation of MnO_x creates an interfacial effect between MnO_x and CeO₂, which significantly alters the physicochemical properties of the Mn/Ce catalysts. Due to the interfacial effect, the concentration of Ce³⁺ and Mn³⁺ ions and the oxygen vacancy in the 10Mn/Ce catalyst were not only increased, but also the strength of Ce−O bond on the catalyst surface was reduced, which made it easier for surface lattice oxygen to participate in the catalytic oxidation of toluene, and enhanced the redox performance of the catalyst, thus promoting the catalytic oxidation of toluene. In this study, we not only successfully prepared Mn/Ce catalysts with excellent toluene oxidation activity, but also revealed the mechanism of interfacial effect behind it, which provides a simple and effective method and idea for the design and preparation of efficient oxidation catalysts for VOCs.
- heterogeneous nanostructures /
- Ce-based catalysts /
- manganese oxide /
- interfacial effects /
- toluene oxidation

HTML全文

图 1 xMn/Ce催化剂的甲苯催化氧化性能

Figure 1 Catalytic oxidation performance of xMn/Ce catalysts for toluene Reaction conditions: toluene 0.1%, O₂ 20%, N₂ as equilibrium gas, simulated gas flow 100 mL/min, GHSV 60000 mL/(g·h).

(a): toluene conversion and (b): toluene oxidation reaction rate

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图 2 CeO₂和xMn/Ce的XRD谱图

Figure 2 XRD spectra of CeO₂ and xMn/Ce

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图 3 xMn/Ce催化剂表面拉曼光谱谱图

Figure 3 Raman spectra of xMn/Ce catalysts

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图 4 xMn/ Ce催化剂N₂吸附-脱附曲线

Figure 4 N₂ adsorption-desorption curves for xMn/ Ce catalysts

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图 5 催化剂SEM图像（a）CeO₂（b）1Mn/Ce（c）10Mn/Ce（d）20Mn/Ce和（e）CeO₂（f）10Mn/Ce的HRTEM图像

Figure 5 SEM images of catalysts (a) CeO₂ (b) 1 Mn/Ce (c) 10 Mn/Ce (d) 20 Mn/Ce and HRTEM image of (e) CeO₂(f)10Mn/Ce

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图 6 CeO₂和xMn/Ce催化剂的H₂-TPR谱图

Figure 6 H₂-TPR maps of CeO₂ and xMn/Ce catalysts

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图 7 CeO₂和xMn/Ce催化剂XPS谱图

Figure 7 XPS spectra of CeO₂ and xMn/Ce catalysts

(a): Ce 3d; (b): Mn 2p; (C): O 1s.

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表 1 Mn/Ce催化剂与同类型催化剂活性对比

Table 1 Comparison of the activity of Mn/Ce catalysts with the same type of catalysts

Catalysts	Preparation method	Reaction condition	t₉₀/℃	Reference
K_0.1-Mn-Ce	sol-gel	1.0×10⁻³ toluene 20% O₂/N₂ space velocity: 60000 h⁻¹	229	[20]
MnCe/ZrO	impregnation	0.5×10⁻³ toluene 20% O₂/N₂ space velocity: 50000 h⁻¹	290	[21]
MC-TPAOH	sol-gel	1.0×10⁻³ toluene 20% O₂/N₂ space velocity: 60000 h⁻¹	221	[22]
MnCe-OH	impregnation	1.0×10⁻³ toluene 20% O₂/N₂ space velocity: 36000 h⁻¹	237	[23]
10Mn/Ce	Hydrothermal-impregnation	1.0×10⁻³ toluene 20% O₂/N₂ space velocity: 60000 h⁻¹	233	this work

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表 2 CeO₂和xMn/Ce催化剂的表面化学组成

Table 2 Surface chemical composition of CeO₂ and xMn/Ce catalysts

Catalyst	A_D/ A_{F_2g}^a	H₂ consumption	Ce³⁺/ （Ce³⁺+Ce⁴⁺）^b	Mn³⁺/Mn^4+b	O_α/O_β^b
CeO₂	−	2.9	0.09	−	0.29
1Mn/Ce	0.13	3.5	0.11	0.46	0.25
5Mn/Ce	0.85	4.2	0.13	0.51	0.38
10Mn/Ce	1.81	4.9	0.16	1.61	0.35
20Mn/Ce	0.92	6.0	0.13	1.22	0.64
^a: 通过Raman图谱计算得到；^b: 通过XPS图谱定量分析得到。

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表 3 CeO₂和xMn/Ce催化剂的孔结构

Table 3 Pore structure of CeO₂ and xMn/Ce catalysts

Catalyst	BET surface area/(m²·g⁻¹)	Pore volume/(cm³·g⁻¹)	Pore size/nm
CeO₂	35	−	−
1Mn/Ce	46	0.18	12.26
5Mn/Ce	45	0.17	12.47
10Mn/Ce	44	0.18	12.42
20Mn/Ce	41	0.17	12.38

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