基于氧空位调控的CeO2催化剂催化氧化甲苯性能

doi:10.11949/0438-1157.20250565

摘要/Abstract

摘要：

挥发性有机化合物（VOCs）作为二次有机气溶胶和臭氧的前驱体，对人体和动物健康构成严重威胁。本研究以甲苯为目标污染物，选择铈氧化物作为催化剂，通过调整合成技术进而影响催化剂的物化性质，旨在开发出一种制备简便且高效的催化剂。运用多种表征技术对催化剂进行分析，结果表明，优化合成方法后所得催化剂（以下简称“CeO₂-Y”，其中“Y”表示采用乙酸-乙二醇体系辅助水热法制备，具有疏松球形结构的样品）展现出理想的形貌结构和物理吸附属性。富含的Ce³⁺能够促进氧空位的形成，从而提高氧储存能力和氧迁移效率，并改善其在低温下的氧化还原性能。原位红外测试揭示了甲苯的反应路径，其中，苯环的裂解步骤是整个反应的决速步。本研究不仅为甲苯的催化氧化提供了高效催化剂，也为催化剂的合成方法、形貌调控及反应机制提供了理论和实验依据。

关键词: 甲苯, 催化氧化, 合成方法, 形貌调控, 结构缺陷

Abstract:

Volatile organic compounds (VOCs), as secondary organic aerosols and precursors to ozone, posing a threat to human and animal health. In this study, toluene was selected as the target pollutant, cerium oxide was chosen as the catalyst, and the synthesis technology was adjusted to affect the physicochemical properties of the catalyst, aiming to develop a simple and efficient catalyst for preparation. Using multiple characterization techniques to analyze the catalyst, the results showed that the catalyst obtained after optimizing the synthesis method (hereinafter referred to as "CeO₂-Y", where "Y" indicates a sample with a loose spherical structure prepared using an acetic acid-ethylene glycol system as an auxiliary hydrothermal method) exhibited ideal morphological structure and physical adsorption properties. The enriched Ce³⁺ could promote the formation of oxygen vacancies, which could enhance the oxygen storage capacity and oxygen migration efficiency, and improve its redox performance at low temperatures. In situ DRIFTS testing revealed the reaction pathway of toluene, in which the cracking step of the benzene ring is the rate-determining step of the entire reaction. This study not only provides efficient catalysts for the catalytic oxidation of toluene, but also provides theoretical and experimental bases for the synthesis method, morphological modulation and reaction mechanism of the catalysts.

Key words: toluene, catalytic combustion, synthesis method, morphology regulation, structural defects

中图分类号:

TQ13

张延焱, 周婷玉, 朱慧敏, 李海洋, 于慧鑫, 张学军. 基于氧空位调控的CeO₂催化剂催化氧化甲苯性能[J]. 化工学报, DOI: 10.11949/0438-1157.20250565.

Yanyan ZHANG, Tingyu ZHOU, Huimin ZHU, Haiyang LI, Huixin YU, Xuejun ZHANG. Catalytic performance of CeO₂ catalysts for the oxidation of toluene based on oxygen vacancy modulation[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250565.

图/表 14

图1 所制备催化剂的(a) XRD图，(b) 氮气吸附与解吸等温曲线，以及(c) 孔径分布图

Fig. 1 (a) XRD pattern, (b) nitrogen adsorption and desorption isothermal curves, and (c) pore size distribution of the prepared catalysts

表1 所制备催化剂的结构参数

Table 1 Structural parameters of the prepared catalysts

Sample	D_p (nm)	S_BET (m² g^-1)	V_p(cm³ g^-1)
CeO₂-Y	8.2	62.4	0.30
CeO₂-X	4.2	89.3	0.16
CeO₂-P	5.8	90.4	0.18
CeO₂-H	17.5	40.9	0.22
CeO₂-S	12.4	33.3	0.08

图2 CeO2样品的拉曼光谱(a)和D模型扩大图(b)

Fig. 2 Raman and D-model expanded spectrum of the CeO2 samples

图3 CeO2-Y (a-c)，CeO2-X (d-f)，CeO2-S (g-i)，CeO2-P (j-l)和CeO2-H (m-o)的SEM、TEM和HRTEM图像

Fig. 3 SEM、TEM and HRTEM images of CeO2-Y (a-c), CeO2-X (d-f), CeO2-S(g-i), CeO2-P (j-l) and CeO2-H (m-o)

图4 所制备催化剂的(a) Ce 3d和(b) O 1s的XPS图谱

Fig. 4 XPS profiles of (a) Ce 3d, (b) O 1s for the prepared catalysts

表2 所制备催化剂的XPS结果以及在O2-TPD和H2-TPR测试中涉及的参数

Table 2 XPS results and the parameters involved in the O2-TPD and H2-TPR tests of the prepared catalysts

样品	Ce³⁺/ (Ce³⁺+Ce⁴⁺) %	O_β/ (O_α+O_β+O_γ) %	氧脱附量 (μmol/g)	H₂消耗量 (μmol/g)
CeO₂-Y	14.6	43.9	7.22	291.2
CeO₂-X	11.1	27.0	6.41	213.5
CeO₂-S	9.5	22.2	3.97	199.1
CeO₂-P	10.1	23.7	4.53	199.3
CeO₂-H	13.5	36.7	2.92	467.9

图5 所制备催化剂的(a) O2-TPD谱图和(b) 100 - 900 oC范围的O2-TPD的放大谱图

Fig. 5 (a) O2-TPD and (b) amplified spectra of O2-TPD in the range of 100 - 900 oC for the prepared catalysts

图6 所制备催化剂的(a) H2-TPR谱图和(b)初始耗氢速率图

Fig. 6 (a) H2-TPR and (b) initial H2 consumption rate of the prepared catalysts

图7 所制备催化剂的(a)甲苯降解效率，(b)SBET归一化，(c)Arrhenius图和(d)CeO2-Y在225 oC的稳定性和抗水性测试

Fig. 7 (a) Toluene degradation efficiency, (b) SBET normalization, (c) Arrhenius plots and (d) CeO2-Y stability and water resistance tests at 225 oC for the prepared catalysts

表3 所制备催化剂的T50、T90及表观活化能

Table 3 T50， T90 and apparent activation energy of the prepared catalysts

样品	T₅₀ (^oC)	T₉₀ (^oC)	Ea (kJ/mol)
CeO₂-Y	203	225	63.68
CeO₂-X	213	255	68.49
CeO₂-S	224	276	97.81
CeO₂-P	220	250	93.09
CeO₂-H	305	>320	77.75

表4 近期报道的CeO2催化剂催化氧化甲苯性能

Table 4 Recently reported catalytic oxidation performance of CeO2 catalysts on toluene

催化剂	甲苯浓度 (ppm)	空速 (mL g^-1 h^-1)	T₉₀ (℃)	文献
CeO₂	1000	30 000	375	[25]
CeO₂	1000	50 000	363	[26]
CeO₂	500	60 000	>300	[27]
CeO₂	500	60 000	320	[28]
CeO₂-P	1000	20 000	280	[29]
CeO₂-C	1000	48 000	296	[8]
CeO₂-RS	1000	48 000	249	[30]
CeO₂-Y	500	60 000	225	This work

图8 CeO2-Y随温度变化(a)和随时间变化(b)下甲苯降解的原位红外光谱

Fig. 8 In situ DRIFTS of toluene degradation by CeO2-Y with temperature (a) and with time (b)

表5 不同合成方法对催化剂结构性能的影响

Table 5 Effect of different synthesis methods on the structural properties of catalysts

催化剂	前驱体	合成方法	溶剂体系	添加剂	反应条件	形貌	晶面暴露	Ov
CeO₂-Y	(NH₄)₂ [Ce(NO₃)₆]	水热法	乙酸 + 乙二醇	无	180 °C 10 h	疏松球形	(220)	高
CeO₂-X	Ce(NO₃)₃· 6H₂O	水热法	乙腈 + 三乙二醇	无	200 °C 2 h	实心球形	(111)	中
CeO₂-S	Ce(NO₃)₃· 6H₂O	水热法	甲醇	尿素	180 °C 12 h	不规则颗粒	(200)	高
CeO₂-P	Ce(CH₃COO₃·4H₂O	沉淀法	乙醇 + 草酸	草酸	80 °C 0.5h	块状片层	(111)	中
CeO₂-H	Ce(SO₄)₂· 4H₂O	一锅法	水	尿素	100 °C 12 h	团聚颗粒	(111)	高

图9 CeO2-Y长时间稳定性反应前后的XRD (a)和Raman谱图(b)

Fig. 9 XRD (a) and Raman spectra (b) before and after long time stabilization reaction of CeO2-Y

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基于氧空位调控的CeO₂催化剂催化氧化甲苯性能

Catalytic performance of CeO₂ catalysts for the oxidation of toluene based on oxygen vacancy modulation

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