低负载量Pd/CeO2/γ-Al2O3催化剂用于低温催化氧化VOCs

doi:10.15541/jim20180523

摘要/Abstract

摘要：

采用直接吸附法制备了Pd负载量为0.03% (质量分数)的Pd/γ-Al₂O₃和Pd/CeO₂/γ-Al₂O₃催化剂, 并用于评价VOCs的催化氧化性能。通过X射线衍射(XRD)、N₂吸附-脱附(BET)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)、氢气程序升温还原(H₂-TPR)等对催化剂的结构和表面性能进行了表征。结果表明, 在VOCs体积分数为0.1%, 空速(GHSV)为18000 mL/(g·h)条件下, Pd/CeO₂/γ-Al₂O₃催化剂上甲苯、丙酮和乙酸乙酯实现98%转化率的温度分别为205、220和275 ℃, 比Pd/γ-Al₂O₃分别降低了15、15和20 ℃, 而且即使在较高的气体空速下, Pd/CeO₂/ γ-Al₂O₃催化剂仍能展现出优异的催化氧化性能, 且具有很好的稳定性和选择性。氧化铈的加入对材料的物理化学性质和催化活性有一定的影响, 其中Pd/CeO₂/γ-Al₂O₃含有Ce ³⁺和高含量的PdO, 活性物种主要以PdO形式均匀地分散在载体γ-Al₂O₃表面。另外, PdO与非化学计量的CeO₂之间的金属-载体相互作用增强了Pd/CeO₂/γ-Al₂O₃催化氧化性能。

关键词: Pd/CeO₂/γ-Al₂O₃, 铈, 甲苯, 挥发性有机物, 催化氧化

Abstract:

The Pd/γ-Al₂O₃ and Pd/CeO₂/γ-Al₂O₃catalysts with 0.03wt% Pd loading were successfully synthesized via simple direct-adsorption method, and evaluated for the oxidation of volatile organic compounds (VOCs). The morphology, structure, and surface properties of the synthesized samples were characterized by X-ray diffraction (XRD), N₂ adsorption-desorption (BET method), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction of H₂(H₂-TPR). The temperatures for conversion of 98% toluene, acetone and ethyl acetate over the Pd/CeO₂/γ-Al₂O₃ catalyst were 205, 220 and 275 ℃ under the conditions of VOCs volume fraction at 0.1% and gas hourly space velocity (GHSV) at 18000 mL/(g·h), respectively, which were 15, 15 and 20 ℃ lower than that of Pd/γ-Al₂O₃catalyst. The Pd/CeO₂/γ-Al₂O₃ exhibited outstanding catalytic activity, stability and selectivity even at high gas hourly space velocity. The results indicated the addition of ceria to alumina influenced the physico- chemical properties of the materials and their catalytic activities. It also revealed that Pd/CeO₂/γ-Al₂O₃ possessed Ce ³⁺and high content of PdO, and the main active PdO species were well-dispersed on the surface of the γ-Al₂O₃ support. In addition, the strong metal-support interaction between PdO and non-stoichiometric cerium oxides enhanced catalytic performance of the Pd/CeO₂/γ-Al₂O₃ for oxidation of VOCs.

Key words: Pd/CeO₂/γ-Al₂O₃, cerium, toluene, Volatile organic compounds (VOCs), catalytic oxidation

中图分类号:

O614
O621

李思汉, 张超, 吴辰亮, 张荷丰, 严新焕. 低负载量Pd/CeO₂/γ-Al₂O₃催化剂用于低温催化氧化VOCs[J]. 无机材料学报, 2019, 34(8): 827-833.

LI Si-Han, ZHANG Chao, WU Chen-Liang, ZHANG He-Feng, YAN Xin-Huan. Pd/CeO₂/γ-Al₂O₃ Catalyst with Low Loading for Catalytic Oxidation of VOCs[J]. Journal of Inorganic Materials, 2019, 34(8): 827-833.

图/表 10

图1 Pd/γ-Al2O3和Pd/CeO2/γ-Al2O3催化剂催化氧化(a)甲苯, (b)丙酮和(c)乙酸乙酯

Fig. 1 Catalytic oxidation of VOCs(a) toluene, (b) acetone, (c) ethyl acetate over Pd/γ-Al2O3 and Pd/CeO2/γ-Al2O3

图2 不同空速下Pd/CeO2/γ-Al2O3催化氧化甲苯的研究

Fig. 2 Catalytic oxidation of toluene over Pd/CeO2/γ-Al2O3 at various GHSVs

图3 Pd/CeO2/γ-Al2O3对甲苯氧化的稳定性和对CO2选择性试验

Fig. 3 Stability tests for toluene oxidation with time-on- stream over Pd/CeO2/γ-Al2O3

图4 水蒸气对Pd/ Al2O3 和Pd/Ce2O/Al2O3两种催化剂的催化活性的影响

Fig. 4 Effect of water vapor on toluene conversion over the Pd/Al2O3 and Pd/Ce2O/Al2O3 catalyst under the conditions of toluene concentration = 1×10-3, water vapor concentration = 5.0vol% and GHSV = 18000 mL/(g·h)

表1 为Al2O3、Pd/Al2O3和Pd/CeO2/Al2O3三种样品的物理结构参数

Table 1 Physical structure parameters of Al2O3, Pd/Al2O3 and Pd/CeO2/Al2O3

Sample	Surface area /(m²·g^-1)	Pore size/nm	Pore volume /(cm³·g^-1)
γ-Al₂O₃	357	5.13	0.53
Pd/γ-Al₂O₃	345	5.07	0.52
Pd/CeO₂/γ-Al₂O₃	339	5.02	0.49

图5 (a)γ-Al2O3, (b)Pd/γ-Al2O3, (c)Pd/CeO2/γ-Al2O3样品的XRD图谱

Fig. 5 XRD patterns of (a) γ-Al2O3, (b) Pd/γ-Al2O3 and (c) Pd/CeO2/γ-Al2O3

图6 (a)Pd/γ-Al2O3和(b)Pd/CeO2/γ-Al2O3的TEM照片及其Pd纳米粒子的粒径分布图

Fig. 6 TEM images and Pd NPs size distribution of (a) Pd/γ-Al2O3 and (b) Pd/CeO2/γ-Al2O3

图7 Pd/γ-Al2O3和Pd/CeO2/γ-Al2O3中(a)Pd 3d和(b)Ce 3d图谱

Fig. 7 XPS spectra of (a) Pd 3d and (b) Ce 3d for Pd/γ-Al2O3 and Pd/CeO2/γ-Al2O3

表2 Pd/γ-Al2O3和Pd/CeO2/γ-Al2O3的XPS表征结果

Table 2 XPS results of Pd/γ-Al2O3 and Pd/CeO2/γ-Al2O3

Catalyst	Relative content/wt%
Catalyst	Pd	PdO	Ce³⁺	Ce⁴⁺
Pd/γ-Al₂O₃	34.2	65.8	—	—
Pd/CeO₂/γ-Al₂O₃	0	100	14.5	85.5

图8 (a)Pd/γ-Al2O3和(b)Pd/CeO2/γ-Al2O3的H2-TPR图谱

Fig. 8 H2-TPR profiles of (a) Pd/γ-Al2O3 and (b) Pd/CeO2/γ- Al2O3

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低负载量Pd/CeO₂/γ-Al₂O₃催化剂用于低温催化氧化VOCs

Pd/CeO₂/γ-Al₂O₃ Catalyst with Low Loading for Catalytic Oxidation of VOCs

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