Catalytic performance of MnOx/TiO2 prepared with different precursors in the oxidation of NO with O3
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摘要: 分别以乙酸锰（MnAc）、氯化锰（MnCl2）和硝酸锰（Mn（NO3）2）为前驱物，采用浸渍法制备MnAc/TiO2、MnCl/TiO2和MnN/TiO2三种催化剂，并采用氮吸附、SEM、H2-TPR、O2-TPD、XRD和XPS进行表征。在固定床反应器上研究了三种催化剂的联合臭氧催化氧化NO性能。结果表明，以乙酸锰为前驱物制备的MnAc/TiO2催化剂联合臭氧催化氧化NO活性最高；MnAc/TiO2催化剂颗粒分散性好，比表面积相对较大，催化剂表面Mn3+较多，因而具有较高的催化活性。Abstract: MnAc/TiO2, MnCl/TiO2 and MnN/TiO2 were prepared by impregnation method using manganese acetate (MnAc), manganese chloride (MnCl2) and manganese nitrate (Mn (NO3)2) as precursors, respectively. These catalysts were characterized by SEM, N2 physisorption, H2-TPR, O2-TPD, XRD and XPS; their catalytic performance in the oxidation of NO with ozone (O3) was investigated in a fixed bed reactor. The results illustrate that the MnAc/TiO2 catalyst with manganese acetate as the precursor exhibits the highest activity among three catalysts, which is ascribed to its highly dispersible particles, large surface area and high content of surface Mn3+.
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Key words:
- ozone /
- manganese precursor /
- NO /
- catalytic oxidation
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图 1 实验装置示意图
Figure 1 Schematic diagram of experimental device for the catalytic oxidation of NO with O3
图 2 不同温度下前驱物对催化活性的影响
Figure 2 Effect of manganese precursor on the catalytic activity of MnOx/TiO2 in the oxidation of NO without O3 at different temperatures reaction conditions: 670 mg/m3 NO, 5% O2, balance N2; GHSV = 24 000 h-1
图 3 不同O3/NO物质的量比下前驱物对NO催化氧化效率的影响
Figure 3 Effect of manganese precursor on the catalytic activity of MnOx/TiO2 in the oxidation of NO with O3 at different O3/NO ratiosreaction conditions: 670 mg/m3 NO, 5% O2, balance N2; GHSV = 24 000 h-1; 140 ℃
图 4 不同催化剂与O3联合作用效果比较
Figure 4 Activity of various MnOx/TiO2 catalysts in the oxidation of NO with O3 at different O3/NO ratios reaction conditions: 670 mg/m3 NO, 5% O2, balance N2; GHSV = 24 000 h-1; 140 ℃
: O3/NO=0; : O3/NO=0.3; : O3/NO=0.7
图 8 催化剂的XRD谱图
Figure 8 XRD patterns of various catalysts
▲: anatase; ■: MnO2; ▼: Mn2O3
图 9 MnAc/TiO2、MnCl/TiO2和MnN/TiO2催化剂的Mn 2p3/2、O 1s XPS谱图
Figure 9 Mn 2p3/2 (a) and O 1s (b) XPS spectra of the MnAc/TiO2, MnCl/TiO2 and MnN/TiO2 catalysts
表 1 催化剂的比表面积
Table 1 Surface area of the catalysts
Sample Specific surface area A/(m2·g-1) MnCl/TiO2 5.8 MnN/TiO2 8.7 MnAc/TiO2 8.9 
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表 2 催化剂表面Mn、O原子浓度
Table 2 Concentrations of Mn and O on the catalyst surface
Sample Mn /% Mn/Ti Mn3+/Mn O 1s /% OⅢ/O 1s MnAc/TiO2 3.34 0.49 0.64 47.85 0.61 MnCl/TiO2 1.90 0.27 0.05 47.97 0.75 MnN/TiO2 2.27 0.33 0.29 44.36 0.44
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表 3 Mn 2p3/2和O 1s的结合能及价态
Table 3 Mn 2p3/2 and O 1s binding energies and valance composition
Sample Mn 2p3/2 E/eV O 1s E/eV Mn3+ Mn4+ Mn7+ ststellite peak OⅠ OⅡ OⅢ OⅣ MnAc/TiO2 641.7 643.6 - 645.9 529.8 - 532.0 - MnCl/TiO2 641.8 644.6 646.2 - - - 533.3 535.9 MnN/TiO2 641.4 642.5 - 645.4 529.6 530.9 532.2 -
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