Catalytic performance of La1-xRbxMnO3 perovskite in the simultaneous removal of NO and soot
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摘要: 采用溶剂热法制备了La1-xRbxMnO3（x=0、0.1、0.2、0.3）钙钛矿型复合金属氧化物催化剂，通过XRD、FT-IR、SEM、XPS和H2-TPR等手段对催化剂进行表征，在微型固定床反应器上评价了其同时消除NO和碳烟的催化性能。结果表明，La1-xRbxMnO3催化剂具有单一的钙钛矿结构，样品中Mn物种以Mn3+和Mn4+的形式存在。与LaMnO3催化剂相比，Rb+部分取代La3+，催化剂体系中形成较多的高价Mn4+和氧空位，其氧化还原性能提高，催化性能得到改善。随着Rb+取代量的增加，NO转化率升高，碳烟燃烧温度降低。当x=0.3时，La0.7Rb0.3MnO3催化剂上CO2浓度峰值温度tmax为430 ℃，CO2的选择性为99.0%；反应温度为429 ℃，NO转化率达到最大，为59.7%。Abstract: A series of La1-xRbxMnO3 perovskite catalysts (x=0, 0.1, 0.2, 0.3) were prepared by solvothermal method and characterized by means of XRD, FT-IR, SEM, XPS and H2-TPR; their catalytic performance in the simultaneous removal of NO and soot was investigated in a fixed-bed micro-reactor. The results show that the La1-xRbxMnO3 catalysts have a single perovskite structure and the Mn species exist in the form of Mn3+ and Mn4+. In comparison with LaMnO3, when La3+ is partially substituted by Rb+, more high-valence Mn4+ and oxygen vacancies are formed in La1-xRbxMnO3, which can improve the redox properties and enhance the catalytic performance of La1-xRbxMnO3. With the increase of Rb+ content in La1-xRbxMnO3, the conversion of NO increases and the soot combustion temperature decreases. For NO and soot removal over La0.7Rb0.3MnO3, x=0.3, the peak CO2 formation temperature (tmax) is 430 ℃, with a selectivity of 99.0% to CO2; at 429 ℃, the maximum conversion of NO reaches 59.7%.
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Key words:
- Mn-based perovskite /
- Rb /
- La /
- NO /
- soot
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图 1 催化剂的XRD谱图
Figure 1 XRD patterns of the La1-xRbxMnO3 catalysts
(a): total range; (b): enlarged in the range of 30°-35°
图 3 La1-xRbxMnO3催化剂的SEM照片
Figure 3 SEM images of the La1-xRbxMnO3 catalysts
(a): LaMnO3; (b): La0.9Rb0.1MnO3; (c): La0.8Rb0.2MnO3; (d): La0.7Rb0.3MnO3
图 5 La1-xRbxMnO3催化剂的O 1s态(a)和Mn 2p态(b)的XPS谱图
Figure 5 O 1s (a) and Mn 2p (b) XPS spectra of the in La1-xRbxMnO3 catalysts
图 6 La1-xRbxMnO3 催化剂同时消除NO和碳烟活性评价
Figure 6 Activity of the La1-xRbxMnO3 catalysts in the simultaneous removal NO and soot
(a): CO2 concentration profiles; (b): NO conversion
表 1 La1-xRbxMnO3催化剂的XPS表征
Table 1 XPS data of the La1-xRbxMnO3 catalysts
Sample Binding energy E/eV Oads/Olat Binding energy E/eV Mn4+/Mn3+ Olat Oads Mn3+ Mn4+ LaMnO3 529.32 531.27 0.661 641.38 642.88 0.592 La0.9Rb0.1MnO3 529.00 530.84 0.701 641.21 642.49 0.668 La0.8Rb0.2MnO3 529.05 530.94 0.845 641.11 642.12 0.714 La0.7Rb0.3MnO3 528.99 530.81 0.976 641.05 642.21 0.824 
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