Cu1.5Mn1.5O4 spinel type composite oxide modified with CuO for synergistic catalysis of CO oxidation
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摘要: 铜锰复合氧化物是常用的氧化反应催化剂，一般认为铜锰尖晶石是活性组分；同时氧化铜和氧化锰也具有催化活性，但性能较差。研究表明，发现Cu1.5Mn1.5O4和CuO的协同效应能促进CO的催化氧化。催化剂以柠檬酸络合法制备，采用氮气吸附-脱附、XRD、H2-TPR、TEM、CO-TPD和O2-TPD等手段对系列催化剂进行了表征，测试了对CO氧化的催化性能。结果表明，CuO修饰的Cu1.5Mn1.5O4具有最好的催化性能和最高的单位表面活性（以单位表面积CO转化率计），表明CuO与Cu1.5Mn1.5O4存在协同作用。认为协同作用源自CuO活化的O2和Cu1.5Mn1.5O4活化的CO结合生成CO2提高了活性。Abstract: Composite oxides of copper and manganese are widely used in oxidation reactions, and the main active component is copper-manganese spinel, whereas the copper oxide and manganese oxide show extremely low activity, despite that they are beneficial for CO oxidation. In this paper, it was found that the synergistic effect of Cu1.5Mn1.5O4 and CuO could promote the catalytic oxidation of CO. The catalysts were prepared using the citric acid complexation method and they were characterized through combined the techniques of N2-adsorption desorption, XRD, H2-TPR, TEM, CO-TPD and O2-TPD. The catalytic performance of various catalysts in CO oxidation was then evaluated. The results confirmed that Cu1.5Mn1.5O4 modified with CuO exhibited the best catalytic performance and the highest unit surface activity (defined as the CO conversion rate per unit surface area of catalyst). CuO and Cu1.5Mn1.5O4 had a synergistic effect, where O2 was activated by CuO and it then interacted with CO, activated by Cu1.5Mn1.5O4, to form CO2, thus increasing the catalytic activity.
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Key words:
- spinel type composite oxide /
- copper oxide /
- synergy effect /
- catalytic oxidation /
- manganese oxide
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图 1 12种不同煅烧温度催化剂的低温CO氧化活性 (a)350 ℃、(b) 450 ℃、(c) 550 ℃、(d) 650 ℃
Figure 1 Low-temperature CO oxidation activity of 12 different catalysts with different calcined temperature at (a) 350 ℃, (b) 450 ℃, (c) 550 ℃ and (d) 650 ℃. reaction conditions: catalyst weight 0.10 g; CO 1%, O2 1%, N2 balance; WHSV = 24000 mL/(gcat·h)
图 2 不同催化剂的CO氧化性能
Figure 2 Catalytic oxidation of CO over the Cu-Mn catalysts with various Cu/Mn molar ratio. catalyst weight 0.10 g; CO 1%, O2 1%, N2 balance; WHSV = 24000 mL/(gcat·h)
图 3 不同催化剂的N2吸附-脱附曲线(a)和孔径分布(b)
Figure 3 N2 adsorption-desorption isotherms (a) and pore size distribution curves (b) of the studied samples
图 5 催化反应后不同样品的XRD谱图
Figure 5 XRD patterns of prepared samples after catalytic reaction
图 7 CuO-Cu1.5Mn1.5O4、Mn3O4-Cu1.5Mn1.5O4、Cu1.5Mn1.5O4样品的TEM照片和HRTEM照片
Figure 7 TEM images and HRTEM images of CuO-Cu1.5Mn1.5O4 samples: (a), (a'), (a''); Mn3O4-Cu1.5Mn1.5O4 samples: (b), (b'), (b''); Cu1.5Mn1.5O4 samples: (c), (c')
图 8 (a)不同催化剂的CO-TPD谱图和(b)局部放大的TPD谱图
Figure 8 CO-TPD profiles of (a) the different catalysts; (b) partially enlarged of (a)
图 9 (a) 不同催化剂的O2-TPD谱图和(b)局部放大的TPD谱图
Figure 9 O2-TPD profiles of (a) the different catalysts; (b) partially enlarged of (a)
表 1 低温下（80 ℃）Cu-Mn复合氧化物单位面积CO氧化的本征活性
Table 1 The unit surface activity of samples at low temperature (80 ℃)
Catalyst SBET/(m2·g−1) Rate per catalyst surface area/
（× 10−5 mol·min−1·m−2）CuO-Cu1.5Mn1.5O4 7.0 6.3 Mn3O4-Cu1.5Mn1.5O4 11.1 2.7 Cu1.5Mn1.5O4 13.2 2.5 
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表 2 不同样品的物理性质
Table 2 Physical properties of the studied samples
Sample SBET/(m2·g−1) dpore/nm vpore/(cm3·g−1) Mn3O4-Cu1.5Mn1.5O4 11.1 12 0.10 Cu1.5Mn1.5O4 13.2 18 0.10 CuO-Cu1.5Mn1.5O4 7.0 19 0.06
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表 3 不同催化剂的晶粒尺寸
Table 3 Grain size of different catalysts
Catalyst Grain size/nm
(before reaction)Grain size/nm
(after reaction)Mn3O4-Cu1.5Mn1.5O4 22.1 21.3 Cu1.5Mn1.5O4 29.9 32.8 CuO-Cu1.5Mn1.5O4 11.5 12.0
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表 4 Mn3O4-Cu1.5Mn1.5O4、Cu1.5Mn1.5O4和CuO-Cu1.5Mn1.5O4样品的还原峰面积
Table 4 Reduction peak area of the Mn3O4-Cu1.5Mn1.5O4, Cu1.5Mn1.5O4 and CuO-Cu1.5Mn1.5O4 catalysts
Catalyst Reduction peak area/(a.u.) Mn3O4-Cu1.5Mn1.5O4 90020.88 Cu1.5Mn1.5O4 95156.94 CuO-Cu1.5Mn1.5O4 122509.36
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