Effect of alkaline earth metal doping on the catalytic performance of cobalt-based spinel composite metal oxides in N2O decomposition
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摘要: 采用共沉淀法制备碱土金属掺杂的钴基尖晶石型复合金属氧化物MxCo3-xO4（M=Mg、Ca、Sr、Ba；x=0、0.1、0.3、0.5、0.7、0.9）催化剂，使用XRD、SEM、氮吸附、H2-TPR、O2-TPD-MS和XPS等技术对催化剂进行表征，并在固定床微型反应器中评价了MxCo3-xO4催化剂催化分解N2O的活性，研究了碱土金属掺杂对其催化性能的影响。结果表明，碱土金属掺杂后，MxCo3-xO4催化剂颗粒粒径减小，比表面积增大，表面吸附氧和Co2+数量增加，氧化还原性能增强；在反应气组成为0.68% N2O，3% O2，Ar为平衡气的条件下，碱土金属锶掺杂、掺杂量x为0.7时，Sr0.7Co2.3O4的N2O分解催化活性最高，N2O转化率为10%和95%时所需的温度分别为312和451℃。Abstract: A series of cobalt-based spinel composite metal oxides doped with alkaline earth metals, viz., MxCo3-xO4 (M=Mg, Ca, Sr and Ba; x=0, 0.1, 0.3, 0.5, 0.7 and 0.9), were prepared by the coprecipitation method and characterized by XRD, SEM, nitrogen sorption, H2-TPR, O2-TPD-MS and XPS; the effect of alkaline earth metal doping on the catalytic performance of MxCo3-xO4 composites in N2O decomposition was investigated in a fixed bed micro-reactor. The results showed that after doping with the alkaline earth metals, the particle size of MxCo3-xO4 catalysts is decreased, accompanying with an increase in the specific surface area and the amount of surface adsorbed oxygen and Co2+ species. Meanwhile, the redox performance and catalytic activity of MxCo3-xO4 in N2O decomposition are also greatly enhanced. Under the conditions of 0.68% N2O, 3% O2 and Ar as balance gas, the Sr0.7Co2.3O4 catalyst doped with Sr (x=0.7) exhibits highest activity in N2O decomposition; the reaction temperatures where the N2O conversion reaches 10% and 95% are as low as 312 and 451℃, respectively.
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Key words:
- catalytic decomposition /
- nitrous oxide /
- cobalt-based spinel /
- alkaline earth metal /
- doping /
- composite metal oxides
1) 本文的英文电子版由Elsevier出版社在ScienceDirect上出版(http://www.sciencedirect.com/science/journal/18725813). -
图 1 MxCo3-xO4催化剂的XRD谱图
Figure 1 XRD patterns of MxCo3-xO4 catalysts
a: Co3O4; b: Mg0.5Co2.5O4; c: Ca0.5Co2.5O4; d1: Sr0.1Co2.9O4; d2: Sr0.3Co2.7O4; d3: Sr0.5Co2.5O4; d4: Sr0.7Co2.3O4; d5: Sr0.9Co2.1O4; e: Ba0.5Co2.5O4
图 2 MxCo3-xO4催化剂SEM照片
Figure 2 SEM images of MxCo3-xO4 catalysts
(a): Co3O4; (b): Mg0.5Co2.5O4; (c): Ca0.5Co2.5O4; (d)1: Sr0.1Co2.9O4; (d)2: Sr0.3Co2.7O4; (d3): Sr0.5Co2.5O4; (d4): Sr0.7Co2.3O4; (d5): Sr0.9Co2.1O4; (e): Ba0.5Co2.5O4
图 3 MxCo3-xO4催化剂的O2-TPD-MS谱图
Figure 3 O2-TPD-MS profiles of MxCo3-xO4 catalysts
a: Co3O4; b: Mg0.5Co2.5O4; c: Ca0.5Co2.5O4; d: Ba0.5Co2.5O4; e: Sr0.1Co2.9O4; f: Sr0.3Co2.7O4; g: Sr0.5Co2.5O4; h: Sr0.7Co2.3O4; i: Sr0.9Co2.1O4
图 4 MxCo3-xO4催化剂的H2-TPR谱图
Figure 4 H2-TPR profiles of MxCo3-xO4 catalysts
a: Co3O4; b: Mg0.5Co2.5O4; c: Ca0.5Co2.5O4; d1: Sr0.1Co2.9O4; d2: Sr0.3Co2.7O4; d3: Sr0.5Co2.5O4; d4: Sr0.7Co2.3O4; d5: Sr0.9Co2.1O4; e: Ba0.5Co2.5O4
图 5 MxCo3-xO4催化剂Co 2p(a)和O 1s(b)的XPS谱图
Figure 5 XPS spectra of Co 2p(a)和O 1s (b) of MxCo3-xO4 catalysts
a: Co3O4; b: Ba0.5Co2.5O4; c: Sr0.1Co2.9O4; d: Sr0.3Co2.7O4; e: Sr0.5Co2.5O4; f: Sr0.7Co2.3O4; g: Sr0.9Co2.1O4
图 6 MxCo3-xO4催化剂催化分解N2O活性评价
Figure 6 Activity of various MxCo3-xO4 catalysts in N2O decomposition
表 1 MxCo3-xO4催化剂物性和O2-TPD-MS表征
Table 1 Properties and the O2-TPD-MS results of MxCo3-xO4 catalysts
Sample dXRD/nm dSEM/nm ABET/
(m2·g-1)Oxygen desorption capacity /(mg·g-1) surface oxygen lattice oxygen Co3O4 36.1 200-400 6.4 0.5 68.0 Mg0.5Co2.5O4 35.4 70-300 10.4 1.0 68.1 Ca0.5Co2.5O4 33.9 50-200 10. 8 1.4 68.4 Sr0.5Co2.5O4 29.4 30-200 12.8 1.8 68.3 Ba0.5Co2.5O4 32.6 30-300 12.0 1.5 68.0 Sr0.1Co2.9O4 32.1 70-200 6.8 1.1 70.5 Sr0.3Co2.7O4 26.8 30-180 13.3 1.7 67.9 Sr0.7Co2.3O4 25.3 30-150 13.7 2.1 71.8 Sr0.9Co2.1O4 24.8 30-100 16.7 1.7 72.0 
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表 2 催化剂MxCo3-xO4的XPS数据
Table 2 XPS results of the MxCo3-xO4 catalysts
Catalysts Binding energies of Co 2p E/eV ΔE n(Co2+)/n(Co3+) Binding energies of O 1s E/eV n(Oads)/
n(Osum)Co 2p3/2 Co 2p1/2 OLat Oads OOH Co3O4 779.7 794.7 15.0 0.49 529.8 531.4 533.4 0.31 Ba0.5Co2.5O4 779.4 794.5 15.1 0.55 529.5 531.7 533.3 0.35 Sr0.1Co2.9O4 779.7 794.7 15.0 0.52 529.7 530.9 532.8 0.33 Sr0.3Co2.7O4 779.8 794.7 15.1 0.53 529.7 531.0 532.8 0.34 Sr0.5Co2.5O4 779.7 794.7 15.0 0.59 529.7 530.9 532.8 0.36 Sr0.7Co2.3O4 779.7 797.7 15.0 0.67 529.6 530.9 532.8 0.37 Sr0.9Co2.1O4 779.6 784.7 14.9 0.58 529.7 531.0 532.8 0.35
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