Paper
Catalysis Science & Technology
carried out. As shown in Fig. 9, the HCHO molecules were
8 C. Ma, X. Li and T. Zhu, Carbon, 2011, 49, 2873.
desorbed at around 50 °C and then reached their peaks at
about 75 °C on the α-, β-, and γ-MnO catalysts, while no
2
HCHO desorption was observed on δ-MnO2. CO2 was
detected on all samples during the HCHO-TPD starting at
around 75 °C, with peaks at 144 °C, 201 °C, 176 °C and
9 C. Zhang, F. Liu, Y. Zhai, H. Ariga, N. Yi, Y. Liu, K. Asakura,
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1
27 °C, for the α–δ-MnO catalysts respectively. CO -TPD exper-
2 2
iments were also performed, and the results (ESI ,† Fig. S5)
show that the CO desorption temperatures for the four cata-
2
lysts were all lower than 100 °C, confirming that the CO in
2
the HCHO-TPD experiments was mainly produced by the oxi-
47
dation of some adsorbed HCHO or intermediates. There-
fore, HCHO desorption and CO production should be closely
2
dependent on the activity of the surface lattice oxygen spe-
cies. When the lattice oxygen species are highly active at low
temperature, such as on the δ-MnO2 catalyst, all adsorbed
16 X. Tang, J. Chen, X. Huang, Y. Xu and W. Shen, Appl. Catal.,
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HCHO would be oxidized into CO without desorption during
2
the ramping temperature.
1
2
2
2
2
2
2
2
2
2
2
3
9 C. Shi, B. Chen, X. Li, M. Crocker, Y. Wang and A. Zhu,
4
. Conclusions
Chem. Eng. J., 2012, 200, 729.
0 Z. Qu, S. Shen, D. Chen and Y. Wang, J. Mol. Catal. A:
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4 L. Ma, D. Wang, J. Li, B. Bai, L. Fu and Y. Li, Appl. Catal., B,
2
In summary, we prepared α-, β-, γ- and δ-type MnO catalysts
and observed their very different activities for the catalytic
oxidation of HCHO. This enormous difference in activities
originates from their different physical properties at the sur-
+
face, K content, tunnel structures, the mobility of oxygen
species, lattice oxygen abundances and also HCHO adsorp-
tion/desorption properties. However, the tunnel structures
and lattice oxygen mobility and abundances might play a
more important role in the HCHO oxidation reaction.
δ-MnO has a special 2D layer tunnel structure and also con-
2
tains the most active oxygen species and the highest amount
of lattice oxygen species on the catalyst surface, therefore,
presenting the highest activity of the four types of MnO cata-
2
lyst. Moreover, due to the high catalytic performance and fac-
ile preparation process, δ-MnO may potentially be used as a
support in applications of supported catalysts.
2
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Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (21422706) and the Program of
the Ministry of Science and Technology of China
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