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Low-temperature oxidation of CO catalysed by Co3O4 nanorods

Nature volume 458, pages 746–749 (2009)Cite this article

Abstract

Low-temperature oxidation of CO, perhaps the most extensively studied reaction in the history of heterogeneous catalysis, is becoming increasingly important in the context of cleaning air and lowering automotive emissions1,2. Hopcalite catalysts (mixtures of manganese and copper oxides) were originally developed for purifying air in submarines, but they are not especially active at ambient temperatures and are also deactivated by the presence of moisture3,4. Noble metal catalysts, on the other hand, are water tolerant but usually require temperatures above 100 °C for efficient operation5,6. Gold exhibits high activity at low temperatures and superior stability under moisture, but only when deposited in nanoparticulate form on base transition-metal oxides7,8,9. The development of active and stable catalysts without noble metals for low-temperature CO oxidation under an ambient atmosphere remains a significant challenge. Here we report that tricobalt tetraoxide nanorods not only catalyse CO oxidation at temperatures as low as –77 °C but also remain stable in a moist stream of normal feed gas. High-resolution transmission electron microscopy demonstrates that the Co3O4 nanorods predominantly expose their {110} planes, favouring the presence of active Co3+ species at the surface. Kinetic analyses reveal that the turnover frequency associated with individual Co3+ sites on the nanorods is similar to that of the conventional nanoparticles of this material, indicating that the significantly higher reaction rate that we have obtained with a nanorod morphology is probably due to the surface richness of active Co3+ sites. These results show the importance of morphology control in the preparation of base transition-metal oxides as highly efficient oxidation catalysts.

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Figure 1: TEM images of Co 3 O 4 nanorods.
Figure 2: Effects of moisture content, regeneration and temperature on the oxidation of CO over Co 3 O 4 nanorods.
Figure 3: Possible reaction pathway for CO oxidation on Co 3 O 4 nanorod.
Figure 4: Reaction kinetics of CO oxidation.

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References

  1. Shelef, M. & McCabe, R. W. Twenty-five years after introduction of automotive catalysts: what next? Catal. Today 62, 35–50 (2000)

    Article  CAS  Google Scholar 

  2. Twigg, M. V. Progress and future challenges in controlling automotive exhaust gas emissions. Appl. Catal. B 70, 2–15 (2007)

    Article  CAS  Google Scholar 

  3. Merrill, D. R. & Scalione, C. C. The catalytic oxidation of carbon monoxide at ordinary temperatures. J. Am. Chem. Soc. 43, 1982–2002 (1921)

    Article  CAS  Google Scholar 

  4. Yoon, C. & Cocke, D. L. The design and preparation of planar models of oxidation catalysts: I. Hopcalite. J. Catal. 113, 267–280 (1988)

    Article  CAS  Google Scholar 

  5. Trimm, D. L. & Önsan, Z. I. Onboard fuel conversion for hydrogen-fuel-cell-driven vehicles. Catal. Rev. Sci. Eng. 43, 31–84 (2001)

    Article  CAS  Google Scholar 

  6. Oh, S. H. & Hoflund, G. B. Low-temperature catalytic carbon monoxide oxidation over hydrous and anhydrous palladium oxide powders. J. Catal. 245, 35–44 (2007)

    Article  CAS  Google Scholar 

  7. Date, M., Okumura, M., Tsubota, S. & Haruta, M. Vital role of moisture in the catalytic activity of supported gold nanoparticles. Angew. Chem. Int. Edn Engl. 43, 2129–2132 (2004)

    Article  CAS  Google Scholar 

  8. Haruta, M., Kobayashi, T., Sano, H. & Yamada, N. Novel gold catalysts for the oxidation of carbon monoxide at a temperature far below 0 °C. Chem. Lett. 16, 405–408 (1987)

    Article  Google Scholar 

  9. Haruta, M. et al. Low-temperature oxidation of CO over gold supported on TiO2, α-Fe2O3 and Co3O4 . J. Catal. 144, 175–192 (1993)

    Article  CAS  Google Scholar 

  10. Yao, Y. Y. The oxidation of hydrocarbons and CO over metal oxides. III. Co3O4 . J. Catal. 33, 108–122 (1974)

    Article  CAS  Google Scholar 

  11. Perti, D. & Kabel, R. L. Kinetics of CO oxidation over Co3O4/Al2O3 . AIChE J. 31, 1420–1440 (1985)

    Article  CAS  Google Scholar 

  12. Cunningham, D. A. H., Kobayashi, T., Kamijo, N. & Haruta, M. Influence of dry operating conditions: observation of oscillations and low temperature CO oxidation over Co3O4 and Au/ Co3O4 catalysts. Catal. Lett. 25, 257–264 (1994)

    Article  CAS  Google Scholar 

  13. Grillo, F., Natile, M. M. & Glisenti, A. Low-temperature oxidation of carbon monoxide: the influence of water and oxygen on the reactivity of a Co3O4 powder surface. Appl. Catal. B 48, 267–274 (2004)

    Article  CAS  Google Scholar 

  14. Thormählen, P., Skoglundh, M., Fridell, E. & Andersson, B. Low-temperature CO oxidation over platinum and cobalt oxide catalysts. J. Catal. 188, 300–310 (1999)

    Article  Google Scholar 

  15. Saalfrank, J. W. & Maier, W. F. Directed evolution of noble-metal-free catalysts for the oxidation of CO at room temperature. Angew. Chem. Int. Edn Engl. 43, 2028–2031 (2004)

    Article  CAS  Google Scholar 

  16. Fortunato, G., Oswald, H. R. & Reller, A. Spinel-oxide catalysts for low temperature CO oxidation generated by use of an ultrasonic aerosl pyrolysis process. J. Mater. Chem. 11, 905–911 (2001)

    Article  CAS  Google Scholar 

  17. Szegedi, Á., Hegedüs, M., Margitfalvi, J. L. & Kiricsi, I. Low-temperature CO oxidation over iron-containing MCM-41 catalysts. Chem. Commun. 1441–1443 (2005)

  18. Petitto, S. C., Marsh, E. M., Carson, G. A. & Langell, M. A. Cobalt oxide surface chemistry: the interaction of CoO (100), Co3O4 (110) and Co3O4 (111) with oxygen and water. J. Mol. Catal. A 281, 49–58 (2008)

    Article  CAS  Google Scholar 

  19. Jansson, J. et al. On the catalytic activity of Co3O4 in low-temperature CO oxidation. J. Catal. 211, 387–397 (2002)

    Article  CAS  Google Scholar 

  20. Omata, K., Takada, T., Kasahara, S. & Yamada, M. Active site of substituted cobalt spinel oxide for selective oxidation of CO/H2. Part II. Appl. Catal. A 146, 255–267 (1996)

    Article  CAS  Google Scholar 

  21. Beaufils, J. P. & Barbaux, Y. Study of adsorption on powders by surface differential diffraction measurements. Argon on Co3O4 . J. Appl. Cryst. 15, 301–307 (1982)

    Article  CAS  Google Scholar 

  22. Ziólkowski, J. & Barbaux, Y. Identification of sites active in oxidation of butene-1 to butadiene and CO2 on Co3O4 in terms of the crystallochemical model of solid surfaces. J. Mol. Catal. 67, 199–215 (1991)

    Article  Google Scholar 

  23. Broqvist, P., Panas, I. & Persson, H. A. DFT study on CO oxidation over Co3O4 . J. Catal. 210, 198–206 (2002)

    Article  CAS  Google Scholar 

  24. Jansson, J. Low-temperature CO oxidation over Co3O4/Al2O3 . J. Catal. 194, 55–60 (2000)

    Article  CAS  Google Scholar 

  25. Heck, R. M. & Farrauto, R. J. Automobile exhaust catalysts. Appl. Catal. A 221, 443–457 (2001)

    Article  CAS  Google Scholar 

  26. Sharma, S., Hegde, M. S., Das, R. N. & Pandey, M. Hydrocarbon oxidation and three-way catalytic activity on a single step directly coated cordierite monolith: High catalytic activity of Ce0. 98Pd0. 02O2-δ . Appl. Catal. A 337, 130–137 (2008)

    Article  CAS  Google Scholar 

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Acknowledgements

We thank C. Li, L. Lin and X. Bao of the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, for their encouragement and discussions. We also acknowledge financial supports for this research work from the National Natural Science Foundation of China and the National Basic Research Program of China.

Author Contributions X.X. and Y.L. performed the synthesis of Co3O4 nanorods/nanoparticles and the catalytic tests. Z.-Q.L. conducted the transmission electron microscopy observations and structural analysis. M.H. and W.S. designed the study, analysed the data and wrote the paper. All authors discussed the results and commented on the manuscript.

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  1. Xiaowei Xie and Yong Li: These authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

    Xiaowei Xie, Yong Li & Wenjie Shen

  2. Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

    Zhi-Quan Liu

  3. Department of Applied Chemistry, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 Minami-osawa, Hachioji 192-0397, Tokyo, Japan,

    Masatake Haruta

  4. Japan Science and Technology Agency, CREST, 4-1-8 Hon-Cho, Kawaguchi 332-0012, Saitama, Japan ,

    Masatake Haruta

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  1. Xiaowei Xie
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Correspondence to Wenjie Shen.

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Xie, X., Li, Y., Liu, ZQ. et al. Low-temperature oxidation of CO catalysed by Co3O4 nanorods. Nature 458, 746–749 (2009). https://doi.org/10.1038/nature07877

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