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High NOx Reduction Activity of an Ultrathin Zirconia Film Covering a Cu Surface: A DFT Study

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Abstract

NO reduction by CO over a c-ZrO2(110) ultrathin film covering a Cu(110) surface (ZrO2/Cu) has been examined by means of density-functional theory calculations. Spontaneous transfer of electronic charge from Cu to zirconia gives the latter an ability to reduce oxidants. Gaining this excess charge, NO adsorbs and activates on the cationic Zr site of the oxide surface. Thus activated, two NO on adjacent Zr sites can react to form ONNO with an activation energy of 0.39 eV (8.9 kcal/mol), which readily decomposes into N2O and an O adatom. N2O also decomposes into N2 and an O adatom with negligible activation energy of 0.06 eV (1.4 kcal/mol). CO reacts off the O adatoms left on the surface as CO2 with an activation energy of 0.36 eV (8.2 kcal/mol), completing a redox cycle. These results indicate high potentials of oxide-covered metal catalysts (metal@oxide) for NOx abatement.

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Acknowledgements

This work was performed under a management of ‘Elements Strategy Initiative for Catalysts and Batteries (ESICB)’ supported by Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT). K. Tada was supported by the JSPS Research Fellowship for Young Scientists.

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Authors and Affiliations

  1. Elements Strategy Initiative for Catalysts and Batteries (ESICB), Kyoto University, 1-30 Goryo Ohara, Nishikyo, Kyoto, Kyoto, 615-8245, Japan

    Hiroaki Koga & Mitsutaka Okumura

  2. Research Institute of Electrochemical Energy, National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka, 563-8577, Japan

    Kohei Tada

  3. Department of Chemistry, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka, 560-0043, Japan

    Akihide Hayashi, Yoshinori Ato & Mitsutaka Okumura

Authors
  1. Hiroaki Koga
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  2. Kohei Tada
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  3. Akihide Hayashi
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  4. Yoshinori Ato
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  5. Mitsutaka Okumura
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Correspondence to Hiroaki Koga.

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Koga, H., Tada, K., Hayashi, A. et al. High NOx Reduction Activity of an Ultrathin Zirconia Film Covering a Cu Surface: A DFT Study. Catal Lett 147, 1827–1833 (2017). https://doi.org/10.1007/s10562-017-2086-5

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  • DOI: https://doi.org/10.1007/s10562-017-2086-5

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